WO2009056017A1

WO2009056017A1 - A process for comprehensive utilization of stalks of grass-type plants

Info

Publication number: WO2009056017A1
Application number: PCT/CN2008/072057
Authority: WO
Inventors: Hongfa Li; Liangjin Guo; Mingxin Song; Songtao Chen; Xuetao Chen
Original assignee: Shandong Tralin Paper Co Ltd
Current assignee: Shandong Tralin Paper Co Ltd
Priority date: 2007-10-29
Filing date: 2008-08-20
Publication date: 2009-05-07
Anticipated expiration: 2010-04-29

Abstract

A process for comprehensive utilization of stalks of grass-type plants, includes (1) cooking the stalks of said plants to obtain a high-hardness pulp with a potassium permanganate value of 16-28; (2) pressing the high-hardness pulp to obtain coarse pulp and dilute black liquor; (3) separating the solids from the dilute black liquor, discarding said solids, and obtaining the filtrate of the dilute black liquor as fertilizer pre-product, or first concentrating the dilute black liquor by evaporation to obtain a dense black liquor, then separating it, discarding the solids and obtaining the filtrate of the dense black liquor as a fertilizer pre-product. The invention also addresses the fertilizer pre-product obtained by the above process, and fertilizers prepared from said black liquor optionally mixed with other components, such as lignin and humic acid, soluble macro elements fertilizer, or soluble trace elements fertilizer.

Description

一种禾草类秸秆综合利用方法 Method for comprehensive utilization of grass straw

技术领域 Technical field

本发明涉及一种禾草类秸秆综合利用方法，属于造纸和肥料领域。 The invention relates to a comprehensive utilization method of grass straw, belonging to the field of papermaking and fertilizer.

背景技术 Background technique

中国是小麦、水稻等禾草类作物的种植大国，每到收获季节，产生大量秸秆，秸秆的处理、处置也成为人们日常生活中所关注的主要问题,由于无法处理、处置这大量的秸秆，人们只得将大量的秸秆焚烧，或将秸秆入河，以减少大量的秸秆堆压。 China is a large country for the cultivation of grasses such as wheat and rice. Every harvest season, a large amount of straw is produced. The treatment and disposal of straw has become a major concern in people's daily life. Because of the inability to handle and dispose of this large amount of straw, People have to burn a large amount of straw or put straw into the river to reduce the bulk of the straw.

秸秆焚烧、秸秆入河所带来的危害是巨大的。秸秆的焚烧的烟雾造成空气能见度下降、大气环境，严重影响交通运输和人们的身体健康。秸秆入河导致大量的有机物溶解进入水体，使得水体中有机物含量高，色度变深。由于消耗大量的有机物，水中的溶解氧降低，直接影响水生生物生存的环境,造成大面积的水生生物死亡。 The harm caused by straw burning and straw entering the river is enormous. The smog of straw burning causes a decrease in air visibility and the atmospheric environment, which seriously affects transportation and people's health. When the straw enters the river, a large amount of organic matter is dissolved into the water body, so that the organic matter content in the water body is high and the color is deep. Due to the consumption of large amounts of organic matter, the dissolved oxygen in the water is reduced, directly affecting the environment in which aquatic organisms live, causing large areas of aquatic life to die.

随着环保和森林资源的紧缺，以禾草类秸秆为原料造纸越来越受到重视，但是，受工艺限制，以禾草类秸秆为原料造纸产生大量的黑液，虽然部分黑液可以回收作为蒸煮液，大部黑液需要进行处理，一般的处理方法均会造成环境污染。 With the shortage of environmental protection and forest resources, papermaking with grass straw as the raw material has received more and more attention. However, due to process limitations, a large amount of black liquor is produced by using grass straw as raw material, although some black liquor can be recycled. Cooking liquor, most of the black liquor needs to be treated, and the general treatment methods will cause environmental pollution.

现有技术中已经公开了造纸产生的黑液，包括禾草类秸秆为原料造纸产生的黑液用于制备肥料，例如将提取黑液中的木质素、将黑液发酵处理或混合处理制造肥料。 The black liquor produced by papermaking has been disclosed in the prior art, and the black liquor produced by the straw straw as raw material for papermaking is used for preparing fertilizer, for example, the lignin in the black liquor is extracted, the black liquor is fermented or mixed to produce fertilizer. .

CN1397684公开了治理和综合利用碱法制浆造纸黑液的方法，其步骤为向黑液中加入质量 1 %-20 %的絮凝剂，和质量 1 %-25 %的助凝剂，析出木质素，滤出上清液；将木质素分离后进行脱水处理；其中，木质素可作为有机复合肥料、土壤改良剂、填料等，上清液可根据企业需求作不同利用处理。 CN1397684 discloses a method for treating and comprehensively utilizing alkaline pulping black liquor for papermaking, the steps of adding a flocculant having a mass of 1%-20% to a black liquor, and a coagulant having a mass of 1%-25% to precipitate lignin. The supernatant is filtered out; the lignin is separated and dehydrated; wherein, the lignin can be used as an organic compound fertilizer, a soil conditioner, a filler, etc., and the supernatant can be treated differently according to the needs of the enterprise.

CN1537830公开了一种利用造纸制浆黑液生产肥料的方法，其特征是以 KOH碱法造纸制浆黑液处理植物性材料，使黑液中的残碱 (KOH)和植物性材料反应，制成肥料。制成的肥料可以添加其它成分或进一步发酵或进一步造粒，形成多种有机肥、有机无机复合肥、生物有机肥尤其是新型有机钾肥。 CN1537830 discloses a method for producing fertilizer by using papermaking pulping black liquor, which is characterized in that KOH alkali papermaking pulping black liquor is used to treat plant material, and residual alkali (KOH) and plant material in black liquor are reacted. Into fertilizer. The prepared fertilizer can be added with other ingredients or further fermented or further granulated to form a variety of organic fertilizers, organic-inorganic compound fertilizers, bio-organic fertilizers, especially new organic potash fertilizers.

CN1552640、 CN1436895、 CN101209932 和 CN101210395均公开了公开了将黑液发酵制备肥料的方法。 Both CN1552640, CN1436895, CN101209932 and CN101210395 disclose methods of fermenting black liquor to produce fertilizer.

采用从黑液中分离木质素的方法，絮凝难以将黑液中的固体分离，得到的上清液需要复杂的后处理，而且难以达到排放标准，利用发酵法处理黑液需要大量的场地、处理时间长，难以利用和广泛利用。 Using the method of separating lignin from black liquor, flocculation is difficult to separate the solids in the black liquor, and the obtained supernatant requires complicated post-treatment, and it is difficult to meet the discharge standard. The treatment of black liquor by fermentation requires a large amount of site and treatment. Long time, difficult to use and widely used.

有鉴于此，本申请提供了一种造纸黑液综合利用方法，彻底解决了秸秆堆压合纸厂黑液处理问题，并能取得良好的经济效益。 In view of this, the present application provides a comprehensive utilization method of papermaking black liquor, which completely solves the black liquor treatment problem of the straw stacking and papermaking factory, and can achieve good economic benefits.

发明内容 Summary of the invention

本发明的目的第一目的在于提供一种禾草类秸秆的综合利用方法。 A first object of the present invention is to provide a method for comprehensive utilization of grass straw.

一种禾草类秸秆综合利用方法，包括： (1) 将禾草类秸秆进行蒸煮，得到硬度为高锰酸钾值 16— 28的高硬度浆；优选硬度为高锰酸钾值 18— 27的高硬度浆；最优选硬度为高锰酸钾值 20— 25的高硬度浆； A comprehensive utilization method of grass straws, comprising: (1) The grass straw is steamed to obtain a high hardness pulp having a hardness of potassium permanganate of 16-28; a high hardness pulp having a hardness of 18-27 is preferred; the hardness is preferably permanganic acid. High hardness pulp with a potassium value of 20-25;

(2) 将高硬度浆进行挤浆，得到挤浆后的浆料和稀黑液； (2) Squeeze the high-hardness slurry to obtain a slurry after slurrying and a thin black liquor;

(3)将稀黑液进行固液分离，弃去固体，得到的滤液即为肥料前产品；或先将稀黑液蒸发浓缩得到浓黑液，再进行固液分离，弃去固体，得到的滤液即为肥料前产品。 (3) The solid black liquor is subjected to solid-liquid separation, and the solid is discarded, and the obtained filtrate is the product before the fertilizer; or the concentrated black liquor is concentrated by evaporation to obtain a concentrated black liquor, and then solid-liquid separation is performed, and the solid is discarded. The filtrate is the pre-fertilizer product.

本发明所述的禾草类秸秆包括麦草、稻草、棉秆、甘蔗渣、芦竹或芦苇中的一种或者一种以上的混合；所述的蒸煮方法包括亚铵法和碱法中的一种或一种以上的组合，所述的碱法包括蒽醌一烧碱法、硫酸盐法或碱性亚钠法。 The grass straw of the present invention comprises one or more of a mixture of wheat straw, straw, cotton stalk, bagasse, arundo donax or reed; the cooking method comprises one of an ammonium imide method and an alkali method. Or a combination of one or more of the above, the alkaline method comprising a sulphuric acid caustic method, a sulphate method or an alkaline sodium sulphate method.

所述的亚铵法蒸煮为： The ammonium imide process is:

①在禾草类秸秆原料中加入蒸煮药液，其中亚硫酸铵用量为对绝干原料量的 9-13%，配氢氧化钠量为绝干原料量的 0-8%，液比为 1: 2-4； 1 Adding cooking liquor to the grass straw raw materials, wherein the amount of ammonium sulfite is 9-13% of the amount of dry raw materials, and the amount of sodium hydroxide is 0-8% of the amount of dry raw materials, and the liquid ratio is 1 : 2-4;

②通入蒸汽进行加热，加热升温至温度 165-173°C，升温、小放气、保温全程时间 160-210分钟；所述的蒽醌-烧碱法蒸煮为： 2 It is heated by steam, heated to a temperature of 165-173 ° C, heated, deflated, and insulated for 160-210 minutes; the strontium-soda cooking is:

①在禾草类秸秆原料中加入蒸煮药液，其中用碱量为以氢氧化钠计对绝干原料量 9-15%，液比为 1: 2-4，蒽醌加入量为绝干原料量的 0.05-0.08%; 1 Adding cooking liquor to the grass straw raw material, wherein the amount of alkali is 9-15% based on the amount of dry sodium hydroxide, and the liquid ratio is 1: 2-4, and the amount of strontium added is dry raw material. 0.05-0.08% of the amount;

②通入蒸汽进行加热，加热升温至温度 160-165°C，升温、小放气、保温全程时间 140-190分钟；所述的硫酸盐法蒸煮为： 2 is heated by steam, heated to a temperature of 160-165 ° C, heated, deflated, and insulated for 140-190 minutes; the sulphate cooking is:

①在禾草类秸秆原料中加入蒸煮药液，其中用碱量为氢氧化钠计对绝干原料量 8-11%，液比为 1: 2-4, 硫化度为 5-8%; 1 adding a cooking liquid to the grass straw raw material, wherein the amount of the dry raw material is 8-11%, the liquid ratio is 1: 2-4, and the degree of sulfurization is 5-8%;

②通入蒸汽进行加热，加热升温至温度 165-173°C，升温、小放气、保温全程时间 150-200分钟；所述的碱性亚钠法蒸煮包括： 2 is heated by steam, heated to a temperature of 165-173 ° C, heating, small venting, heat preservation time of 150-200 minutes; the alkaline sodium cooking comprises:

①在禾草类秸秆中加入蒸煮药液，其中，氢氧化钠用量以绝干原料重量计为 9一 15%，亚硫酸钠为 2-6%, 蒽醌为 0.04— 0.08%，蒸煮液比为 1:3 - 4; 1 Adding a cooking liquid to the straw of the grass, wherein the amount of sodium hydroxide is 9-15% by weight of the dry raw material, 2-6% of sodium sulfite, 0.04-0.08% of strontium, and the ratio of cooking liquor is 1. :3 - 4;

②通入蒸汽进行加热，加热升温至温度 160-165°C，升温、小放气、保温全程时间 140-190分钟。 2 Heated by steam, heated to a temperature of 160-165 ° C, heating, small venting, heat preservation time of 140-190 minutes.

本发明所述的稀黑液为亚铵法和碱法分别制浆后处理得到亚铵法稀黑液和碱法稀黑液，然后混合形成的亚铵法和碱法混合稀黑液。本发明所述的稀黑液也可以为亚铵法蒸煮后挤浆的得到的稀黑液。 The dilute black liquor of the present invention is separately prepared by an ammonium imide method and an alkali method to obtain an ammonium imide black liquor and an alkali black liquor, and then mixed to form an ammoniumimine method and an alkali method to mix a thin black liquor. The dilute black liquor of the present invention may also be a dilute black liquor obtained by extrusion after cooking by an ammonium iodide method.

本发明所述的亚铵法和碱法混合稀黑液中亚铵法稀黑液和碱法稀黑液的混合比例为 1: 100- 100： 1，优选 1: 10-10： 1，更优选 1: 4-4： 1，所述的亚铵法稀黑液波美度 2— 9，固含量为 4 -15%, pH为 7— 10; 所述的碱法稀黑液波美度 2— 9，固含量为 4一 15%， pH为 9一 13。 The mixing ratio of the ammonium imide method and the alkaline black liquor in the ammonium sulfite method and the alkali method mixed rare black liquor according to the present invention is 1:100-100:1, preferably 1:10-10:1 Preferably, 1:4-4: 1, the ammonium imide black liquor Baume 2-9, solid content 4-15%, pH 7-10; the alkali method black liquor Baume 2-9, the solid content is 4-15%, and the pH is 9-13.

本发明所述的浓黑液的固含量为 15.1— 65%，波美度为 9一 40; 优选固含量为 30— 65%，波美度为 18— 40，更优选固含量为 40— 47%，波美度为 25— 29，所述浓黑液的 pH优选为 5— 11；更优选 pH为 6— 8。 The concentrated black liquor of the present invention has a solid content of 15.1-65%, a Baume degree of 9-40, a preferred solid content of 30-65%, a Baume degree of 18-40, and more preferably a solid content of 40-47. %, Baume degree is 25-29, the pH of the concentrated black liquor is preferably 5-11; more preferably pH is 6-8.

本发明所述的固液分离包括在稀黑液中或浓黑液中加入酸调节 pH值至 5以下，然后加入絮凝剂，过滤除去木素固体，得到滤液。 The solid-liquid separation according to the present invention comprises adding acid in a dilute black liquor or a concentrated black liquor to adjust the pH to below 5, and then adding flocculation. The lignin solid was removed by filtration to obtain a filtrate.

本发明所述的酸包括有机酸和无机酸，优选所述有机酸包括甲酸、乙酸、丙酸或苯甲酸中的一种或一种以上；优选的无机酸为盐酸、硫酸、硝酸或磷酸的一种或一种以上，所述的调节 pH 值至 2— 4。 The acid of the present invention includes an organic acid and an inorganic acid, and preferably the organic acid includes one or more of formic acid, acetic acid, propionic acid or benzoic acid; the preferred inorganic acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid. One or more of the above, the pH is adjusted to 2-4.

本发明所述的絮凝剂加入量为黑液重量的 2— 50ppm; 优选 5— 15ppm，最优选 5ppm; 所述的絮凝剂包括聚合硫酸铁、碱式氯化铝或聚丙烯酸铵中的一种。 The flocculating agent of the present invention is added in an amount of 2-50 ppm by weight of the black liquor; preferably 5-15 ppm, most preferably 5 ppm; the flocculating agent comprises one of polyferric sulfate, basic aluminum chloride or ammonium polyacrylate. .

本发明所述的蒸发浓缩为多效蒸发，优选六效蒸发，更优选的六效蒸发过程为逆流六效蒸发，混合草浆黑液自 VI效流入，加热蒸汽自 I效流入，闪蒸后的混合草浆黑液依次经过 VI效、 V效、 IV效、 III效加热蒸发后，变为半浓黑液，半浓黑液依次经过 II效、 I效加热蒸发后，变为浓黑液，即为碱法和亚铵法混合浓缩草浆黑液。 The evaporation concentration according to the present invention is multi-effect evaporation, preferably six-effect evaporation, and more preferably the six-effect evaporation process is counter-current six-effect evaporation, the mixed straw black liquor flows from the VI effect, and the heated steam flows from the I effect, after flashing The mixed black liquor of the straw pulp is heated by the VI effect, the V effect, the IV effect, and the III effect, and then becomes a semi-rich black liquor. The semi-dense black liquor is then subjected to the II effect, the I effect heating and evaporation, and then becomes a concentrated black liquor. That is, the alkali liquor and the ammonium imide method are mixed to concentrate the straw black liquor.

本发明所述的六效蒸发各效温度为：1效 100-110°C、II效 90-100°C、III效 80-90°C、IV效 70-80 °C、 V效 60-70°C、 VI效 50-6CTC ; 各效黑液波美度分别为： VI效 5— 8、 V效 7— 10、 IV效 9-12、 III ¾ 11-14；经过 II效和 I效时， II效 14—17、 I效 18—21 ; 各效的压力为： I效 20—38 kPa、 II 效 10〜- 10kPa、 III效— 20〜― 30 kPa、 IV效 50〜一 60kPa、 V效—60〜一 70kPa、 VI效一 75〜一 85kPa，文中所有压力都为相对压力，相对大气压而言。 The six-effect evaporation effect temperature of the invention is: 1 effect 100-110 ° C, II effect 90-100 ° C, III effect 80-90 ° C, IV effect 70-80 ° C, V effect 60-70 °C, VI effect 50-6CTC; each effect black liquor wave beauty is: VI effect 5-8, V effect 7-10, IV effect 9-12, III 3⁄4 11-14; After II effect and I effect , II effect 14-17, I effect 18-21; The pressure of each effect is: I effect 20-38 kPa, II effect 10~- 10kPa, III effect - 20~― 30 kPa, IV effect 50~60kPa, V Effect - 60 ~ a 70kPa, VI effect a 75 ~ a 85kPa, all pressures in the text are relative pressure, relative atmospheric pressure.

本发明的第二目的在于提供一种肥料前产品。所述的肥料前产品可以进行干燥得到固体肥料，也可以进一步提纯得到黄腐酸。 A second object of the present invention is to provide a pre-fertilizer product. The pre-fertilizer product can be dried to obtain a solid fertilizer, or can be further purified to obtain fulvic acid.

为了实现上述目的，本发明采用的技术方案为： In order to achieve the above object, the technical solution adopted by the present invention is:

一种肥料前产品，所述的肥料前产品的制备方法包括： A pre-fertilizer product, the preparation method of the pre-fertilizer product comprises:

( 1 ) 将禾草类秸秆进行蒸煮，得到硬度为高锰酸钾值 16 28的高硬度浆；优选硬度为高锰酸钾值 18— 27的高硬度浆；最优选硬度为高锰酸钾值 20— 25的高硬度浆； (1) The grass straw is cooked to obtain a high-hardness pulp having a hardness of 1628 potassium permanganate; a high-hardness pulp having a hardness of 18-27 is preferred; the hardness is potassium permanganate. a high hardness pulp of 20-25;

(2 ) 将高硬度浆进行挤浆，得到挤浆后的浆料和稀黑液； (2) squeezing the high-hardness slurry to obtain a slurry after slurrying and a thin black liquor;

( 3 )将稀黑液进行固液分离，弃去固体，得到的滤液即得到所述的肥料前产品；或先将稀黑液蒸发浓缩得到浓黑液，再进行固液分离，弃去固体，得到的滤液即得到所述的肥料前产品。 (3) The solid black liquor is subjected to solid-liquid separation, and the solid is discarded, and the obtained filtrate is obtained as the pre-fertilizer product; or the diluted black liquor is first concentrated by evaporation to obtain a concentrated black liquor, and then solid-liquid separation is performed, and the solid is discarded. The obtained filtrate obtained the pre-fertilizer product.

所述的禾草类包括麦草、稻草、棉秆、甘蔗渣、芦竹或芦苇中的一种或者两种以上的混合；所述的蒸煮方法包括亚铵法和碱法中的一种或一种以上的组合，所述的碱法包括蒽醌一烧碱法、硫酸盐法或碱性亚钠法。 The grass includes one or a mixture of two or more of wheat straw, straw, cotton stalk, bagasse, arundo donax or reed; the cooking method comprises one or one of an ammonium imide method and an alkali method. In the above combination, the alkali method includes a samarium caustic soda method, a sulphate method or an alkaline sodium sulphate method.

所述的亚铵法蒸煮为： The ammonium imide process is:

①在禾草类秸秆原料中加入蒸煮药液，其中亚硫酸铵用量为对绝干原料量的 9-13%，配氢氧化钠量为绝干原料量的 0-8%，液比为 1 : 2-4； 1 Adding cooking liquor to the grass straw raw materials, wherein the amount of ammonium sulfite is 9-13% of the amount of dry raw materials, and the amount of sodium hydroxide is 0-8% of the amount of dry raw materials, and the liquid ratio is 1 : 2-4;

①在禾草类秸秆原料中加入蒸煮药液，其中用碱量为以氢氧化钠计对绝干原料量 9-15%，液比为 1 : 2-4，蒽醌加入量为绝干原料量的 0. 05-0. 08%； ②通入蒸汽进行加热，加热升温至温度 160-165°C，升温、小放气、保温全程时间 140-190分钟；所述的硫酸盐法蒸煮为： 1 Adding cooking liquor to the grass straw raw materials, wherein the amount of alkali is 9-15% based on sodium hydroxide, and the liquid ratio is 1:2-4, and the amount of strontium added is dry raw material. 0. 05-0. 08%; 2 steaming to heat, heating to a temperature of 160-165 ° C, heating, small venting, heat preservation time of 140-190 minutes; the kraft cooking is:

本发明所述的稀黑液为亚铵法和碱法分别制浆后处理得到亚铵法稀黑液和碱法稀黑液，然后混合形成的亚铵法和碱法混合稀黑液。所述的稀黑液也可以为亚铵法蒸煮后挤浆得到的稀黑液。 The dilute black liquor of the present invention is separately prepared by an ammonium imide method and an alkali method to obtain an ammonium imide black liquor and an alkali black liquor, and then mixed to form an ammoniumimine method and an alkali method to mix a thin black liquor. The diluted black liquor may also be a diluted black liquor obtained by slurrying after the ammonium imide process.

本发明所述的固液分离包括在稀黑液中或浓黑液中加入酸调节 pH值至 5以下，然后加入絮凝剂，过滤除去木素固体，得到滤液。 The solid-liquid separation according to the present invention comprises adding an acid to a diluted black liquor or a concentrated black liquor to adjust the pH to 5 or less, then adding a flocculant, and filtering to remove the lignin solid to obtain a filtrate.

本发明的第三目的在于提供一种肥料。该肥料可以由浓黑液制备，也可以加入木质素和腐殖酸等其它成分。 A third object of the invention is to provide a fertilizer. The fertilizer can be prepared from concentrated black liquor or other ingredients such as lignin and humic acid.

一种肥料，所述肥料包括将所述的浓黑液进行喷雾干燥或喷浆造粒，优选喷浆造粒后得到。本发明所述喷浆造粒时喷浆造粒机头温度 550〜600°C，机尾温度 47— 55°C，返料量 50%。本发明所述的肥料包括将所述浓黑液、木质素和腐殖酸混合后进行喷雾干燥或喷浆造粒，优选喷浆造粒后得到；或者将所述浓黑液、木质素和腐殖酸分别进行喷雾干燥或喷浆造粒，优选喷浆造粒后混合得到；混合时上述各组分的重量百分比为：浓黑液 30— 80%; 木质素 1一 45%; 腐殖酸 1一 25%; 优选各组分的重量百分比为：浓黑液 50— 60%; 木质素 15— 35%; 腐殖酸 10— 15%。本发明所述的浓黑液的固含量为 15.1— 65%，波美度为 9一 40; 优选固含量为 30— 65%，波美度为 18— 40，更优选固含量为 40— 47%，波美度为 25— 29，所述浓黑液的 pH优选为 5— 11；更优选 pH为 6— 8。 A fertilizer comprising the spray-drying or spray granulation of the concentrated black liquor, preferably after spray granulation. In the spray granulation of the invention, the temperature of the spray granulator head is 550~600 °C, the tail temperature is 47-55 °C, and the return amount is 50%. The fertilizer according to the present invention comprises: mixing the concentrated black liquor, lignin and humic acid, followed by spray drying or spray granulation, preferably after spray granulation; or the concentrated black liquor, lignin and The humic acid is spray-dried or spray-granulated separately, preferably after spray granulation and mixing; the weight percentage of the above components during mixing is: concentrated black liquor 30-80%; lignin 1 -45%; humic The acid is 1 to 25%; preferably, the weight percentage of each component is: 50-60% of concentrated black liquor; 15-35% of lignin; 10-15% of humic acid. The concentrated black liquor of the present invention has a solid content of 15.1-65%, a Baume degree of 9-40, a preferred solid content of 30-65%, a Baume degree of 18-40, and more preferably a solid content of 40-47. %, Baume degree is 25-29, the pH of the concentrated black liquor is preferably 5-11; more preferably pH is 6-8.

本发明所述的肥料包括将所述浓黑液和可溶性大量元素肥料混合后进行喷雾干燥或喷浆造粒，优选喷浆造粒后得到；或者所述浓黑液和可溶性大量元素肥料分别进行喷雾干燥或喷浆造粒，优选喷浆造粒后混合得到；混合时各组分的重量百分比为：浓黑液 20— 98%; 可溶性大量元素肥料 2— 80%; 优选各组分的重量百分比为：浓黑液 50— 90%; 可溶性大量元素肥料 10— 50%。 The fertilizer according to the present invention comprises: mixing the concentrated black liquor and the soluble large amount of element fertilizer, followed by spray drying or spray granulation, preferably after spray granulation; or the concentrated black liquor and the soluble large amount of element fertilizer respectively Spray drying or spray granulation, preferably after spray granulation, mixing; the weight percentage of each component during mixing is: 20-9% of concentrated black liquor; 2 - 80% of soluble large amount of elemental fertilizer; The percentages are: 50-90% of concentrated black liquor; 10-50% of soluble large amount of elemental fertilizer.

本发明所述的可溶性大量元素肥料为可溶性氮肥、可溶性磷肥和可溶性钾肥的一种或一种以上；优选加入可溶性氮肥和可溶性钾肥。 The soluble large amount element fertilizer according to the present invention is one or more of soluble nitrogen fertilizer, soluble phosphate fertilizer and soluble potassium fertilizer; preferably soluble nitrogen fertilizer and soluble potassium fertilizer are added.

所述的浓黑液的固含量为 15.1— 65%，波美度为 9一 40; 优选固含量为 30— 65%，波美度为 The solid content of the concentrated black liquor is 15.1-65%, the Baume degree is 9-40; the preferred solid content is 30-65%, and the Baume degree is

18— 40，更优选固含量为 40— 47%，波美度为 25— 29，所述浓黑液的 pH优选为 5— 11；更优选 pH为 6— 8。 More preferably, the solid content is 40 to 47%, the Baume degree is 25 to 29, and the pH of the concentrated black liquor is preferably 5 to 11; more preferably, the pH is 6 to 8.

本发明所述肥料的制备方法为将各组分混合均匀后进行喷雾干燥或喷浆造粒，得到固体肥料。所述喷浆造粒时喷浆造粒机头温度 550〜600°C，机尾温度 47— 55°C，返料量 50%。 The preparation method of the fertilizer of the invention is that the components are uniformly mixed and then spray-dried or spray-granulated to obtain a solid fertilizer. The spray granulation head temperature is 550~600 °C, the tail temperature is 47-55 °C, and the return amount is 50%.

本发明的第四目的在于提供提供另一种肥料，所述的肥料可以作为黄腐酸肥料。 A fourth object of the present invention is to provide another fertilizer which can be used as a fulvic acid fertilizer.

一种肥料，所述肥料包括稀黑液或浓黑液、木质素和腐殖酸，上述各组分的重量百分比为：稀黑液或浓黑液 30— 80%; 木质素 1一 45%; 腐殖酸 1一 25%; 优选各组分的重量百分比为：稀黑液或浓黑液 50— 60%; 木质素 15— 35%; 腐殖酸 10— 15%; 所述的稀黑液为固含量为 4一 15%,波美度为 2— 9的黑液；所述的浓黑液为将上述稀黑液进行蒸发浓缩除去一部分水分后所得到的黑液。 A fertilizer comprising dilute black liquor or concentrated black liquor, lignin and humic acid, wherein the weight percentage of each component is: 30-80% of diluted black liquor or concentrated black liquor; lignin 1 - 45% Humic acid 1 to 25%; preferably the weight percentage of each component is: dilute black liquor or concentrated black liquor 50-60%; lignin 15-35%; humic acid 10-15%; The liquid is a black liquor having a solid content of 4-15% and a Baume degree of 2-9; and the concentrated black liquor is a black liquor obtained by evaporating and concentrating the diluted black liquor to remove a part of water.

本发明所述的稀黑液为将禾草类秸秆进行蒸煮所产生的黑液，所述的蒸煮包括亚铵法和碱法中的一种或一种以上的组合，所述的碱法包括蒽醌一烧碱法、硫酸盐法或碱性亚钠法。 The diluted black liquor according to the present invention is a black liquor produced by cooking grass straw, and the cooking includes one or a combination of one of an ammoniumimine method and an alkali method, and the alkali method includes A caustic soda method, a sulfate method or an alkaline sodium method.

本发明所述的禾草类秸秆包括麦草、稻草、棉秆、甘蔗渣、芦竹或芦苇中的一种或者两种以上的混合。 The grass straw of the present invention comprises one or a mixture of two or more of wheat straw, straw, cotton stalk, bagasse, arundo donax or reed.

本发明所述的稀黑液优选亚铵法和碱法分别制浆后处理得到亚铵法稀黑液和碱法稀黑液，然后混合形成的亚铵法和碱法混合稀黑液；所述的亚铵法和碱法混合稀黑液中亚铵法稀黑液和碱法稀黑液的混合比例为 1: 100-100： 1，优选 1: 10-10： 1，更优选 1: 4-4： 1，所述的亚铵法稀黑液波美度 2— 9，固含量为 4一 15%， pH为 7— 10; 所述的碱法稀黑液波美度 2— 9，固含量为 4-15%, pH为 9— 13。 The dilute black liquor of the present invention is preferably prepared by an ammonium imide method and an alkali method, respectively, to obtain an ammonium imide black liquor and an alkali dilute black liquor, and then mixed to form an ammonium imide method and an alkali method to mix a dilute black liquor; The mixed ratio of the ammonium imide method and the alkaline black liquor in the iminium method and the alkali method mixed rare black liquor is 1:100-100:1, preferably 1:10-10:1, more preferably 1: 4-4: 1, the ammonium imide black liquor Baume degree 2-9, the solid content is 4-15%, the pH is 7-10; the alkali method black liquor Baume degree 2-9 The solid content is 4-15% and the pH is 9-13.

本发明所述肥料的制备方法为将各组分混合均匀后进行喷雾干燥或喷浆造粒，得到固体肥料。所述喷浆造粒时喷浆造粒机头温度 550〜600°C，机尾温度 47— 55°C，返料量 50%。 The preparation method of the fertilizer of the invention is that the components are uniformly mixed and then spray-dried or spray-granulated to obtain a solid fertilizer. When the spray granulation is performed, the temperature of the spray granulator head is 550 to 600 ° C, the tail temperature is 47-55 ° C, and the return amount is 50%.

本发明的第五目的在于提供提供另一种肥料，所述的肥料是一种可以作为冲施肥的肥料。一种肥料，所述肥料包括稀黑液或浓黑液、可溶性大量元素肥料两组分，各组分的重量百分比为：稀黑液或浓黑液 20— 98%; 可溶性大量元素肥料 2— 80%; A fifth object of the present invention is to provide another fertilizer which is a fertilizer which can be used as a fertilizer. A fertilizer comprising two components of a diluted black liquor or a concentrated black liquor and a soluble large amount of element fertilizer, wherein the weight percentage of each component is: diluted black liquor or concentrated black liquor 20-98%; soluble large amount of element fertilizer 2 80%;

优选各组分的重量百分比为：稀黑液或浓黑液 50— 90%; 可溶性大量元素肥料 10— 50%; 所述的稀黑液为固含量为 4一 15%，波美度为 2—9的黑液； Preferably, the weight percentage of each component is: 50-90% of diluted black liquor or concentrated black liquor; 10-50% of soluble large-scale element fertilizer; the diluted black liquor has a solid content of 4-15%, and a Baume degree of 2 -9 black liquor;

所述的浓黑液为将上述稀黑液进行蒸发浓缩除去一部分水分后所得到的黑液。 The concentrated black liquor is a black liquor obtained by evaporating and concentrating the diluted black liquor to remove a part of water.

本发明所述的稀黑液或浓黑液中还可加入污泥和 /或磷石膏；其重量百分比为污泥： 3— 45%; 磷石膏： 3— 30%; 优选重量百分比为污泥： 10— 20%; 磷石膏： 5— 15%; 所述污泥为造纸污水处理过程产生的生化污泥，有机质含量大于等于 50%。 Sludge and/or phosphogypsum may also be added to the diluted black liquor or concentrated black liquor of the present invention; the weight percentage is sludge: 3-45%; phosphogypsum: 3-30%; preferably the weight percentage is sludge : 10-20%; Phosphogypsum: 5-15%; The sludge is a biochemical sludge produced by the papermaking sewage treatment process, and the organic matter content is 50% or more.

本发明所述的稀黑液或浓黑液中还可加入无机辅料，所述无机辅料为含 N、 P或 K的无机盐，或者其中 2种以上的混合物，优选 KC1，无机辅料加入量为使得^ P₂0₅和 K₂0的总量占各组分总重量干重的质量百分比 4一 30%，优选 5-10%。 The inorganic black material may be added to the diluted black liquor or the concentrated black liquor according to the present invention, and the inorganic auxiliary material is an inorganic salt containing N, P or K, or a mixture of two or more thereof, preferably KC1, and the inorganic auxiliary material is added in an amount of The total amount of ^ P ₂ 0 ₅ and K ₂ 0 is 4 to 30%, preferably 5 to 10% by mass based on the total dry weight of each component.

本发明所述可溶性氮肥为尿素、碳酸氢铵、硫酸铵、氯化铵、磷酸二氢铵或磷酸氢二铵的一种或几种的组合，优选尿素，可溶性氮肥在黄腐酸冲施肥的重量百分比含量为 2— 60%，优选为 2 The soluble nitrogen fertilizer of the present invention is a combination of urea, ammonium hydrogencarbonate, ammonium sulfate, ammonium chloride, ammonium dihydrogen phosphate or diammonium hydrogen phosphate, preferably urea, soluble nitrogen fertilizer in the application of fulvic acid The content by weight is 2 - 60%, preferably 2

-30%；所述的可溶性磷肥为磷酸二氢铵、磷酸氢二铵、磷酸二氢钾或磷酸氢二钾的一种或几种的组合，优选磷酸二氢铵，可溶性磷肥在占肥料产品总重量的重量百分比含量为 2— 60%，优选为 2— 30%; 所述的可溶性钾盐为硫酸钾、氯化钾、磷酸二氢钾或磷酸氢二钾的一种或几种的组合，优选氯化钾，可溶性钾盐在重量百分比含量为 2— 50%，优选为 2— 30%。 -30%; the soluble phosphate fertilizer is a combination of one or more of ammonium dihydrogen phosphate, diammonium phosphate, potassium dihydrogen phosphate or dipotassium hydrogen phosphate, preferably ammonium dihydrogen phosphate, soluble phosphate fertilizer in the fertilizer product The total weight content is 2 to 60% by weight, preferably 2 to 30%; and the soluble potassium salt is one or a combination of potassium sulfate, potassium chloride, potassium dihydrogen phosphate or dipotassium hydrogen phosphate. Preferably, potassium chloride is present, and the soluble potassium salt is present in an amount of from 2 to 50% by weight, preferably from 2 to 30% by weight.

本发明所述的稀黑液优选亚铵法和碱法分别制浆后处理得到亚铵法稀黑液和碱法稀黑液，然后混合形成的亚铵法和碱法混合稀黑液；所述的亚铵法和碱法混合稀黑液中亚铵法稀黑液和碱法稀黑液的混合比例为 1: 100-100： 1，优选 1: 10-10： 1，更优选 1: 4-4： 1，所述的亚铵法稀黑液波美度 2— 9，固含量为 4一 15%， ρΗ为 7— 10; 所述的碱法稀黑液波美度 2— 9，固含量为 The dilute black liquor of the present invention is preferably prepared by an ammonium imide method and an alkali method, respectively, to obtain an ammonium imide black liquor and an alkali dilute black liquor, and then mixed to form an ammonium imide method and an alkali method to mix a dilute black liquor; The mixed ratio of the ammonium imide method and the alkaline black liquor in the iminium method and the alkali method mixed rare black liquor is 1:100-100:1, preferably 1:10-10:1, more preferably 1: 4-4: 1, the ammonium imide black liquor Baume degree 2-9, the solid content is 4-15%, ρΗ is 7-10; the alkali method black liquor Baume degree 2-9 , the solid content is

4-15%, ρΗ为 9一13。 4-15%, ρΗ is 9-13.

本发明所述的浓黑液的固含量为 15.1— 65%，波美度为 9一 40; 优选固含量为 30— 65%，波美度为 18— 40，更优选固含量为 40— 47%，波美度为 25— 29，所述浓黑液的 ρΗ优选为 5— 11；更优选 ρΗ为 6— 8。 The concentrated black liquor of the present invention has a solid content of 15.1-65%, a Baume degree of 9-40, a preferred solid content of 30-65%, a Baume degree of 18-40, and more preferably a solid content of 40-47. %, Baume degree is 25-29, ρΗ of the concentrated black liquor is preferably 5-11; more preferably ρΗ is 6-8.

本发明的第六目的在于提供提供另一种肥料，所述的肥料是一种可作为叶面肥的肥料。为了实现上述目的，本发明采用的技术方案为： A sixth object of the present invention is to provide another fertilizer which is a fertilizer which can be used as a foliar fertilizer. In order to achieve the above object, the technical solution adopted by the present invention is:

一种肥料，所述肥料包括稀黑液或浓黑液、可溶性微量元素肥料两种成分；所述的微量元素包括铁、铜、硼、锌或镁中的一种或一种以上组合。 a fertilizer comprising a black liquor or a concentrated black liquor, a soluble trace element fertilizer; the trace element Including one or more combinations of iron, copper, boron, zinc or magnesium.

本发明所述肥料中黄腐酸重量百分比含量为 5— 40 %，还包括重量百分比含量为 3— 25 %的氮和 /或重量百分比以 P₂0₅计为 3— 25 %的磷和 /或重量百分比以 K₂0计为 3-25 %的钾。 The fertilizer according to the present invention has a content of fulvic acid in a percentage by weight of 5 to 40%, and further comprises a nitrogen content of 2-35% by weight and/or a weight percentage of phosphorus and/or 5% to 25% by weight of P ₂ 0 ₅ . Or the weight percentage is 3-25% potassium in terms of K ₂ 0.

本发明中在所述稀黑液中或浓黑液中加入可溶性微量元素肥料，稀黑液或浓黑液与可溶性微量元素肥料的体积重量比为 1000ml: 0.2-45go In the present invention, a soluble trace element fertilizer is added to the diluted black liquor or concentrated black liquor, and the volumetric weight ratio of the diluted black liquor or the concentrated black liquor to the soluble micronutrient fertilizer is 1000 ml: 0.2-45go

本发明所述的可溶性微量元素肥料为亚铁盐和锌盐，其加入量为每 1000ml碱法和亚铵法混合草浆黑液中分别加入 0. l_15g和 0. 1— 20g，可用作大田作物叶面肥；或所述的可溶性微量元素肥料为硼肥和锌盐，其加入量为每 1000ml碱法和亚铵法混合草浆黑液中分别加入 0. l-15g和 0. 1 一 20g，可用作蔬菜叶面肥；或所述的可溶性微量元素肥料为硼盐、锌盐和亚铁盐，其加入量为每 1000ml碱法和亚铵法混合草浆黑液中分别加入 0. l-15g、 0. 1一 20g和 0. 1— 15g，可用作果树叶面肥。 L_15g和0. 1—20g, can be used as the ferrous salt and the zinc salt, and the amount of the sulphate and the sulphate is 0. l_15g and 0. 1-20g, respectively. L-15g和0. 1。 0-15 l and 0. l-15g and 0. 1-15. a 20g, can be used as a vegetable foliar fertilizer; or the soluble trace element fertilizer is a boron salt, a zinc salt and a ferrous salt, the amount of which is added per 1000 ml of the alkali and ammonium ammonium mixed straw black liquor respectively 0. l-15g, 0. 1-20g and 0. 1-15g, can be used as fruit leaf noodles.

本发明所述的亚铁盐为硫酸亚铁；所述的锌盐为硫酸锌和 /或氯化锌，优选硫酸锌；所述的硼肥为硼酸和 /或硼砂，优选硼砂。 The ferrous salt of the present invention is ferrous sulfate; the zinc salt is zinc sulfate and/or zinc chloride, preferably zinc sulfate; and the boron fertilizer is boric acid and/or borax, preferably borax.

本发明所述肥料的 pH值为 6— 10，黄腐酸重量含量为 5— 40 %。 The fertilizer of the invention has a pH of 6-10 and a fulvic acid weight of 5-40%.

本发明所述的稀黑液优选亚铵法和碱法分别制浆后处理得到亚铵法稀黑液和碱法稀黑液，然后混合形成的亚铵法和碱法混合稀黑液；所述的亚铵法和碱法混合稀黑液中亚铵法稀黑液和碱法稀黑液的混合比例为 1 : 100- 100： 1，优选 1 : 10- 10： 1，更优选 1 : 4-4： 1，所述的亚铵法稀黑液波美度 2— 9，固含量为 4一 15 %， pH为 7— 10; 所述的碱法稀黑液波美度 2— 9，固含量为 4- 15 % , pH为 9一13。 The dilute black liquor of the present invention is preferably prepared by an ammonium imide method and an alkali method, respectively, to obtain an ammonium imide black liquor and an alkali dilute black liquor, and then mixed to form an ammonium imide method and an alkali method to mix a dilute black liquor; The mixed ratio of the ammonium imide method and the alkaline black liquor in the mixed ammonium black liquor and the alkali method is 1:100-100:1, preferably 1:10-10:1, more preferably 1: 4-4: 1, the ammonium imide method black liquor Baume 2-9, solid content is 4-15%, pH is 7-10; the alkali method black liquor Baume 2-9 The solid content is 4-15% and the pH is 9-13.

本发明所述的浓黑液的固含量为 15.1— 65 %，波美度为 9一 40; 优选固含量为 30— 65 %，波美度为 18— 40，更优选固含量为 40— 47 %，波美度为 25— 29，所述浓黑液的 pH优选为 5— 11；更优选 pH为 6— 8。 The concentrated black liquor of the present invention has a solid content of 15.1-65%, a Baume degree of 9-40, a preferred solid content of 30-65%, a Baume degree of 18-40, and more preferably a solid content of 40-47. %, Baume degree is 25-29, the pH of the concentrated black liquor is preferably 5-11; more preferably pH is 6-8.

本发明的大体思路如下，由于禾草类秸秆的主要组成为纤维素和木质素，因此，本发明从此着手，首先制浆，利用秸秆中的纤维素和半纤维素，在制浆过程中，在高温蒸煮液的作用下进行长时间的蒸煮条件下，大多数木质素溶解于蒸煮液中，经挤浆后称为黑液中固含物的主要成分，由于木质素经过蒸煮后充分细化，降解容易，作物易于吸收，因此它成为很好的有机肥料，同时，制浆过程中禾草类秸秆在高温、高压条件下可形成数量可观的黄腐酸，因此挤浆后的黑液可制成肥料，而秸秆中纤维素通过制浆步骤形成纸浆，作为副产品，可用于多种用途。通过上述步骤，达到综合利用禾草类秸秆的目的，而且纸浆和黄腐酸类产品价格不菲，可取得良好的经济效益。 The general idea of the present invention is as follows. Since the main components of grass straw are cellulose and lignin, the present invention proceeds from the first, first pulping, using cellulose and hemicellulose in straw, in the pulping process, Under the action of high-temperature cooking liquid under long-term cooking conditions, most of the lignin is dissolved in the cooking liquid, and after being squeezed, it is called the main component of the solid content in the black liquor, because the lignin is fully refined after being cooked. It is easy to degrade and easy to absorb, so it becomes a good organic fertilizer. At the same time, grass straw can form a considerable amount of fulvic acid under high temperature and high pressure during the pulping process, so the black liquor after extrusion can be It is made into a fertilizer, and the cellulose in the straw is formed into a pulp by a pulping step, and as a by-product, it can be used for various purposes. Through the above steps, the purpose of comprehensive utilization of straw straw is achieved, and the pulp and fulvic acid products are expensive, and good economic benefits can be obtained.

以下是本发明的详细步骤： The following are the detailed steps of the invention:

( 1 ) 蒸煮得到高硬度浆 (1) Cooking to obtain a high hardness pulp

将禾草类秸秆通过蒸煮方法进行制浆，得到浓度为 8— 15%的浆；浆的硬度为高锰酸钾值 16 -28；优选硬度为高锰酸钾值 18— 27; 最优选硬度为高锰酸钾值 20— 25。 The grass straw is pulped by a cooking method to obtain a pulp having a concentration of 8-15%; the hardness of the pulp is a potassium permanganate value of 16 -28; The preferred hardness is potassium permanganate 18-27; the most preferred hardness is potassium permanganate 20-25.

禾草类秸秆可为任意一年生草本植物秸秆，考虑到工业化生产需要大量的原料，包括但不限于麦草、稻草、棉秆、甘蔗渣、芦竹或芦苇等常见大规模种植的禾草类秸秆，可为其中的一种或两种以上的组合；蒸煮方法包括亚铵法和碱法，碱法包括蒽醌-烧碱法、硫酸盐法或碱性亚钠法，各种方法详细工艺如下： Grass straw can be any annual herbaceous straw, considering the large amount of raw materials required for industrial production, including but not limited to common straw grasses such as wheat straw, straw, cotton stalk, bagasse, arundo donax or reed, It may be one or a combination of two or more; the cooking method includes an ammonium imide method and an alkali method, and the alkali method includes a bismuth-soda method, a sulphate method or an alkaline sodium method, and the detailed processes of various methods are as follows:

亚铵法包括如下步骤： The ammonium imide process includes the following steps:

( 1 )在禾草类秸秆中加入蒸煮药液，其中亚硫酸铵的用量为绝干原料量 9一 13%，液比为 1 : (1) adding a cooking liquid to the grass straw, wherein the amount of ammonium sulfite is 9-13% of the absolute dry material, and the liquid ratio is 1:

2-4； 2-4;

(2 ) 通入蒸汽进行加热，加热升温至温度为 100— 120°C时保温 20— 40分钟，进行小放汽，继续加热升温至 165— 173 °C，保温 60— 90分钟； (2) heating with steam, heating to a temperature of 100-120 ° C for 20-40 minutes, a small steam, continue heating to 165-173 ° C, heat 60-90 minutes;

蒽醌-烧碱法包括如下步骤： The bismuth-soda method includes the following steps:

( 1 ) 在禾草类秸秆中加入蒸煮药液，其中用碱量为以氢氧化钠计对绝干原料量 9一 12%，液比为 1 : 2—4，蒽醌加入量为绝干原料量的 0.5— 0.8%; (1) Adding a cooking liquid to the straw of the grass, wherein the amount of the alkali is 9-12% of the dry raw material, and the liquid ratio is 1:2-4, and the amount of the mash is absolutely dry. 0.5-0.8% of the amount of raw materials;

硫酸盐法包括如下步骤： The sulfate method includes the following steps:

( 1 ) 在禾草类秸秆中加入蒸煮药液，其中用碱量为以氢氧化钠计对绝干原料量 8— 11%，液比为 1 : 2-4, 硫化度为 5— 15%; (1) Adding a cooking liquid to the grass straw, wherein the alkali amount is 8-11% of the dry raw material, the liquid ratio is 1:2-4, and the sulfurization degree is 5-15%. ;

(2 ) 通入蒸汽进行加热，加热升温至温度为 110— 140°C时保温 20— 40分钟，进行小放汽，继续加热升温至 165— 173 °C，保温 60— 90分钟； (2) heating with steam, heating and heating to a temperature of 110-140 ° C for 20-40 minutes, a small steam, continue heating to 165-173 ° C, heat 60-90 minutes;

所述碱性亚钠法包括： The alkaline sodium method includes:

( 1 )在禾草类秸秆中加入蒸煮药液，其中，氢氧化钠用量以绝干原料重量计为 11一 15%，亚硫酸钠为 2—6%，蒽醌为 0.02— 0.08%，蒸煮液比为 1 :3-4; (1) adding a cooking liquid to the straw of the grass, wherein the amount of sodium hydroxide is 11-15% by weight of the dry raw material, 2-6% of sodium sulfite, 0.02-0.08% of strontium, cooking ratio Is 1:3-4;

(2 ) 通入蒸汽进行加热，加热升温至温度为 100— 120°C时保温 20— 40分钟，进行小放汽，继续加热升温至 160-165°C，保温 60-90分钟。 (2) Heated with steam, heated to a temperature of 100-120 ° C for 20-40 minutes, a small steam, continue heating to 160-165 ° C, and keep warm for 60-90 minutes.

上述四种方法的步骤（1 )中还可以包括对禾草类秸秆进行浸渍的过程，包括将浸渍液浸渍禾草类秸秆，使液比达到 1 : 2-4, 在常压下于 85°C以上于螺旋浸渍器中保温和混合 10分钟以上，优选在 85— 95°C之间保温混合 10— 40分钟，这样使浸渍液与原料充分接触，使原料的浸渍均匀完全。所述的浸渍液可以为一定浓度的碱溶液，如对绝干原料量为 4%的氢氧化钠溶液，也可以是碱与黑液的混合液，所用黑液的波美度为 11一 14。对原料进行了浸渍预处理，利用了作为废料的黑液，使黑液得到了循环再利用，减少了环境对黑液处理的压力，由于对原料浸渍预处理，使得在加热处理时所脱出的杂细胞、半纤维素、木素为主的黑液分离排出，为下一步的蒸煮过程作准备。 The step (1) of the above four methods may further comprise a process of impregnating grass straw, comprising impregnating the straw with grass straw to achieve a liquid ratio of 1:2-4, at 85° under normal pressure. The above C is incubated and mixed in a spiral impregnator for 10 minutes or more, preferably at 80-95 ° C for 10 to 40 minutes, so that the impregnation liquid is sufficiently contacted with the raw material to make the impregnation of the raw material uniform and complete. The immersion liquid may be a certain concentration of an alkali solution, such as a sodium hydroxide solution having a 4% dry raw material amount, or a mixture of alkali and black liquid, and the black liquid used has a Baume degree of 11-14. . The raw material is immersed and pretreated, and the black liquor as the waste material is utilized to recycle the black liquor, thereby reducing the pressure of the environment on the black liquor treatment, and the immersion pretreatment of the raw material causes the heat treatment to be released. The heterogeneous cells, hemicellulose, and lignin-based black liquor are separated and discharged to prepare for the next cooking process.

在对原料进行浸渍之前，可以采用现有技术对原料进行初步处理，即采用常规的干、湿法备料，以除去叶、穗、谷粒、髓等杂质，这样可以减轻后续工艺的压力，并提高草浆的质量。干、湿法备料可采用现有常规设备，如切草机、筛选机、除尘机、湿法洗涤搓草机、斜螺旋脱水机等。经过备料后的去除水分的禾草类纤维原料也可以为精料，扣除禾草的水分为绝干草，一般草片的长度在 15— 30mm，原料的备料工艺为本领域技术人员公知技术。 Prior to impregnation of the raw materials, the raw materials may be subjected to preliminary treatment using conventional techniques, that is, conventional dry and wet preparations are used. In order to remove impurities such as leaves, ears, grains, and marrow, this can reduce the pressure of subsequent processes and improve the quality of the straw. Dry and wet preparations can be carried out by conventional equipment such as lawn mowers, screening machines, dust removers, wet scrubbers, oblique spiral dewatering machines, and the like. The moisture-removing grass fiber raw material after preparation can also be a fine material, and the moisture of the grass is deducted from the hay. Generally, the length of the grass piece is 15-30 mm, and the raw material preparation process is well known to those skilled in the art.

此外，研究人员还发现，采用上述方法制浆，不仅可以减少对纤维素和半纤维素的损伤和降解，而且蒸煮残液中黄腐酸含量较高。事实上，原生的黄腐酸，是由植物残体在空气和水份存在的条件下，经历漫长的自然过程部分分解而形成. 而蒸煮残液中的黄腐酸，通过调研和分析，是由于在高温、加压下蒸煮植物纤维的过程，相当于加速了原来的自然过程，除了主要生成供造纸用的纸浆外，也生成了数量可观的黄腐酸。将蒸煮后的浆料进行挤浆后所形成的黑液进行分析，采用上述方法中的亚铵法黑液固含物中黄腐酸含量为 10— 20 %，碱法黑液固含物中黄腐酸含量为 5 - 10 % , 而按照普通亚铵法制浆方法得到的黑液固含物中黄腐酸含量为 6— 12 %，碱法黑液固含物中黄腐酸含量为 1一 6 % ; 究其原因，是普通制浆方法虽然蒸煮液浓度较高、保温时间较长，有利于植物残体降解生成黄腐酸，但是过高的蒸煮液浓度和过长的保温时间将黄腐酸进一步降解，生成更小的分子，因此黄腐酸的得率反而降低。 In addition, the researchers also found that pulping by the above method not only reduces the damage and degradation of cellulose and hemicellulose, but also the high content of fulvic acid in the cooking residue. In fact, the native fulvic acid is formed by the decomposition of plant residues in the presence of air and moisture, which is partially decomposed by a long natural process. The fulvic acid in the cooking residue is investigated and analyzed. Since the process of cooking plant fibers under high temperature and pressure is equivalent to accelerating the original natural process, in addition to mainly producing pulp for papermaking, a considerable amount of fulvic acid is also produced. The black liquor formed after the steamed slurry is squeezed is analyzed, and the content of fulvic acid in the black liquor solid content in the above method is 10-20%, and the alkali black liquor solid content The content of fulvic acid is 5 - 10%, and the content of fulvic acid in the black liquor solid content obtained by the ordinary ammonium imide method is 6-12%, and the content of fulvic acid in the alkali black liquor solid content is 1 to 6 %; The reason is that the common pulping method, although the concentration of the cooking liquid is high, and the holding time is long, is beneficial to the degradation of plant residues to produce fulvic acid, but the excessive cooking liquid concentration and the long holding time The fulvic acid is further degraded to form smaller molecules, so the yield of fulvic acid is reduced.

(2 )高硬度浆后处理得到挤浆后的浆料和稀黑液；所述挤浆后的浆料用于制备漂白化学浆以及纸制品。 (2) Post-treatment of high-hardness pulp to obtain a slurry after slurrying and a dilute black liquor; the slurry after slurching is used to prepare a bleaching chemical pulp and a paper product.

将高硬度浆进行挤浆得到固含量为 4一 15 %，波美度为 2— 9的稀黑液。 The high-hardness pulp is subjected to slurrying to obtain a diluted black liquor having a solid content of 4 to 15% and a Baume degree of 2-9.

本发明中在挤浆过程中所使用的挤浆机，优选现有技术中用来提取黑液的螺旋挤浆机。使用挤浆机进行挤浆时，由于在挤浆的过程会产生很大的挤压力，温度迅速上升，促使纤维分离、分丝、帚化、压溃，初生壁遭到破坏，纤维吸收足够能量，使纤维内部产生很大的应力，浆的反应性能得到很大提高。同时，纤维产生细纤维化，表皮有机物及纤维间杂质溶解到蒸煮黑液中，通过出液槽排出，纤维纯度得到极大提高。黑液中的一些灰分和杂质也随着黑液被排出。本发明所述的挤浆机为现有技术中提取黑液用的螺旋挤浆机为单螺旋挤浆机和双螺旋挤浆机；优选所述的挤浆机为变径或变螺距的螺旋挤浆机。 The extruder used in the squeezing process in the present invention is preferably a screw extruder for extracting black liquor in the prior art. When using a squeezer for squeezing, the temperature will rise rapidly due to the large squeezing force during the squeezing process, which will cause the fibers to separate, separate, smash, crush, and the primary wall is destroyed. The energy causes a large stress inside the fiber, and the reaction performance of the slurry is greatly improved. At the same time, the fiber is fibrillated, and the impurities of the epidermis and interfibers are dissolved in the cooking black liquor, and the fiber purity is greatly improved by discharging through the liquid discharge tank. Some of the ash and impurities in the black liquor are also discharged with the black liquor. The squeezing machine of the present invention is a single-screw extruder and a double-screw extruder for extracting black liquor in the prior art; preferably, the squeezing machine is a spiral with variable diameter or variable pitch Squeezing machine.

本发明中优选的挤浆机为变径变螺距的螺旋挤浆机，利用变径变螺距挤浆机，使浆料在缓慢变小的空间里，使被压缩的浆层里外脱水一致。本发明所选用的螺旋挤浆机，在对浆进行挤浆后，浆的叩解度变化不大，也就是说，浆经过挤浆机挤浆之后，能将禾草类纤维固有的纤维长度保持得比较好，最大限度地减少了纤维的损伤。 The preferred extruder in the present invention is a screw-type extruder with a variable pitch and a variable pitch pitch extruder, so that the slurry is dewatered in and out of the compressed slurry layer in a slowly decreasing space. The screw extruder selected in the invention has little change in the degree of enthalpy of the slurry after the slurry is squeezed. That is to say, after the slurry is squeezed by the extruder, the inherent fiber length of the grass fiber can be maintained. Better, minimize fiber damage.

挤浆机挤出的浆的硬度也比较高，为高硬度浆，高锰酸钾值为 16— 28 ; 优选硬度为高锰酸钾值 18— 27;最优选硬度为高锰酸钾值 20— 25，由于硬度较高，因此减少了污染，降低了生产成本。更重要的是，由于挤浆机的使用，而在挤浆的过程中，由于高硬度浆中木质素以及其它杂质如灰分等含量较高，而且纤维与纤维之间通过木质素粘连到一起，且木质素含量较高，挤浆的过程中将一些粘连在一起的纤维束松开，为以后步骤的洗涤和漂白做好了充分的准备。 The hardness of the pulp extruded by the extruder is also relatively high. It is a high hardness pulp with a potassium permanganate value of 16-28; the preferred hardness is a potassium permanganate value of 18-27; the most preferred hardness is a potassium permanganate value of 20 — 25, due to the higher hardness, it reduces pollution and reduces production costs. More importantly, due to the use of the squeezer, during the process of squeezing, due to the high content of lignin and other impurities such as ash in the high-hardness pulp, and the fibers and fibers are adhered together by lignin, The lignin content is relatively high, and some of the bundles of fibers that are stuck together are loosened during the squeezing process, and are fully prepared for washing and bleaching in the subsequent steps.

本发明中所得到的高硬度浆用途广泛，可作为模塑产品的原料，用于制作快餐盒、工业用缓冲包装纸、医用器具、儿童玩具等，具有可自然降解、良好的抗震性能、高温下不易产生变形、不产生静电、具套叠性可节省储运空间、回收利用率 100 %等多种优点。还可以经过常规漂白后制备高质量的漂白浆，进而制作高档用纸。 The high-hardness pulp obtained in the invention is widely used as a raw material of a molded product, and is used for making a snack box and industrial use. Wrapping paper, medical equipment, children's toys, etc., with natural degradation, good seismic performance, no deformation at high temperature, no static electricity, socketing can save storage and transportation space, recycling rate of 100%, etc. . High-quality bleached pulp can also be prepared after conventional bleaching to produce high-grade paper.

(3)将稀黑液中进行处理，得到肥料前产品。 (3) The black liquor is treated to obtain a pre-fertilizer product.

将稀黑液直接处理，得到肥料产品或先将稀黑液蒸发浓缩除去一部分水分得到浓黑液，再进行处理，得到肥料前产品。 The diluted black liquor is directly treated to obtain a fertilizer product or the diluted black liquor is first evaporated to remove a part of the water to obtain a concentrated black liquor, which is then treated to obtain a pre-fertilizer product.

上述经蒸煮、挤浆后得到的稀黑液或浓黑液是本发明肥料产品的主要原料。其中所述稀黑液为上述制浆方法之一后处理得到的稀黑液；或 2种以上制浆方法分别后处理得到的稀黑液混合后形成的混合稀黑液；其中，亚铵法制浆后得到的亚铵法稀黑液波美度 2— 9，固含量为 4一 15 %， pH为 7— 10; 碱法制浆得到的碱法稀黑液波美度 2— 9，固含量为 4一 15 %， pH为 9一 13。 The above-mentioned dilute black liquor or concentrated black liquor obtained by cooking and squeezing is the main raw material of the fertilizer product of the present invention. Wherein the diluted black liquor is a diluted black liquor obtained by one of the above-mentioned pulping methods; or a mixed diluted black liquor formed by mixing the diluted black liquor obtained by the two or more pulping methods respectively; wherein, the ammonium imide method The ammonium imide black liquor obtained after pulping has a Baume degree of 2-9, a solid content of 4-15%, a pH of 7-10; an alkali method of a rare black liquor Baume degree 2-9 The solid content is 4-15% and the pH is 9-13.

优选亚铵法稀黑液或亚铵法稀黑液和碱法稀黑液混合形成的亚铵法和碱法混合稀黑液。这是由于亚铵法稀黑液的营养组分含量一般较碱法高，因此实际生产中优选亚铵法稀黑液，但由于亚铵法黑液在蒸发浓缩时存在 NH₃的挥发，会造成黑液 pH的急剧下降，对设备造成严重的腐蚀，因此更优选将亚铵法稀黑液和碱法稀黑液混合后得到亚铵法和碱法混合稀黑液，即可使制得的肥料中含有较多的养分，肥效较高，又可减少对设备的腐蚀，还可以同时处理两种黑液。而将碱法和亚铵法草浆黑液混合，利用不同的混合比例来得到所需要的 pH值，得到的亚铵法和碱法混合稀黑液可作为工业生产的原料，也可以直接用于农田灌溉。亚铵法和碱法混合稀黑液中这两种黑液的混合比例为 1 : 100- 100： 1，优选 1 : 10- 10： 1，更优选 1 : 4-4： 1。 Preferably, the iminium method and the alkali method are used to mix the dilute black liquor or the ammonium imide black liquor and the alkali black liquor. This is because the content of nutrient components of the ammonium blackish solution is generally higher than that of the alkali method. Therefore, in the actual production, the ammonium imide black liquor is preferred, but due to the volatilization of NH ₃ in the black liquor of the ammonium imide method during evaporation and concentration, The pH of the black liquor is drastically lowered, causing serious corrosion to the equipment. Therefore, it is more preferable to mix the ammonium imide black liquor and the alkali black liquor to obtain an ammonium sulfite method and an alkali method to mix the black liquor. The fertilizer contains more nutrients, higher fertilizer efficiency, and can reduce the corrosion of the equipment. It can also treat two kinds of black liquor at the same time. The alkali method and the ammonium imide grass black liquor are mixed, and different mixing ratios are used to obtain the required pH value, and the obtained ammonium imide method and the alkali method mixed black liquor can be used as raw materials for industrial production, or can be directly used. Irrigation on farmland. The mixing ratio of the two black liquors in the ammonium chloride and alkali mixed black liquor is 1: 100-100: 1, preferably 1: 10- 10: 1, more preferably 1: 4-4: 1.

考虑到有利于后续工艺干燥步骤的工业化生产喷雾干燥或喷浆造粒，因此最好减少黑液中的水分含量，将上述稀黑液蒸发浓缩，得到浓黑液后加入有机辅料。浓黑液的固含量为 15.1— 65 %，波美度为 9一 40; 优选固含量为 30— 65 %，波美度为 18— 40，更优选固含量为 40— 47 %，波美度为 25— 29，由于蒸发浓缩中 NH₃的挥发，黑液的 pH会有所下降，一般为 5— 11，优选 pH为 6— 8，以免制得的肥料造成土壤 pH的急剧变化，对作物产生不良影响。 In view of industrial production spray drying or spray granulation which is advantageous for the subsequent process drying step, it is preferred to reduce the moisture content in the black liquor, and evaporate and concentrate the above-mentioned diluted black liquor to obtain a concentrated black liquor and then add the organic adjuvant. The solid content of concentrated black liquor is 15.1-65%, the Baume degree is 9-40; the preferred solid content is 30-65%, the Baume degree is 18-40, and the solid content is 40-47%, Baume degree 25-29, the pH of the black liquor will decrease due to the volatilization of NH ₃ in the evaporation concentration, generally 5-11, preferably pH 6-8, so as to avoid the rapid change of soil pH caused by the prepared fertilizer. Have an adverse effect.

将稀黑液蒸发浓缩为浓黑液，优选使用多效蒸发工艺，这是因为多效蒸发工艺以蒸汽为热源，每吨蒸汽可带走 3— 5吨黑液中的水分，效率高，而且能够节约能源。但随着多效蒸发器效数的增力口，单位蒸汽消耗量逐渐减小，因此综合考虑的话，最好使用六效蒸发工艺。下面以本发明最优选固含量为 40— 47 %，波美度为 25— 29的浓黑液的六效蒸发工艺为例进行介绍： Evaporating and diluting the diluted black liquor into concentrated black liquor, preferably using a multi-effect evaporation process, because the multi-effect evaporation process uses steam as a heat source, and each ton of steam can carry away water in 3 to 5 tons of black liquor, which is highly efficient, and Can save energy. However, with the increase in the efficiency of the multi-effect evaporator, the unit steam consumption is gradually reduced, so it is preferable to use the six-effect evaporation process in consideration of comprehensive consideration. The following is an example of a six-effect evaporation process of a concentrated black liquor having an optimum solid content of 40 to 47% and a Baume degree of 25-29;

六效蒸发工艺的设备为六效蒸发器，六效蒸发器中的每一效通常分为三部分，可参见图 3，最上部为分配盘，作用是将循环泵抽上的黑液平均分配到各管中，中间为气室，为蒸汽与黑液的热交换区域，黑液在此区域蒸发浓缩，最下部为液室，蒸发浓缩后的黑液流入此部位，所述的六效蒸发器每一效的结构也可以为现有技术中蒸发器的结构。 The equipment of the six-effect evaporation process is a six-effect evaporator. Each effect of the six-effect evaporator is usually divided into three parts. See Figure 3, the upper part is the distribution plate, and the function is to distribute the black liquor evenly on the circulation pump. In each tube, the middle is a gas chamber, which is a heat exchange area between steam and black liquor. The black liquor is evaporated and concentrated in this area, and the lowermost part is a liquid chamber. The black liquor evaporated and concentrated flows into this part, and the six-effect evaporation The structure of each effect of the device can also be the structure of the evaporator in the prior art.

总的来说，六效蒸发器中的物质可分为气相和液相两部分，液相即黑液，气相即蒸汽，流向分别如下所示： 1、液相即黑液流向：如图 1所示。 2、气相即蒸汽流向：如图 2所示。混合草浆黑液流入 VI效蒸发器，被来自 V效蒸发器的蒸汽加热浓缩，进入 V效蒸发器，被来自 IV效的蒸汽加热浓缩，进入 IV效蒸发器，被来自 III效的蒸汽加热浓缩进入半浓黑液槽，变为半浓黑液，固含量为 30— 35 %，波美度为 18-21。半浓黑液然后依次进入 II效蒸发器和 I效蒸发器，被蒸汽加热浓缩后进入浓黑液槽，变为浓黑液，流入浓黑液槽。浓黑液即碱法和亚铵法混合浓缩草浆黑液，其固含量为 40— 47 %，波美度为 25-29， pH = 5— 11。 In general, the material in the six-effect evaporator can be divided into two parts: gas phase and liquid phase. The liquid phase is black liquor, and the gas phase is steam. The flow directions are as follows: 1. The liquid phase is the black liquor flow direction: Shown. 2. Gas phase is the flow direction of steam: as shown in Figure 2. The mixed straw black liquor flows into the VI effect evaporator, is heated and concentrated by the steam from the V effect evaporator, enters the V effect evaporator, and is steamed from the IV effect. It is heated and concentrated, and enters the IV effect evaporator. It is heated and concentrated from the III effect steam into the semi-rich black liquor tank to become a semi-rich black liquor with a solid content of 30-35% and a Baume degree of 18-21. The semi-concentrated black liquor then enters the II effect evaporator and the I effect evaporator in turn, is heated and concentrated by steam, and then enters the concentrated black liquor tank, becomes a concentrated black liquor, and flows into the concentrated black liquor tank. The concentrated black liquor, that is, the alkali method and the ammonium imide method, is mixed with the concentrated straw black liquor, and has a solid content of 40 to 47%, a Baume degree of 25-29, and a pH of 5-11.

在六效蒸发器中，气相即蒸汽的流向刚好相反，目的在于增加气相和液相间的温度差，提高热交换效率。其中，从蒸汽发生器出来的初始蒸汽温度为 200— 210°C，压力 =0. 8-1 MPa，经过减压阀降到 0. 2-0. 4MPa、 14CTC左右，通入 I效，此时的蒸汽为清洁蒸汽，与 I效的黑液进行热交换后，变为清洁冷凝水贮藏在清洁冷凝水槽中，清洁冷凝水的温度为 105°C-120°C，为了充分利用其热量，将其通过一个闪蒸罐，闪蒸的蒸汽通入 II效蒸发器，排出的清洁冷凝水可以用于制浆工艺中的洗浆。 In the six-effect evaporator, the gas phase, that is, the flow of steam, is just the opposite, in order to increase the temperature difference between the gas phase and the liquid phase, and to improve the heat exchange efficiency. Wherein, the initial steam temperature from the steam generator is 200-210 ° C, the pressure is 0.8-1 MPa, and the pressure reducing valve is lowered to 0. 2-0. 4MPa, 14CTC or so, the I effect is applied, The steam is clean steam, and after heat exchange with the I effect black liquor, it becomes clean and condensed water is stored in the clean condensate tank, and the temperature of the condensed water is cleaned from 105 ° C to 120 ° C. In order to fully utilize the heat, Passing it through a flash tank, the flashed steam is passed to the II effect evaporator, and the discharged clean condensate can be used for washing in the pulping process.

I效的黑液蒸发的蒸汽进入 II效，作为 II效的加热蒸汽，同样， II效的黑液蒸发的蒸汽作为 in效的蒸发蒸汽，依次类推， II、 III、 IV、 V、 VI效黑液蒸发的蒸汽为污蒸汽，因其为前一效沸腾黑液产生，其与该效黑液进行热交换后，即形成污冷凝水， II、 III、 IV、 V、 VI效的污冷凝水最终汇总在一起，其中 COD含量在 1500mg/L左右，流向污水处理厂进行处理。 The I-effect black liquor evaporates the steam into the II effect, as the II-effect heating steam, likewise, the II-effect black liquor evaporates the steam as the in-effect evaporative vapor, and so on, II, III, IV, V, VI black The vapor evaporated by the liquid is the dirty steam, which is produced by the former boiling black liquor, and after the heat exchange with the black liquor, the sewage condensed water is formed, and the condensed water of the II, III, IV, V, and VI effects is formed. Finally, they are put together, and the COD content is about 1500mg/L, which is sent to the sewage treatment plant for treatment.

上述各效中黑液的温度依次为：1效 100-110°C、 II效 90-100°C、 III效 80-90°C、 IV效 70-80 The temperature of the black liquor in each of the above effects is: 1 effect 100-110 ° C, II effect 90-100 ° C, III effect 80-90 ° C, IV effect 70-80

°C、 V效 60- 70°C、 VI效 50- 60°C ; 各效黑液波美度分别为： VI效 5— 8、 V效 7— 10、 IV效 9 - 12、 III效 11-14; 经过 II效和 I效时， II效 14一 17、 I效 18— 21。各效的压力为： I效 20— 38 kPa、 II效 10〜- 10kPa、 III效一 20〜一 30 kPa、 IV效一 50〜一 60kPa、 V效一 60〜一 70kPa、 VI效一 75〜一 85kPa，文中所有压力都为相对压力，相对大气压而言。 °C, V effect 60-70 °C, VI effect 50-60 °C; each effect black liquor wave beauty is: VI effect 5-8, V effect 7-10, IV effect 9 - 12, III effect 11 -14; II effect 14-17, I effect 18-21 after II effect and I effect. The pressure of each effect is: I effect 20-38 kPa, II effect 10~- 10kPa, III effect one 20~30 kPa, IV effect one 50~ one 60kPa, V effect one 60~ one 70kPa, VI effect one 75~ At 85 kPa, all pressures in the text are relative pressures, relative to atmospheric pressure.

各效的热交换面积可以视设计处理能力而定，以设计处理能力：蒸发水 70 吨 /h，每天处理 The heat exchange area of each effect can be determined according to the design processing capacity to design the processing capacity: Evaporated water 70 tons / h, daily processing

2000m3的亚铵和碱的混合黑液；正常负荷下通蒸汽量为 17. 5吨 /h而言，每效的热交换面积为： I 效 1600m²、 II效 1200 m²、 III效、 IV效、 V效、 VI效都是 900 m²。 2000m3 of mixed black liquor of ammonium and alkali; under normal load, the amount of steam is 17.5 tons / h, the heat exchange area per effect is: I effect 1600m ² , II effect 1200 m ² , III effect, IV The effect, V effect, and VI effect are both 900 m ² .

现有技术中的六效以下的蒸发器无法满足本发明的一步提浓的要求。六效蒸发器则可满足此要求。此外，在设计中为了提高热交换效率，往往需要将各效蒸发器中 N2等不凝性气体除去，因此在气室处连接一个真空泵，在气室和真空管道连接处有节流孔板，只允许不凝性气体通过，而水蒸气无法通过。 The evaporators of the six-effect or less in the prior art cannot satisfy the one-step enrichment requirement of the present invention. Six-effect evaporators meet this requirement. In addition, in order to improve the heat exchange efficiency in the design, it is often necessary to remove the non-condensable gas such as N2 in each effect evaporator, so that a vacuum pump is connected at the gas chamber, and an orifice plate is connected at the junction of the gas chamber and the vacuum pipe. Only non-condensable gases are allowed to pass, and water vapor cannot pass.

将稀黑液中或浓黑液中进行处理，得到肥料产品，下面分别加以描述： The diluted black liquor or concentrated black liquor is treated to obtain a fertilizer product, which is described below:

( 1 ) 肥料前产品 (1) Pre-fertilizer products

在稀黑液中或浓黑液中加入酸调节 pH5以下，使之析出木素，然后加入絮凝剂，过滤除去木素，得到滤液。所得滤液即为肥料前产品。 Acid is added to the diluted black liquor or concentrated black liquor to adjust pH below 5, to precipitate lignin, then flocculant is added, and lignin is removed by filtration to obtain a filtrate. The filtrate obtained is the pre-fertilizer product.

考虑到酸的成本和析出效率，优选的 pH为 2— 4，所用的酸可以为有机酸和无机酸，有机酸包括但不限于甲酸、乙酸、丙酸、苯甲酸等；无机酸包括但不限于盐酸、硫酸、硝酸、磷酸等。酸析木素后，溶液中主要为木质素和木素磺酸铵的混合物。 Considering the cost of the acid and the precipitation efficiency, the preferred pH is 2-4, the acid used may be an organic acid and an inorganic acid, and the organic acid includes, but not limited to, formic acid, acetic acid, propionic acid, benzoic acid, etc.; Limited to hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like. After acid lignin, the solution is mainly a mixture of lignin and ammonium lignosulfonate.

酸析木素后，由于有部分木素是悬浮在黑液中的，因此加入黑液重量 2— 50ppm的絮凝剂，使之沉淀，优选 5— 15ppm，最优选 5ppm; 絮凝剂包括但不限于聚合硫酸铁、碱式氯化铝、聚丙烯酸铵等，加入絮凝剂后，将黑液过滤，除去木素，得到滤液。 After the acid lignin is extracted, since some lignin is suspended in the black liquor, a flocculant having a black liquor weight of 2 to 50 ppm is added. Precipitating, preferably 5-15 ppm, most preferably 5 ppm; flocculating agent including but not limited to polymeric ferric sulfate, basic aluminum chloride, ammonium polyacrylate, etc., after adding flocculating agent, filtering black liquor to remove lignin, obtaining filtrate .

将上述滤液进行蒸发浓缩，可得到不同浓度的溶液，可以将其进行喷雾干燥或者喷浆造粒，所述喷浆造粒时喷浆造粒机头温度 550〜600°C，机尾温度 47— 55 °C，返料量 50%。即可得到固体肥料，也可以将滤液进一步提纯后再进行干燥得到固体肥料。提纯方法包括但不限于用离子交换树脂或加入丙酮萃取。 The filtrate is concentrated by evaporation to obtain different concentrations of the solution, which can be spray-dried or spray-granulated. The spray granulation head temperature is 550~600 ° C, and the tail temperature is 47. — 55 °C, 50% return. The solid fertilizer can be obtained, or the filtrate can be further purified and then dried to obtain a solid fertilizer. Purification methods include, but are not limited to, ion exchange of the resin or addition of acetone.

对本发明制得的肥料产品进行检验，从其结构特征的元素组成、功能团含量、数控分子量来看，性能介于矿源黄腐酸和生化黄腐酸之间，活性大于矿源黄腐酸而小于生化黄腐酸，但与矿源黄腐酸相比，原料成本低廉，与生化黄腐酸相比，省略了耗时的发酵过程，生产效率更高。 The fertilizer product prepared by the invention is tested, and the performance is between the ore source fulvic acid and the biochemical fulvic acid, and the activity is greater than the ore source fulvic acid and less than the elemental composition, functional group content and numerical control molecular weight. Biochemical fulvic acid, but compared with the source fulvic acid, the raw material cost is low, compared with biochemical fulvic acid, the time-consuming fermentation process is omitted, and the production efficiency is higher.

本发明肥料前产品以及进一步提纯得到固体肥料中含有多种活性基团和生理活性物质，是分子量较小的高分子有机化合物，酸性基团多，渗透性强，能溶于酸、碱和水，易被植物吸收。它作为无公害的有机物质，可广泛的在农业生产上应用，在实际应用效果上表现为提高农作物的抗旱、抗寒能力，增强作物的抗病能力，刺激作物的生长，从而提高作物的产量，改善作物的品质。 The pre-fertilizer product of the invention and the further purification of the solid fertilizer contain a plurality of active groups and physiologically active substances, and are small-molecular polymer organic compounds, have many acidic groups, are highly permeable, and are soluble in acids, alkalis and water. , easily absorbed by plants. As a non-polluting organic substance, it can be widely used in agricultural production. In practical application, it can improve the drought resistance and cold resistance of crops, enhance the disease resistance of crops, stimulate crop growth, and increase crop yield. , improve the quality of crops.

本发明方法提供了黄腐酸的一种新来源，可同时治理两种黑液，而且提取的黄腐酸价格不菲，副产品木素也有广泛的用途，可用作减水剂或土壤改良剂，可取得良好的经济效益 The method of the invention provides a new source of fulvic acid, which can simultaneously treat two kinds of black liquor, and the extracted fulvic acid is expensive, and the by-product lignin has a wide range of uses, and can be used as a water reducing agent or a soil conditioner. , can achieve good economic benefits

( 2 ) 肥料 (2) Fertilizer

在稀黑液中或浓黑液中加入有机辅料形成料浆，有机辅料为木质素和腐殖酸。其中木质素的作用在于调整浓缩的黑液的粘度以及调整 pH，以利于后续生产的进行。腐殖酸的作用在于改变肥料的外观和颜色，同时还能增加肥料的肥效。 The organic auxiliary material is added to the black liquor or the concentrated black liquor to form a slurry, and the organic auxiliary materials are lignin and humic acid. The role of lignin is to adjust the viscosity of the concentrated black liquor and adjust the pH to facilitate subsequent production. The role of humic acid is to alter the appearance and color of the fertilizer while also increasing the fertilizer efficiency.

各组分的重量百分比为： The weight percentage of each component is:

稀黑液或浓黑液 30— 80 % ; 木质素 1一 45 % ; 腐殖酸 1一 25 % ; Dilute black liquor or concentrated black liquor 30-80 %; lignin 1 45 %; humic acid 1-25 %;

优选各组分的重量百分比为： Preferably, the weight percentage of each component is:

稀黑液或浓黑液 50— 60 % ; 木质素 15— 35 % ; 腐殖酸 10— 15 %。 Dilute black liquor or concentrated black liquor 50-60%; lignin 15-35%; humic acid 10-15%.

上述肥料，混合形成料浆时还可以包括重量百分比为 0— 45 %污泥；优选重量百分比为 10— 20 % , 所述污泥为造纸污水处理过程产生的生化污泥，有机质含量大于等于 50 %，通常其中全氮含量 2— 3 %、全磷含量 0.2— 0.6 %，全钾含量 2— 4 %。污泥可以增加黑液的固含物浓度，调整 pH。此外，由于生化污泥极易造成二次污染，常规处理费用不菲，在配方中加入生化污泥，既可以节省处理生化污泥的费用，还变废为宝，降低了生产的成本。 The above fertilizer may further comprise a slurry of 0-45% by weight when mixed to form a slurry; preferably 10-20% by weight, the sludge is a biochemical sludge produced by a papermaking sewage treatment process, and the organic matter content is 50 or more. %, usually with a total nitrogen content of 2-3 %, a total phosphorus content of 0.2-0.6%, and a total potassium content of 2-4%. The sludge can increase the solid concentration of the black liquor and adjust the pH. In addition, since biochemical sludge is highly susceptible to secondary pollution, conventional treatment costs are high, and biochemical sludge is added to the formulation, which not only saves the cost of processing biochemical sludge, but also turns waste into treasure, reducing the cost of production.

此外，为了增加肥料的肥效，还可在黑液中加入无机辅料，无机辅料为含 N、 P或 K的无机盐，或者其中 2种以上的混合物，目的在于调整肥料中 N、 P、 K的含量，使得肥料中的 Ν、 Ρ、 Κ含量总和 4— 30 %，出于成本考虑，优选 5 %。其中 Ρ含量以 Ρ₂0₅计， Κ以 Κ₂0计，符合并优于农业部有关有机肥的标准，由于实际生产中干燥温度一般比较高， Ν盐容易挥发，造成养分的损失，而目前的土壤中缺 Ρ情况较少，而土壤中普遍缺 Κ，因此优选加入的无机盐为 KC1，当然也可视实际情况加入其它种类的无机盐和铁、铜、硼、锌或镁等微量元素。此外，混合形成料浆时还可以包括重量百分比为 0— 30 %的磷石膏，优选重量百分比为 5— 15 %。磷石膏是指在磷酸生产中用硫酸处理磷矿时产生的固体废渣,其主要成分为硫酸钙，此外还含有多种其他杂质。同时，生产过程中，溶液中的 HP04² 取代石膏晶格中部分 S04²_，磷石膏杂质分两大类，不溶性杂质：如石英、未分解的磷灰石、不溶性 P₂0₅、共晶 P₂0₅、氟化物及氟、铝、镁的磷酸盐和硫酸盐；可溶性杂质：如水溶性 P₂0₅，溶解度较低的氟化物和硫酸盐。磷石膏的大量堆存，不仅侵占了土地资源，由于风蚀、雨蚀还会造成了大气、水系及土壤的污染。在本发明肥料配方中增加磷石膏，既可以利用其中含有的可溶性 P₂0₅，增加大量元素的含量，还可以处理工业废澄，防止对环境的污染。同时，磷石膏中的主要成分为硫酸钙，对盐碱土有良好的化学改良作用。 In addition, in order to increase the fertilizer efficiency, inorganic adjuvants may also be added to the black liquor. The inorganic adjuvants are inorganic salts containing N, P or K, or a mixture of two or more thereof, in order to adjust the N, P, K in the fertilizer. The content is such that the total content of lanthanum, cerium and lanthanum in the fertilizer is 4-30%, and for cost reasons, 5% is preferred. The strontium content is Ρ ₂ 0 ₅ , Κ Κ ₂₀ , which is in line with and better than the Ministry of Agriculture's relevant organic fertilizer standards. Because the drying temperature in actual production is generally high, strontium salt is easily volatilized, resulting in loss of nutrients. At present, there are few defects in the soil, and the soil is generally deficient. Therefore, it is preferable to add the inorganic salt to KC1. Of course, other kinds of inorganic salts and iron, copper, boron, zinc or magnesium may be added depending on the actual situation. element. In addition, the slurry may also be included in the mixing to form a slurry of 0 to 30% by weight, preferably 5 to 15% by weight. Phosphogypsum refers to the solid waste residue produced when phosphate rock is treated with sulfuric acid in the production of phosphoric acid. Its main component is calcium sulfate, and it also contains various other impurities. At the same time, in the production process, HP04 ² in the solution replaces part of S04 ² _ in the gypsum crystal lattice. Phosphogypsum impurities are divided into two categories, insoluble impurities: such as quartz, undecomposed apatite, insoluble P ₂ 0 ₅ , eutectic P ₂ 0 ₅ , fluoride and fluoride, aluminum, magnesium phosphate and sulfate; soluble impurities: such as water-soluble P ₂ 0 ₅ , less soluble fluoride and sulfate. The massive accumulation of phosphogypsum not only encroachs on land resources, but also causes pollution of the atmosphere, water system and soil due to wind erosion and rain erosion. The addition of phosphogypsum in the fertilizer formulation of the present invention can utilize the soluble P ₂ 0 ₅ contained therein, increase the content of a large amount of elements, and can also treat industrial waste to prevent environmental pollution. At the same time, the main component of phosphogypsum is calcium sulfate, which has a good chemical improvement effect on saline-alkali soil.

将料浆干燥，即得到肥料。 The slurry is dried to obtain a fertilizer.

肥料中黄腐酸重量百分比含量为 5— 40 %，有机质含量为 20— 85 %，如果加入无机辅料的话， N、 P和 K总含量通常为 4一 30 %。干燥可以采用喷浆造粒制成颗粒有机肥，也可以喷雾干燥制成粉状有机肥或采用其它方法干燥。鉴于一般肥料溶解过快，养分容易流失，肥效短，因此优选采用喷浆造粒造成粒肥，下面对其工艺做详细描述： The percentage of fulvic acid in the fertilizer is 5-40%, and the organic matter content is 20-85%. If inorganic adjuvant is added, the total content of N, P and K is usually 4-30%. Drying can be carried out by spray granulation to form granulated organic fertilizer, or spray-dried to make powdered organic fertilizer or dried by other methods. In view of the fact that the general fertilizer dissolves too fast, the nutrients are easily lost, and the fertilizer efficiency is short, it is preferable to use the spray granulation to cause the granular fertilizer, and the process is described in detail below:

首先在稀黑液或浓黑液中加入木质素和腐殖酸形成料浆，优选浓黑液，也可以选择加入污泥和 /或无机辅料，然后，料浆进入喷浆造粒机进行喷浆造粒，喷浆造粒机的机头温度 550〜600°C，机尾温度 47— 55°C，为了保证生产的连续进行，返料量要 50%，粗产物经过滚筒筛后，小颗粒和破碎后的大颗粒返回喷浆造粒机，粒度在 3— 5mm的颗粒形成产品，打包、进仓即可。 First, adding lignin and humic acid to the diluted black liquor or concentrated black liquor to form a slurry, preferably concentrated black liquor, or optionally adding sludge and/or inorganic auxiliary materials, and then, the slurry enters the spray granulator for spraying. Pulp granulation, the head temperature of the spray granulator is 550~600°C, and the tail temperature is 47-55°C. In order to ensure continuous production, the return amount is 50%. After the coarse product passes through the trommel, it is small. The granules and the broken large particles are returned to the spray granulator, and the granules with a particle size of 3 - 5 mm form a product, which can be packed and put into the warehouse.

得到的产品即为肥料，粒度 3— 5mm (实际产品中为 3— 5mm的质量分数 80% )，硬度 6— 30N, 有机质含量 20— 85 %，黄腐酸重量百分比含量为 5— 40%。 The obtained product is fertilizer, the particle size is 3-5 mm (the actual product is 3-5 mm mass fraction 80%), the hardness is 6-30N, the organic matter content is 20-85%, and the fulvic acid weight percentage is 5-140%.

如果干燥方法选择喷雾干燥的话，得到的产品为粉状，不做粒度要求，因此除了粒度和硬度夕卜，其它指标与上同。 If the drying method is spray-dried, the obtained product is in powder form and does not require particle size. Therefore, in addition to the particle size and hardness, other indexes are the same as above.

上述肥料除了符合农业部有机肥标准外，其含有丰富的黄腐酸含量 5%，黄腐酸的来源除了加入的腐殖酸中含有的一部分外，主要来自于黑液。黄腐酸含有多种活性基团和对植物的生理活性物质，是分子量较小的高分子有机化合物，酸性基团多，渗透性强，能溶于酸、碱和水，易被植物吸收。它作为无公害的有机物质，广泛的在农业生产上应用，在实际应用效果上表现为提高农作物的抗旱、抗寒能力，增强作物的抗病能力，刺激作物的生长，从而提高作物的产量，改善作物的品质。 In addition to meeting the organic fertilizer standards of the Ministry of Agriculture, the above-mentioned fertilizers are rich in fulvic acid content of 5%. The source of fulvic acid is mainly derived from black liquor except for a part of the humic acid added. The fulvic acid contains a plurality of active groups and physiologically active substances for plants, and is a high molecular weight organic compound having a small molecular weight, has many acidic groups, is highly permeable, is soluble in acids, alkalis and water, and is easily absorbed by plants. As a non-polluting organic substance, it is widely used in agricultural production. In practical application, it is used to improve the drought resistance and cold resistance of crops, enhance the disease resistance of crops, stimulate the growth of crops, and thus increase crop yield. Improve the quality of crops.

此外，上述肥料中有机质主要为细化木质素，降解容易，作物易于吸收，而且与动物粪便、城市垃圾等现阶段主要有机肥来源相比， Na离子含量低，一般不大于 3 %，适用于缺乏有机质和 N、 P、 K等肥力低、通气好的砂土和碱性土壤上施用，不会引起土壤盐碱化；并且无后两者中不可避免含有的砷、镉、铅、铬、汞等重金属，防止了二次污染。 In addition, the organic matter in the above fertilizer is mainly refined lignin, which is easy to degrade, and the crop is easy to absorb, and the Na ion content is low, generally not more than 3%, compared with the main organic fertilizer sources such as animal manure and urban garbage. Lack of organic matter and N, P, K and other low fertility, well ventilated sand and alkaline soil application, will not cause soil salinization; and there is no arsenic, cadmium, lead, chromium, which are inevitably contained in the latter two. Heavy metals such as mercury prevent secondary pollution.

肥料黄腐酸含量高，肥效持久，利用率高，适应范围广，不易流失，无任何污染，环保、高效，颗粒均一，光泽度强；该肥料施入土壤后，能平衡作物对氮、磷、钾的吸收，改良土壤，改善作物品质，提高作物抗逆性，促进作物早熟，提高作物的产量；是适用于大田作物、经济作物的高效有机肥料。 The fertilizer has high content of fulvic acid, long-lasting fertilizer efficiency, high utilization rate, wide adaptability, no loss, no pollution, environmental protection, high efficiency, uniform particle and strong gloss. After the fertilizer is applied to the soil, it can balance crops with nitrogen and phosphorus. , absorption of potassium, improvement of soil, change Good crop quality, improve crop stress resistance, promote crop early maturity, and increase crop yield; It is a high-efficiency organic fertilizer suitable for field crops and cash crops.

( 3 ) 可作为冲施肥的肥料 (3) Can be used as fertilizer for fertilizer application

在稀黑液中或浓黑液中加入可溶性大量元素肥料得到可作为冲施肥的肥料； Adding soluble large amount of element fertilizer to the black liquor or concentrated black liquor to obtain a fertilizer that can be used as a fertilizer;

各组分的重量百分比为： The weight percentage of each component is:

稀黑液或浓黑液 20— 98 % ; 可溶性大量元素肥料 2— 80 % ; Diluted black liquor or concentrated black liquor 20-98 % ; soluble large amount of element fertilizer 2 - 80 % ;

稀黑液或浓黑液 50— 90 % ; 可溶性大量元素肥料 10— 50 %。 Dilute black liquor or concentrated black liquor 50-90%; soluble large amount of elemental fertilizer 10-50%.

之所以需要在稀黑液或浓黑液中加入可溶性大量元素肥料，是因为稀黑液或浓黑液中养分很不均衡，因此，需要加入来达到平衡施肥的目的。可溶性大量元素肥料为可溶性氮肥、可溶性磷肥和可溶性钾肥的一种或一种以上，这是因为： The reason why it is necessary to add soluble large amount of elemental fertilizer to the dilute black liquor or concentrated black liquor is because the nutrients in the dilute black liquor or the concentrated black liquor are very uneven, so it is necessary to join to achieve the purpose of balanced fertilization. The soluble large amount of elemental fertilizer is one or more of soluble nitrogen fertilizer, soluble phosphate fertilizer and soluble potassium fertilizer because:

稀黑液或浓黑液中， C/N 比较大，如果直接施入土壤，微生物分解作用很慢，而且要消耗土壤中的有效态氮，因此可以加入可溶性氮肥以调整 C/N比，所加的可溶性氮肥在黄腐酸冲施肥的重量百分比含量为 2— 60 %，优选为 2— 30 %。可溶性氮肥为尿素或可溶性铵盐的一种或一种以上，可溶性铵盐为硫酸铵、碳酸氢铵、氯化铵、磷酸二氢铵或磷酸氢二铵的一种或一种以上的组合，但由于尿素中 N的含量最高，而且不含硫酸根离子和氯离子等可能引起土壤不良反应的离子，因此优选尿素。 In dilute black liquor or concentrated black liquor, C/N is relatively large. If it is directly applied to the soil, the microbial decomposition is slow, and the effective nitrogen in the soil is consumed. Therefore, soluble nitrogen fertilizer can be added to adjust the C/N ratio. The added soluble nitrogen fertilizer is in the range of 2 to 60% by weight, preferably 2 to 30% by weight of the fulvic acid. The soluble nitrogen fertilizer is one or more of urea or a soluble ammonium salt, and the soluble ammonium salt is one or a combination of ammonium sulfate, ammonium hydrogencarbonate, ammonium chloride, ammonium dihydrogen phosphate or diammonium phosphate. However, since urea has the highest content of N and does not contain ions such as sulfate ions and chloride ions which may cause adverse reactions in the soil, urea is preferred.

磷肥，可以增加作物产量，改善产品品质，还能提高作物抗旱、抗寒和抗盐碱等抗逆性，因此，在黑液中可以加入可溶性磷肥，可溶性磷肥为磷酸二氢铵、磷酸氢二铵、磷酸二氢钾或磷酸氢二钾的一种或一种以上的组合，优选磷酸二氢铵，所加的可溶性磷肥在黄腐酸冲施肥的重量百分比含量为 2— 60 %，优选为 2— 30 %。 Phosphate fertilizer can increase crop yield, improve product quality, and improve crop drought resistance, cold resistance and salt and alkali resistance. Therefore, soluble phosphate fertilizer can be added to black liquor. Soluble phosphate fertilizer is ammonium dihydrogen phosphate and hydrogen phosphate. One or a combination of ammonium, potassium dihydrogen phosphate or dipotassium hydrogen phosphate, preferably ammonium dihydrogen phosphate, the added soluble phosphate fertilizer in the amount of fulvic acid fertilizer is 2 - 60% by weight, preferably 2-30%.

另外，由于目前土壤中普遍缺钾，因此，还可在黑液中加入可溶性钾肥，所加可溶性钾肥在黄腐酸冲施肥的重量百分比含量为 2— 50 %，优选为 2— 30 %。可溶性钾肥为硫酸钾、氯化钾、磷酸二氢钾或磷酸氢二钾的一种或一种以上的组合，优选氯化钾或硫酸钾。钾能够促进光合作用、明显地提高植物对氮的吸收和利用，并很快转化为蛋白质。钾还能促进植物经济用水，有助于作物的抗逆性。 In addition, due to the current lack of potassium in the soil, soluble potassium fertilizer can also be added to the black liquor. The weight percentage of the added soluble potassium fertilizer in the fulvic acid fertilizer is 2-50%, preferably 2-30%. The soluble potassium fertilizer is one or a combination of potassium sulfate, potassium chloride, potassium dihydrogen phosphate or dipotassium hydrogen phosphate, preferably potassium chloride or potassium sulfate. Potassium promotes photosynthesis, significantly increases plant uptake and utilization of nitrogen, and is rapidly converted to protein. Potassium also promotes water use in plants and contributes to the resistance of crops.

实际上，由于目前土壤中普遍不缺乏磷，因此，优选在黑液中加入可溶性氮肥和可溶性钾肥。除了上述各添加组分外，还可以根据实际情况加入其它种类的无机盐和可溶性铁、铜、硼、锌或镁等微量元素肥料。 In fact, since phosphorus is generally not absent in the soil, it is preferred to add soluble nitrogen fertilizer and soluble potassium fertilizer to the black liquor. In addition to the above-mentioned additional components, other kinds of inorganic salts and soluble elemental fertilizers such as iron, copper, boron, zinc or magnesium may be added according to actual conditions.

根据上述配方和方法制得可作为冲施肥的肥料，黄腐酸重量百分比为 5— 40 %，还可包括重量百分比含量为 3— 25 %的氮，和 /或重量百分比以 P₂0₅计为 3— 25 %的磷和 /或重量百分比以 K₂0 计为 3-25 %的钾，肥效显著。 According to the above formula and method, the fertilizer can be used as a fertilizer, the percentage of fulvic acid is 5-40%, and may also include nitrogen in a weight percentage of 3-25%, and/or the weight percentage is P ₂ 0 ₅ 3-25% of phosphorus and / or percentages by weight calculated as K ₂ 0 3-25% potassium fertilizer efficiency significantly.

黄腐酸含有多种活性基团和对植物的生理活性物质，是分子量较小的高分子有机化合物，酸性基团多，渗透性强，能溶于酸、碱和水，易被植物吸收。它作为无公害的有机物质，广泛的在农业生产上应用，在实际应用效果上表现为提高农作物的抗旱、抗寒能力，增强作物的抗病能力，刺激作物的生长，从而提高作物的产量，改善作物的品质。 The fulvic acid contains a variety of active groups and physiologically active substances for plants, and is a high molecular weight organic compound having a small molecular weight, has many acidic groups, is highly permeable, is soluble in acids, alkalis and water, and is easily absorbed by plants. It acts as a pollution-free organic substance, widely Applied in agricultural production, the actual application effect is to improve the drought resistance and cold resistance of crops, enhance the disease resistance of crops, stimulate the growth of crops, thereby increasing crop yield and improving crop quality.

本发明可作为冲施肥的肥料，由于添加额外的氮、磷或钾等成分平衡肥料的元素组分，把平衡施肥的技术贯彻在肥料配方之中，施用后养分容易被吸收，不易被土壤固定，不板结土壤，无毒害残留；施用方便，省工省力；营养成分多而全面，肥效快，有利于作物增产。在作物生长旺盛季节，克服了普通肥料追肥肥料养分释放转化慢、肥效迟缓、影响作物产量和品质的缺点。 The invention can be used as fertilizer for flushing fertilizer, and the balance fertilization technology is implemented in the fertilizer formula by adding additional nitrogen, phosphorus or potassium to balance the elemental components of the fertilizer, and the nutrients are easily absorbed after application, and are not easily fixed by the soil. , does not bind soil, no toxic residue; easy to apply, saves labor and effort; nutrient composition is comprehensive and comprehensive, fertilizer effect is fast, which is conducive to crop yield increase. In the season of vigorous crop growth, it overcomes the shortcomings of slow release of common nutrient fertilizers, slow fertilizer efficiency, and affect crop yield and quality.

(4 ) 可作为叶面肥的肥料 (4) Fertilizer that can be used as foliar fertilizer

在稀黑液中或将稀黑液蒸发浓缩除去一部分水分得到的浓黑液中加入可溶性微量元素肥料即得可作为叶面肥的肥料，二者的体积重量比为 1000ml: 0.2— 45g。 Adding a soluble trace element fertilizer to the concentrated black liquor obtained by evaporating and concentrating a part of the black liquor in a dilute black liquor or the like can be used as a fertilizer for foliar fertilizer, and the volume-to-weight ratio of the two is 1000 ml: 0.2-45 g.

由于黑液中含有丰富的肥料，因此很适宜以之为基础制成液态肥。由于叶面肥直接吸收见效快、养分利用率高、能迅速改善作物养分供应状况，因此，本发明将其制成叶面肥。此外，基于目前商品性肥料中大量营养元素的浓度与纯度不断加大，微量元素的肥效也越来越明显，如增施微量元素肥料可明显增产、增收与改善产品品质，因此在稀黑液或浓黑液中加入微量元素可显著的增强肥效，提高作物的产量和品质。 Since black liquor is rich in fertilizer, it is suitable to make liquid fertilizer based on it. Since the direct absorption of the foliar fertilizer is effective, the nutrient utilization rate is high, and the crop nutrient supply condition can be rapidly improved, the present invention is made into a foliar fertilizer. In addition, based on the current concentration and purity of large amounts of nutrients in commercial fertilizers, the fertilizer efficiency of trace elements is becoming more and more obvious. For example, the application of trace element fertilizers can significantly increase production, increase income and improve product quality. Or the addition of trace elements in concentrated black liquor can significantly enhance fertilizer efficiency and increase crop yield and quality.

微量元素是指土壤和植物中含量很低的营养元素，目前研究和使用较多的有铁、铜、锌、锰、钼、硼等 6种。微量元素在作物体内含量虽少，但具有很强的专一性，是作物生长发育所不可缺少和不可相互替代的。因此，当作物缺乏任何一种微量元素时，生长发育就受到抑制，导致减产和品质下降，严重的甚至绝收。反之，如果这些元素过多，又会出现中毒现象，影响作物产量和质量，还会引起人、畜的某些地方病的发生。 Trace elements refer to nutrients with low content in soil and plants. At present, there are six kinds of iron, copper, zinc, manganese, molybdenum and boron which are mostly studied and used. Although trace elements are small in crops, they have strong specificity and are indispensable and irreplaceable for crop growth and development. Therefore, when the crop lacks any trace elements, growth and development are inhibited, resulting in reduced yield and quality, severe or even severe. On the other hand, if there are too many of these elements, poisoning will occur, affecting crop yield and quality, and causing some local diseases in humans and animals.

基于上述微量元素的作用，本发明可作为叶面肥的肥料根据所加入的微量元素和量的不同，可分为以下三个系列： Based on the action of the above-mentioned trace elements, the present invention can be used as a fertilizer for foliar fertilizers, and can be classified into the following three series depending on the amount of trace elements and amounts added:

( I ) 大田作物叶面肥其中所加的可溶性微量元素肥料为亚铁盐和锌盐，其加入量为每 1000ml碱法和亚铵法混合草浆黑液中加入 0.1-15g和 0.1— 20g; 适用于玉米、小麦、水稻、大豆等大田作物。 (I) The soluble trace element fertilizer added to the field crop foliar fertilizer is ferrous salt and zinc salt, and the addition amount is 0.1-15g and 0.1-20g per 1000ml of alkali and ammonium ammonium mixed straw black liquor. Suitable for field crops such as corn, wheat, rice, and soybeans.

(II )蔬菜叶面肥其中所加的可溶性微量元素肥料为硼肥和锌盐，其加入量为每 1000ml碱法和亚铵法混合草浆黑液中加入 0.1-15g和 0.1— 20g，适用于菠菜、芹菜、黄瓜、大蒜、辣椒等蔬菜。 (II) The soluble trace element fertilizer added to the vegetable foliar fertilizer is boron fertilizer and zinc salt, and the addition amount is 0.1-15 g and 0.1-20 g per 1000 ml of the mixed alkali liquor of the alkali method and the ammonium imide method. Vegetables such as spinach, celery, cucumber, garlic, and pepper.

( III ) 果树叶面肥其中所加的可溶性微量元素肥料为硼盐、锌和亚铁盐，其加入量为每 1000ml碱法和亚铵法混合草浆黑液中加入 0.1-15g、 0.1— 20g和 0.1— 15g，适用于苹果、桃、杏等果树。上述的亚铁盐包括硫酸亚铁；上述的锌盐包括硫酸锌和 /或氯化锌，优选硫酸锌；上述的硼肥为硼酸和 /或硼砂，优选硼砂。 (III) The soluble trace element fertilizer added to the fruit leaf noodle fertilizer is boron salt, zinc and ferrous salt, and the addition amount is 0.1-15g, 0.1- added per 1000ml alkali and ammonium solution mixed straw black liquor. 20g and 0.1-15g, suitable for apple, peach, apricot and other fruit trees. The above ferrous salt includes ferrous sulfate; the above zinc salt includes zinc sulfate and/or zinc chloride, preferably zinc sulfate; and the above boron fertilizer is boric acid and/or borax, preferably borax.

本发明系列叶面肥中黄腐酸含量很高，可到 5— 40 %，黄腐酸含有多种活性基团和对植物的生理活性物质，是分子量较小的高分子有机化合物，酸性基团多，渗透性强，能溶于酸、碱和水，易被植物吸收。它作为无公害的有机物质，广泛的在农业生产上应用，在实际应用效果上表现为提高农作物的抗旱、抗寒能力，增强作物的抗病能力，刺激作物的生长，从而提高作物的产量，改善作物的品质。 The foliar fertilizer of the invention has high content of fulvic acid, and can reach 5% to 40%. The fulvic acid contains a plurality of active groups and physiologically active substances for plants, and is a polymer organic compound having a small molecular weight, and an acidic group. It has many groups, strong permeability, soluble in acid, alkali and water, and is easily absorbed by plants. As a non-polluting organic substance, it is widely used in agricultural production, and it is expressed in practical application. Improve the drought and cold resistance of crops, enhance the disease resistance of crops, stimulate the growth of crops, thereby increasing crop yield and improving crop quality.

本发明制得的可作为叶面肥的肥料，添加额外微量元素组分，把平衡施肥的技术贯彻在肥料配方之中；而且施用后直接吸收见效快、养分利用率高、能迅速改善作物养分供应状况；施用方便，省工省力；营养成分多而全面，肥效快，有利于作物增产。在作物生长旺盛季节，避免了普通肥料追肥肥料养分释放转化慢、肥效迟缓、影响作物产量和品质的缺点。 The fertilizer prepared by the invention can be used as a fertilizer for foliar fertilizer, adding extra trace element components, and the technology of balanced fertilization is implemented in the fertilizer formula; and the direct absorption after application has quick effect, high nutrient utilization rate, and can quickly improve crop nutrient Supply status; Easy to apply, saves labor and effort; Nutrient ingredients are comprehensive and comprehensive, and fertilizer efficiency is fast, which is conducive to crop yield increase. In the season of vigorous crop growth, the shortcomings of slow release, slow fertilizer efficiency and affecting crop yield and quality are avoided in the general fertilizer topdressing fertilizer.

附图说明 DRAWINGS

图 1六效蒸发中液相流动方向；图 2; 六效蒸发中气相流动方向；图 3蒸发器的简要结构示意图具体实施方式 Fig.1 Flow direction of liquid phase in six-effect evaporation; Fig. 2; direction of gas phase flow in six-effect evaporation; Fig.3 Schematic diagram of evaporator structure

实施例 1 Example 1

( 1 ) 亚铵法蒸煮 (1) Ammonium cooking

在稻草秸秆中加入蒸煮药剂，其中亚硫酸铵的用量为绝干原料量 9%，液比为 1 : 2，通入蒸汽进行加热，加热升温至温度为 100°C时保温 20分钟，进行小放汽，继续加热升温至 165°C，保温 60分钟，得到浓度为 8 %的浆，浆的硬度为高锰酸钾值 16。 The retort is added to the straw straw, wherein the amount of ammonium sulfite is 9% of the absolute dry material, the liquid ratio is 1:2, heated by steam, heated to a temperature of 100 ° C for 20 minutes, small The steam was released, heating was continued to 165 ° C, and the temperature was maintained for 60 minutes to obtain a slurry having a concentration of 8 %. The hardness of the slurry was 16 potassium permanganate.

(2 ) 高硬度浆后处理得到稀黑液 (2) High-hardness pulp post-treatment to obtain a dilute black liquor

浆从挤浆机的入口进入，挤出黑液，挤出黑液，得到固含量为 15 %，波美度为 9的稀黑液， pH为 10。 The slurry enters from the inlet of the extruder, extrudes the black liquor, and extrudes the black liquor to obtain a diluted black liquor having a solid content of 15% and a Baume degree of 9, and a pH of 10.

(3)黑液中加入辅料和干燥 (3) Adding excipients and drying in black liquor

将稀黑液、木质素、腐殖酸按照质量百分比 30 %、 45 %、 25 %的比例混合成料浆，直接蒸发干燥，即得肥料。所得肥料中黄腐酸重量百分比含量为 20%，有机质含量为 85 %。 The diluted black liquor, lignin and humic acid are mixed into a slurry according to a mass percentage of 30%, 455%, 255%, and directly evaporated to obtain a fertilizer. The obtained fertilizer has a fulvic acid content of 20% by weight and an organic matter content of 85 %.

实施例 2 Example 2

( 1 ) 将麦草秸秆分别用亚铵法和蒽醌 -烧碱法蒸煮 (1) The wheat straw is separately cooked by the ammonium imide method and the strontium-soda method

浸渍液浸渍麦草秸秆，使液比达到 1 : 2，在常压下于 85°C于螺旋浸渍器中保温和混合 10分钟，浸渍液为绝干原料量为 4%的氢氧化钠溶液。 The impregnating liquid is impregnated with wheat straw to make the liquid ratio reach 1:2, and is kept and mixed in a spiral impregnator at 85 ° C for 10 minutes under normal pressure, and the impregnation liquid is a 4% sodium hydroxide solution with a dry raw material amount.

在一部分麦草秸秆中加入蒸煮药剂，其中亚硫酸铵的用量为绝干原料量 13%，液比为 1 : 4；通入蒸汽进行加热，加热升温至温度为 120°C时保温 40分钟，进行小放汽，继续加热升温至 173 。C，保温 90分钟；得到浓度为 15 %的浆，浆的硬度为高锰酸钾值 28。 Adding a cooking agent to a part of wheat straw, wherein the amount of ammonium sulfite is 13% of the dry raw material, and the liquid ratio is 1:4; heating is carried out by steam, and the temperature is raised to 120 ° C for 40 minutes. Small steam, continue to heat up to 173. C, keep warm for 90 minutes; obtain a pulp with a concentration of 15%, the hardness of the pulp is potassium permanganate value 28.

在另一部分麦草秸秆中加入蒸煮药剂，其中用碱量为以氢氧化钠计对绝干原料量 9%，液比为 1 : 2，蒽醌加入量为绝干原料量的 0.5%; 通入蒸汽进行加热，加热升温至温度为 100°C时保温 20分钟，进行小放汽，继续加热升温至 165°C，保温 60分钟；得到浓度为 8 %的浆，浆的硬度为高锰酸钾值 16。 Adding a cooking agent to another portion of the straw straw, wherein the amount of the alkali is 9% by weight of the dry raw material, the liquid ratio is 1:2, and the amount of the cerium added is 0.5% of the amount of the dry raw material; The steam is heated, heated to a temperature of 100 ° C for 20 minutes, a small steam is released, heating is continued to 165 ° C, and the temperature is maintained for 60 minutes; a pulp having a concentration of 8% is obtained, and the hardness of the pulp is potassium permanganate. The value is 16.

将以上步骤所得的浆用挤浆机分别进行挤浆，得到固含量为 4 %，波美度为 2的稀黑液，其中亚铵法稀黑液 pH为 7，蒽醌-烧碱法稀黑液 pH为 9。 (3)黑液中加入辅料和干燥 The slurry obtained in the above step is separately squeezed by a squeezer to obtain a diluted black liquor having a solid content of 4% and a Baume degree of 2, wherein the pH of the imbibetic black liquor is 7, and the bismuth-salt method is black. The pH of the liquid is 9. (3) Adding excipients and drying in black liquor

将亚铵法稀黑液和蒽醌 -烧碱法稀黑液按照体积比 1: 100的比例混合，得到混合草浆稀黑液，将混合稀草浆黑液直接蒸发浓缩至固含量为 30%，波美度为 18，得到混合浓黑液，其 pH=ll，将混合浓黑液、木质素和腐殖酸按照质量百分比 30%、 45%、 25%的比例混合成料浆，然后直接干燥得到肥料，有机质含量 70%， N+P₂0₅+K₂0总含量 4%，黄腐酸 5%。 Mixing the ammonium imide black liquor and the bismuth-caustic black liquor in a ratio of 1:100 by volume to obtain a mixed straw black liquor, and directly concentrating the mixed straw black liquor to a solid content of 30%. , Baume degree is 18, the mixed concentrated black liquor is obtained, its pH=11, the mixed concentrated black liquor, lignin and humic acid are mixed into a slurry according to the mass percentage of 30%, 45%, 25%, and then directly The fertilizer is obtained by drying, the organic matter content is 70%, the total content of N+P ₂ 0 ₅ +K ₂ 0 is 4%, and the fulvic acid is 5%.

实施例 3 Example 3

浸渍液浸渍麦草秸秆，使液比达到 1: 4，在常压下于 95°C于螺旋浸渍器中保温和混合 40分钟，浸渍液为绝干原料量为 4%的氢氧化钠溶液与波美度 11的黑液的混合液。 The impregnation liquid is impregnated with wheat straw to make the liquid ratio reach 1:4, and is kept and mixed in a spiral impregnator at 95 ° C for 40 minutes under normal pressure, and the impregnation liquid is a 4% sodium hydroxide solution and wave with a dry raw material amount of 4%. A mixture of meto 11 black liquor.

在一部分麦草秸秆中加入蒸煮药液，其中亚硫酸铵的用量为绝干原料量 10%，液比为 1: 3；通入蒸汽进行加热，加热升温至温度为 110°C时保温 30分钟，进行小放汽，继续加热升温至 170 。C，保温 80分钟；得到浓度为 9%的浆，浆的硬度为高锰酸钾值 18。 Adding a cooking liquid to a part of wheat straw, wherein the amount of ammonium sulfite is 10% of the absolute dry material, and the liquid ratio is 1:3; heating is carried out by steam, and the temperature is raised to 110 ° C for 30 minutes. Perform a small steam release and continue heating to 170 °C. C, heat preservation for 80 minutes; a slurry with a concentration of 9% is obtained, and the hardness of the slurry is potassium permanganate value 18.

在另一部分麦草秸秆中加入蒸煮药剂，其中用碱量为以氢氧化钠计对绝干原料量 12%，液比为 1: 4，蒽醌加入量为绝干原料量的 0.8%; 通入蒸汽进行加热，加热升温至温度为 120 °C时保温 40分钟，进行小放汽，继续加热升温至 173 °C，保温 90分钟；得到浓度为 15%的浆，浆的硬度为高锰酸钾值 28。 Adding a cooking agent to another part of the straw straw, wherein the amount of the alkali is 12% of the dry raw material, the liquid ratio is 1:4, and the amount of the cerium is 0.8% of the dry raw material; The steam is heated, heated to a temperature of 120 ° C for 40 minutes, a small steam is released, heating is continued to 173 ° C, and the temperature is maintained for 90 minutes; a pulp having a concentration of 15% is obtained, and the hardness of the pulp is potassium permanganate. The value is 28.

(2) 高硬度浆后处理得到稀黑液 (2) High hardness pulp post-treatment to obtain a dilute black liquor

将以上步骤所得的浆用挤浆机分别进行挤浆，得到固含量为 8%, 波美度为 5的稀黑液，其中亚铵法稀黑液 pH为 8，蒽醌-烧碱法稀黑液 pH为 13。 The slurry obtained in the above step is separately squeezed by a squeezer to obtain a diluted black liquor having a solid content of 8% and a Baume degree of 5, wherein the pH of the imbibetic black liquor is 8, and the bismuth-salt method is black. The pH of the solution was 13.

将亚铵法稀黑液和蒽醌一烧碱法稀草浆黑液按照体积比 100: 1的比例混合，得到混合草浆稀黑液，将混合草浆黑液直接蒸发浓缩至固含量为 65%，波美度为 40，得到混合浓黑液， pH=5，将混合浓黑液、木质素和腐殖酸按照质量百分比 80%、 5%, 15%的比例混合成料浆，加入 KC1，然后喷雾干燥，得到固态肥料，有机质含量 67%， N+P₂0₅+K₂0总含量 4%，黄腐酸 40%。实施例 4 The ammonium imide black liquor and the samarium caustic soda pulp black liquor are mixed according to a volume ratio of 100:1 to obtain a mixed straw pulp black liquor, and the mixed straw pulp black liquor is directly evaporated to a solid content of 65. %, Baume degree is 40, the mixed concentrated black liquor is obtained, pH=5, and the mixed concentrated black liquor, lignin and humic acid are mixed into a slurry according to the mass percentage of 80%, 5%, 15%, and added to KC1. Then spray-drying to obtain a solid fertilizer with an organic matter content of 67%, a total content of 4% of N+P ₂ 0 ₅ +K ₂ 0, and 40% of fulvic acid. Example 4

(1) 亚铵法蒸煮 (1) Ammonium cooking

浸渍液浸渍麦草秸秆，使液比达到 1: 3，在常压下于 90°C于螺旋浸渍器中保温和混合 30分钟，浸渍液为绝干原料量为 4%的氢氧化钠溶液与波美度 14的黑液的混合液。 The impregnating liquid is impregnated with wheat straw to make the liquid ratio reach 1:3, and is kept and mixed in a spiral impregnator at 90 ° C for 30 minutes under normal pressure, and the impregnation liquid is a 4% sodium hydroxide solution and wave with a dry raw material amount of 4%. A mixture of meto 14 black liquor.

麦草秸秆中加入蒸煮药液，其中亚硫酸铵的用量为绝干原料量 9.5%，液比为 1: 3；通入蒸汽进行加热，加热升温至温度为 110°C时保温 30分钟，进行小放汽，继续加热升温至 165°C，保温 80分钟；得到浓度为 9%的浆，浆的硬度为高锰酸钾值 20。 The retort liquid is added to the wheat straw, wherein the amount of ammonium sulfite is 9.5% of the dry raw material, and the liquid ratio is 1:3; the steam is heated, and the temperature is raised to 110 ° C for 30 minutes, and the temperature is small. The steam was released, and the heating was continued until the temperature was raised to 165 ° C for 80 minutes; the slurry having a concentration of 9% was obtained, and the hardness of the slurry was 20 potassium permanganate.

浆从挤浆机的入口进入，挤出黑液之后，进行洗浆，合并挤出的黑液和洗浆的黑液，得到固含量为 8%，波美度为 5的稀黑液， pH为 9。 (3)黑液中加入辅料和干燥 The slurry enters from the inlet of the extruder, and after the black liquor is squeezed, it is washed, and the black liquor and the black liquor of the washing are combined to obtain a diluted black liquor having a solid content of 8% and a Baume degree of 5, pH. Is 9. (3) Adding excipients and drying in black liquor

稀黑液首先蒸发浓缩至固含量 15.1 %，波美度 9，得到浓黑液，将浓黑液直接蒸发干燥，即得肥料。所得肥料中黄腐酸重量百分比含量为 5 %，有机质含量为 15 %。 The diluted black liquor is first evaporated to a solid content of 15.1%, Baume degree 9, and a concentrated black liquor is obtained, and the concentrated black liquor is directly evaporated and dried to obtain a fertilizer. The obtained fertilizer had a fulvic acid content of 5% by weight and an organic matter content of 15%.

实施例 5 Example 5

( 1 ) 将芦竹秸秆分别用亚铵法和硫酸盐法蒸煮 (1) The arundo stalks are cooked by the ammonium sulfite method and the sulphate method respectively.

在一部分芦竹秸秆中加入蒸煮药剂，其中亚硫酸铵的用量为绝干原料量 10%，液比为 1 : 3.5；通入蒸汽进行加热，加热升温至温度为 115°C时保温 35分钟，进行小放汽，继续加热升温至 172 。C，保温 70分钟；得到浓度为 14 %的浆，浆的硬度为高锰酸钾值 27; The retort is added to a part of the bamboo straw, wherein the amount of ammonium sulfite is 10% of the absolute dry material, and the liquid ratio is 1:3.5; the steam is heated, and the temperature is raised to 115 ° C for 35 minutes. Perform a small steam release and continue heating to 172. C, holding for 70 minutes; obtaining a slurry with a concentration of 14%, the hardness of the pulp is potassium permanganate value 27;

在另一部分芦竹秸秆中加入蒸煮药剂，其中用碱量为以氢氧化钠计对绝干原料量 11%，液比为 1 : 4，硫化度为 15%; 通入蒸汽进行加热，加热升温至温度为 140°C时保温 40分钟，进行小放汽，继续加热升温至 173 °C，保温 90分钟；得到浓度为 15 %的浆，浆的硬度为高锰酸钾值 25 ; Adding a cooking agent to another part of the bamboo straw, wherein the alkali amount is 11% of the absolute dry material, the liquid ratio is 1:4, and the degree of sulfurization is 15%; heating is carried out by steam, heating is heated When the temperature is 140 ° C for 40 minutes, carry out small steam release, continue heating to 173 ° C, heat preservation for 90 minutes; obtain a concentration of 15% pulp, the hardness of the pulp is 25 potassium permanganate;

将以上步骤所得的浆用挤浆机分别进行挤浆，得到固含量为 10%，波美度为 6的稀黑液，其中亚铵法稀黑液 pH为 9，硫酸盐法稀黑液 pH为 10。 The slurry obtained in the above step is separately squeezed by a squeezer to obtain a dilute black liquor having a solid content of 10% and a Baume degree of 6, wherein the pH of the blackish solution of the ammonium imide method is 9, the pH of the black liquor of the sulfate method Is 10.

将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 1 : 4的比例混合，得到混合草浆稀黑液，将混合草浆黑液采用六效蒸发，六效蒸发各效压力为： I效 20 kPa， II效一 19kPa、 III效一 30 kPa 、 IV效—50kPa、 V效— 60kPa、 VI效 -75 kPa; 各效黑液温度为： I效 100 °C、 II效 90 °C 、 III效 80 °C 、 IV效 70°C、 V效 60°C、 VI效 50°C ; 各效黑液波美度分别为： VI效 5、 V效 7、 IV效 9、 III效 11 ; 经过 II效和 I效时， II效 14、 I效 18。得到的混合浓黑液其固含量为 40 %，波美度为 20， pH=6，将混合浓黑液、木质素、腐殖酸、污泥按照质量百分比 40 %、 14 %、 1 %、 45 %的比例混合成料浆，加入 KC1和氯化铵，然后喷浆造粒，喷浆造粒时机头温度 550°C，机尾温度 47 °C，得到固态肥料，粒度 3— 5mm，硬度 23.4N, 有机质含量 20%， N+P₂0₅+K₂0总含量 30 %，黄腐酸 9%。 The ammonium imide black liquor and the sulfate black liquor are mixed according to a volume ratio of 1:4 to obtain a mixed straw black liquor, and the mixed straw black liquor is subjected to six-effect evaporation, and the six-effect evaporation effect pressure is : I effect 20 kPa, II effect one 19kPa, III effect one 30 kPa, IV effect - 50kPa, V effect - 60kPa, VI effect -75 kPa; each effect black liquor temperature is: I effect 100 °C, II effect 90 ° C, III effect 80 °C, IV effect 70 °C, V effect 60 °C, VI effect 50 °C; each effect black liquor wave beauty is: VI effect 5, V effect 7, IV effect 9, III effect 11; II effect 14, I effect 18 after II effect and I effect. The obtained mixed concentrated black liquor has a solid content of 40%, a Baume degree of 20, and a pH=6, and the mixed concentrated black liquor, lignin, humic acid, and sludge are 40% by mass, 14%, 1% by mass, 45 % of the mixture is mixed into a slurry, KC1 and ammonium chloride are added, and then sprayed and granulated. When the spray granulation is carried out, the head temperature is 550 ° C, the tail temperature is 47 ° C, and the solid fertilizer is obtained, the particle size is 3-5 mm, and the hardness is 23.4N, organic matter content 20%, N+P ₂ 0 ₅ +K ₂ 0 total content 30%, fulvic acid 9%.

实施例 6 Example 6

亚铵法蒸煮同实施例 3，在另一部分麦草秸秆中加入蒸煮药液，其中用碱量为以氢氧化钠计对绝干原料量 11%，液比为 1 : 3，蒽醌加入量为绝干原料量的 0.7%; 通入蒸汽进行加热，加热升温至温度为 110°C时保温 30分钟，进行小放汽，继续加热升温至 169°C，保温 75分钟；得到浓度为 14 %的浆，浆的硬度为高锰酸钾值 27。 The ammonium imide method is the same as in the third embodiment. In another part of the wheat straw, a cooking liquid is added, wherein the alkali amount is 11% of the absolute dry material, and the liquid ratio is 1:3. 0.7% of the dry raw material; heated by steam, heated to a temperature of 110 ° C for 30 minutes, a small steam, continue heating to 169 ° C, held for 75 minutes; obtained a concentration of 14% The hardness of the pulp and pulp is 27 potassium permanganate.

将以上步骤所得的浆用挤浆机分别进行挤浆，得到固含量为 12 %，波美度为 7的稀黑液，其中亚铵法稀黑液 pH为 8，蒽醌一烧碱法稀黑液 pH为 12。 The slurry obtained in the above step is separately squeezed by a squeezer to obtain a dilute black liquor having a solid content of 12% and a Baume degree of 7, wherein the pH of the imbibetic black liquor is 8, and the caustic soda method is black. The pH of the liquid is 12.

(3)黑液中加入辅料和干燥将亚铵法稀黑液和蒽醌一烧碱法稀黑液按照体积比 4: 1的比例混合，得到混合草浆稀黑液，将混合草浆稀黑液采用六效蒸发，六效蒸发各效压力为：1效 38 kPa， II效 -5kPa、 III效一 40 kPa 、 IV效— 60kPa、 V效— 70kPa、 VI效—85kPa; 各效黑液温度为： I效 110°C、 II效 100°C 、 III 效 90°C、 IV效 80°C、 V效 65°C；各效黑液波美度分别为： VI效 8、 V效 10、 IV效 12、 III效 14; II效 15、 I效 18。得到的混合浓黑液其固含量为 47 %，波美度为 29， pH=6，将混合浓黑液、木质素、腐殖酸、污泥按照质量百分比 60 %、 25 %、 10 %、 5 %的比例混合成料浆，然后喷浆造粒，喷浆造粒时机头温度 600 °C，机尾温度 55°C，得到固态肥料，粒度 3— 5mm，硬度 9.2N, 有机质含量 60%， N+P₂0₅+K₂0总含量 4 %，黄腐酸 30%。 (3) Adding excipients and drying in black liquor Mixing the ammonium imide black liquor and the sulphuric acid caustic black liquor in a ratio of 4:1 by volume to obtain a mixed straw black liquor, and the mixed straw black liquor is subjected to six-effect evaporation and six-effect evaporation. The effective pressure is: 1 effect 38 kPa, II effect - 5 kPa, III effect - 40 kPa, IV effect - 60 kPa, V effect - 70 kPa, VI effect - 85 kPa; each effect black liquor temperature is: I effect 110 ° C, II effect 100 ° C, III effect 90 ° C, IV effect 80 ° C, V effect 65 ° C; each effect black liquor wave beauty is: VI effect 8, V effect 10, IV effect 12, III effect 14; II effect 15, I effect 18. The obtained mixed concentrated black liquor has a solid content of 47%, a Baume degree of 29, and a pH=6, and the mixed concentrated black liquor, lignin, humic acid, and sludge are 60%, 255%, 10% by mass, 5 % of the mixture is mixed into a slurry, and then sprayed and granulated. When the spray granulation is carried out, the head temperature is 600 ° C, the tail temperature is 55 ° C, and the solid fertilizer is obtained. The particle size is 3-5 mm, the hardness is 9.2 N, and the organic matter content is 60%. , N+P ₂ 0 ₅ +K ₂ 0 total content 4%, fulvic acid 30%.

实施例 7 Example 7

( 1 ) 将麦草秸秆分别用亚铵法和硫酸盐法蒸煮 (1) The wheat straw is cooked by the ammonium and sulfate methods, respectively.

亚铵法蒸煮同实施例 5，在另一部分麦草秸秆中加入蒸煮药液，其中用碱量为以氢氧化钠计对绝干原料量 10%，液比为 1 : 3，硫化度为 10%; 通入蒸汽进行加热，加热升温至温度为 130°C 时保温 30分钟，进行小放汽，继续加热升温至 170°C，保温 80分钟；得到浓度为 13 %的浆，浆的硬度为高锰酸钾值 22。 The ammonium imide method is the same as in the example 5, and the cooking liquid is added to another part of the straw straw, wherein the alkali amount is 10% of the absolute dry material, the liquid ratio is 1:3, and the degree of sulfurization is 10%. Steam is heated, heated to a temperature of 130 ° C for 30 minutes, a small steam is released, heating is continued to 170 ° C, and the temperature is maintained for 80 minutes; a slurry having a concentration of 13 % is obtained, and the hardness of the slurry is high. Potassium manganate value 22.

将以上步骤所得的浆用挤浆机分别进行挤浆，得到固含量为 8 % , 波美度为 5的稀黑液，其中亚铵法稀黑液 pH为 9，硫酸盐法稀黑液 pH为 12。 The slurry obtained in the above step is separately squeezed by a squeezer to obtain a diluted black liquor having a solid content of 8 % and a Baume degree of 5, wherein the pH of the imbibetic black liquor is 9, the pH of the sulfuric acid black liquor Is 12.

将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 3 : 1的比例混合，得到混合草浆稀黑液；将混合草浆稀黑液采用六效蒸发，六效蒸发各效压力为： I效 30kPa， II效 10kPa、 III效一 25kPa 、 IV效— 55kPa、 V效— 65kPa、 VI效— 80kPa; 各效黑液温度为： I效 105°C、 II效 95°C 、 III效 85 °C 、 IV效 75°C、 V效 65°C、 VI效 55°C ; 各效黑液波美度分别为: I效 20、 II效 16、 III效 13、 IV效 10、 V效 8、 VI效 6。得到的混合浓黑液其固含量为 45 %，波美度为 28， pH=7，将混合浓黑液、木质素、腐殖酸、污泥按照质量百分比 50 %、 35 %、 10 %、 5 %的比例混合成料浆，加入 KC1, 然后喷浆造粒，喷浆造粒时机头温度 560 °C，机尾温度 52°C，得到固态肥料，粒度 3— 5mm, 硬度 19.4N, 有机质含量 65%， N+P₂0₅+K₂0总含量 5 %，黄腐酸 24%。 The ammonium imide black liquor and the sulfate black liquor are mixed according to a volume ratio of 3:1 to obtain a mixed straw black liquor; the mixed straw black liquor is subjected to six-effect evaporation, and the six-effect evaporation pressure is used. It is: I effect 30kPa, II effect 10kPa, III effect one 25kPa, IV effect - 55kPa, V effect - 65kPa, VI effect - 80kPa; each effect black liquor temperature is: I effect 105 ° C, II effect 95 ° C, III Effectiveness 85 °C, IV effect 75 °C, V effect 65 °C, VI effect 55 °C; each effect black liquor wave beauty is: I effect 20, II effect 16, III effect 13, IV effect 10, V Effect 8, VI effect 6. The obtained mixed concentrated black liquor has a solid content of 45%, a Baume degree of 28, and a pH=7, and the mixed concentrated black liquor, lignin, humic acid, and sludge are 50% by mass, 355%, 10% by mass, 5 % of the mixture is mixed into a slurry, added to KC1, and then sprayed and granulated. When the spray granulation is carried out, the head temperature is 560 ° C, the tail temperature is 52 ° C, and the solid fertilizer is obtained. The particle size is 3-5 mm, the hardness is 19.4 N, and the organic matter is obtained. The content is 65%, the total content of N+P ₂ 0 ₅ +K ₂ 0 is 5%, and the fulvic acid is 24%.

实施例 8 Example 8

步骤（1 ) (2) 同实施例 6，所不同的是亚铵法稀黑液和蒽醌一烧碱稀黑液体积比 10: 1，得到固态肥料，粒度 3— 5mm，硬度 19.4N, 有机质含量 60%， N+P₂0₅+K₂0总含量 4 %，黄腐酸 35%。 Step (1) (2) Same as in Example 6, except that the volume ratio of the iminium black black liquor and the sulphuric acid caustic black liquor is 10:1, the solid fertilizer is obtained, the particle size is 3-5 mm, the hardness is 19.4 N, and the organic matter is obtained. The content is 60%, the total content of N+P ₂ 0 ₅ +K ₂ 0 is 4%, and the fulvic acid is 35%.

实施例 9 Example 9

步骤（1 ) (2 ) 同实施例 7，其它条件同实施例 5，所不同的是：亚铵法稀黑液和硫酸盐法稀黑液体积比 1 : 10，得到固态肥料，粒度 3— 5mm，硬度 14.5N, 有机质含量 60%， N+P₂0₅+K₂0 总含量 16 %，黄腐酸 22%。实施例 10、 Step (1) (2) Same as Example 7, the other conditions are the same as those in Example 5, except that: the volume ratio of the ammonium black and the sulfate black liquor is 1:10, and the solid fertilizer is obtained, and the particle size is 3 5mm, hardness 14.5N, organic matter content 60%, N+P ₂ 0 ₅ +K ₂ 0 total content 16%, fulvic acid 22%. Example 10

其它条件同实施例 7，其中，各组分重量百分比含量分别为混合浓黑液 55%、木质素 1%、腐殖酸 14%、磷石膏 30%; 所得的固态肥料中黄腐酸重量百分比含量为 16%，有机质含量为 40 %, N、 P₂0₅和 K₂0总含量 6%。 Other conditions are the same as those in Embodiment 7, wherein the weight percentage of each component is 55% of mixed concentrated black liquor, 1% of lignin, 14% of humic acid, 30% of phosphogypsum; and the weight percentage of fulvic acid in the obtained solid fertilizer The content is 16%, the organic matter content is 40%, and the total content of N, P ₂ 0 ₅ and K ₂ 0 is 6%.

实施例 11 Example 11

其它条件同实施例 6，其中，各组分重量百分比含量分别为：混合浓黑液 60%、木质素 1%、腐殖酸 14%、污泥 20%、磷石膏 5%; 所得的肥料中黄腐酸重量百分比含量为 25%，有机质含量为 80 %， Ν、 Ρ₂0₅和 Κ₂0总含量 5 %。 Other conditions are the same as those in Embodiment 6, wherein the weight percentage of each component is: mixed concentrated black liquor 60%, lignin 1%, humic acid 14%, sludge 20%, phosphogypsum 5%; fulvic acid content of 25% by weight, the organic matter content of _{80%, Ν, Ρ 2 0} 5 and Κ ₂ 0 total content of 5%.

实施例 12 Example 12

(1) 碱性亚纳法蒸煮在芦竹秸秆中加入蒸煮药液，其中氢氧化钠用量以绝干原料重量计为 11%，亚硫酸钠为 2%，蒽醌为 0.02%，蒸煮液比为 1:3; 通入蒸汽进行加热，加热升温至温度为 100°C时保温 20分钟，进行小放汽，继续加热升温至 160°C，保温 60分钟；得到浓度为 8%的浆，浆的硬度为高锰酸钾值 20; 其余条件同实施例 4，所得的肥料中黄腐酸重量百分比含量为 6 %, 有机质含量为 22%。 (1) Alkaline sub-nano cooking is carried out by adding cooking liquor to the straw of Luzhu, wherein the amount of sodium hydroxide is 11% by weight of the dry raw material, 2% of sodium sulfite, 0.02% of bismuth, and the ratio of cooking liquor is 1. :3; steamed for heating, heated to a temperature of 100 ° C for 20 minutes, a small steam, continue heating to 160 ° C, heat retention for 60 minutes; to obtain a concentration of 8% pulp, pulp hardness The potassium permanganate value was 20; the remaining conditions were the same as in Example 4, and the obtained fertilizer had a fulvic acid content of 6% by weight and an organic matter content of 22%.

实施例 13 Example 13

(1)碱性亚纳法蒸煮在棉秆秸秆中加入蒸煮药液，其中氢氧化钠用量以绝干原料重量计为 15%，亚硫酸钠为 6%，蒽醌为 0.08%，蒸煮液比为 1: 4; 通入蒸汽进行加热，加热升温至温度为 120°C时保温 40分钟，进行小放汽，继续加热升温至 165°C，保温 90分钟；得到浓度为 10%的浆，浆的硬度为高锰酸钾值 20; 其余条件同实施例 4，所得的肥料中黄腐酸重量百分比含量为 7%，有机质含量为 24%。 (1) Alkaline sub-nano cooking The retort liquid is added to the cotton stalk straw, wherein the amount of sodium hydroxide is 15% by weight of the dry raw material, 6% sodium sulfite, 0.08% bismuth, and the cooking liquor ratio is 1 : 4; steaming to heat, heating to a temperature of 120 ° C for 40 minutes, a small steam, continue heating to 165 ° C, heat preservation for 90 minutes; to obtain a concentration of 10% pulp, pulp hardness The potassium permanganate value was 20; the remaining conditions were the same as in Example 4, and the obtained fertilizer had a fulvic acid content of 7% by weight and an organic matter content of 24%.

实验例 1 Experimental example 1

2006年在花生、玉米各 100亩的实验对比中，使用本发明实施例 1制备的黄腐酸肥 X— 1，用量 50kg/亩，对照农家肥料 2000kg /亩施用量，结果为使用本发明黄腐酸肥的花生亩产比使用农家肥亩产增加 90千克，增产 10.2% ：玉米比使用农家肥亩产增加 132千克，增产 19.5%。 In the experimental comparison of 100 mu of peanuts and corn in 2006, the amount of xanthate fertilizer X-1 prepared in Example 1 of the present invention was 50 kg/mu, and the amount of application of farmer fertilizer 2000 kg/mu was used. The per mu yield of humic acid fertilizer increased by 90 kg compared with the use of farmyard manure, and the yield increased by 10.2%: corn increased by 132 kg compared with the use of farmyard manure, and the yield increased by 19.5%.

由此可见，根据本发明配方制备的肥料较之农家肥的肥分更为集中，在施用量远远小于农家肥的情况下，依旧有明显的增产效果，有利于节省田间劳动成本。 It can be seen that the fertilizer prepared according to the formula of the present invention is more concentrated than the fertilizer of the farmyard manure, and in the case that the application amount is far less than that of the farmyard manure, there is still a significant yield increase effect, which is conducive to saving field labor costs.

实验例 2 Experimental example 2

本实验例连续 4季对小麦进行长效实验，小麦品种：扬麦 7号，实验设 2个组，一组施用本发明实施例 2制备的肥料，对照组为市售艳阳天复合肥，用量均为 50kg/亩。实验结果如表 1: In this experimental example, the wheat was subjected to a long-term experiment for four consecutive seasons. The wheat variety: Yangmai No.7, the experiment was set up in two groups, one group was applied with the fertilizer prepared in Example 2 of the present invention, and the control group was a commercially available Yanyangtian compound fertilizer. Both are 50kg/mu. The experimental results are shown in Table 1:

表 1 小麦长效实验 Table 1 Wheat long-acting experiment

本发明产量（kg/亩) 对照组产量（kg/亩) 增产百分比第一季 427.38 414.82 0 第二季 424.56 409.05 3.8 第三季 440.32 413.08 6.6 第四季 409.13 392.52 4.2 The yield of the invention (kg/mu) The yield of the control group (kg/mu) The percentage increase of the first season 427.38 414.82 0 The second season 424.56 409.05 3.8 The third quarter 440.32 413.08 6.6 Fourth Quarter 409.13 392.52 4.2

可见本发明肥料肥效时间长、后劲足、增产作用明显。 It can be seen that the fertilizer fertilizer of the invention has a long effect on the effect of the fertilizer, and has a significant effect on increasing the yield.

实验例 3 Experimental example 3

2006年对本发明实施例 3制备的肥料在小麦上的应用效果进行了研究。 In 2006, the application effect of the fertilizer prepared in Example 3 of the present invention on wheat was studied.

小麦品种：扬麦 7号，土壤为砂壤土，肥力中等。试验设 3 个组，于小麦拔节期分别施用: ( 1 ) 本发明实施例 3制备的肥料，用量 50kg /亩；（2 ) 市售东方红复合肥 50kg /亩；（3 ) 空白对照 Wheat variety: Yangmai No. 7, the soil is sandy loam and the fertility is medium. The experiment was set up in three groups and applied in the jointing stage of wheat: (1) The fertilizer prepared in Example 3 of the present invention was used in an amount of 50 kg/mu; (2) 50 kg/mu of commercially available oriental red compound fertilizer; (3) blank control

试验结果如表 2所示： The test results are shown in Table 2:

表 2小麦经济性状及产量 Table 2 Economic characteristics and yield of wheat

株 1¾ 最高分有效分穗数穗粒数千粒理论产量增产率处理蘖数蘖数重 Plant 13⁄4 highest score effective number of spikes spike number of grains thousand particles theoretical yield increase yield treatment number of turns number of weight

cm 万 /亩万 /亩万 /亩粒 /穗 g kg/亩 % 本发明肥料 92.7 47.62 20.95 39.58 29.02 38.0 436.47 22.28 复合肥 91.0 40.01 17.14 37.08 28.55 37.7 399.1 11.30 Cm 10,000 / a million / a million / acre granule / ear g kg / acre % Fertilizer of the invention 92.7 47.62 20.95 39.58 29.02 38.0 436.47 22.28 Compound fertilizer 91.0 40.01 17.14 37.08 28.55 37.7 399.1 11.30

CK 91.7 43.81 13.33 34.86 26.18 37.2 339.22 CK 91.7 43.81 13.33 34.86 26.18 37.2 339.22

从表 2 可见， ( 1 ) 施本发明肥料的小麦最高分蘖数、有效分蘖数和成穗率分别比施复合肥提高了 3.5%、 22.2%和 6.75%,比未施肥对照提高了 8.7 %、 57.2%和 13.5%。 It can be seen from Table 2 that (1) the highest tiller number, effective tiller number and panicle rate of wheat with the fertilizer of the present invention were increased by 3.5%, 22.2% and 6.75%, respectively, compared with the compound fertilizer, which was 8.7% higher than that of the unfertilized control. 57.2% and 13.5%.

(2 )施本发明肥料以及市售东方红复合肥的小麦产量较未施肥都有所增加。经方差分析和多重比较表明:喷施本发明肥料或市售东方红复合肥对照增产均达极显著水平，增长率分别为 28.67%、 17.65 %。 (2) The yield of wheat with the fertilizer of the invention and the commercially available oriental red compound fertilizer increased compared with the unfertilized fertilizer. Analysis of variance and multiple comparisons showed that the application of the fertilizer of the invention or the commercial Dongfanghong compound fertilizer increased the yield to a very significant level, with growth rates of 28.67% and 17.65%, respectively.

实验例 4 Experimental example 4

实验土壤为赤红壤，有机质含量为 0.62 %， pH值 4.98，将其分为 5组，在土壤中分别加入实施例 3— 6的产品，用量 50kg /亩，剩下的一组作为空白对照 CK，然后分别测各组的土壤比表面积、土壤电荷量、土壤阳离子交换量、和土壤 pH。 The experimental soil was red soil, the organic matter content was 0.62%, the pH value was 4.98, and it was divided into 5 groups. The products of Example 3-6 were added to the soil, the dosage was 50 kg/mu, and the remaining group was used as the blank control CK. Then, the soil specific surface area, soil charge amount, soil cation exchange amount, and soil pH of each group were measured separately.

实验结果如表 3所示： The experimental results are shown in Table 3:

表 3 本发明黄腐酸肥料对土壤性质的影响 Table 3 Effect of fulvic acid fertilizer on soil properties of the present invention

土壤比表面积土壤电荷量土壤阳离子交换 Soil specific surface area soil charge amount soil cation exchange

(m²/g) cmol/kg 量 cmol/kg 土壤 pH (m ² /g) cmol/kg amount cmol/kg soil pH

CK 21.83 17.52 2.61 4.89 实施例 3 41.36 27.72 4.51 6.43 实施例 4 38.12 31.14 4.58 6.02 实施例 5 37.76 44.14 4.86 5.97 实施例 6 36.89 49.23 4.93 6.22 供试土样 pH为 4.89，属于强酸性土壤，不利于植物生长。在土壤中施加了本发明制备的土壤修复剂后，土壤的酸性减弱，土壤的 pH提高。 CK 21.83 17.52 2.61 4.89 Example 3 41.36 27.72 4.51 6.43 Example 4 38.12 31.14 4.58 6.02 Example 5 37.76 44.14 4.86 5.97 Example 6 36.89 49.23 4.93 6.22 The soil sample pH was 4.89, which belongs to strong acid soil and is not conducive to plant growth. After the soil restorative prepared by the present invention is applied to the soil, the acidity of the soil is weakened and the pH of the soil is increased.

可见根据本发明配方制备的肥料对酸性土壤具有良好的改良效果。 It can be seen that the fertilizer prepared according to the formula of the present invention has a good improvement effect on acidic soil.

实验例 5 Experimental example 5

实验用土地为重盐碱荒地，施加实施例 12的产品，用量 60kg/亩，实验前后土壤表层的各种离子含量如表 4 The experimental land was a heavy saline-alkali wasteland, and the product of Example 12 was applied at a dosage of 60 kg/mu. The various ion contents of the soil surface before and after the experiment are shown in Table 4.

表 4 土壤表层的离子含量（单位 g/kg) Table 4 Ion content of soil surface layer (unit g/kg)

co₃ ²- HC0₃" C1— SO4²" Ca²⁺ Mg²⁺ K+Na+ j[∑^ i- pH值处理前 0.101 0.475 15.517 235.613 6.236 0.082 115.877 373.91 10.16 处理后 0.051 0.402 22.960 41.282 2.870 0.016 31.518 99.104 9.22 可见，本发明制备的土壤修复剂在盐碱地上有明显的脱盐效果，脱盐率达 73.50%，同时还土壤中钠离子吸附比也明显减少，处理后土壤钠离子吸附比减少了 60.72%，钠离子吸附比是表明土壤碱化程度的指标之一。再加上土壤的 pH值显著降低，所以根据本发明配方制备的肥料对盐碱地也有明显的改良作用。 Co ₃ ² - HC0 ₃ " C1 - SO4 ² " Ca ²⁺ Mg ²⁺ K+Na+ j[∑^ i- Before pH treatment 0.101 0.475 15.517 235.613 6.236 0.082 115.877 373.91 10.16 After treatment 0.051 0.402 22.960 41.282 2.870 0.016 31.518 99.104 9.22 It can be seen that the soil remediation agent prepared by the invention has obvious desalting effect on the saline-alkali soil, the desalination rate reaches 73.50%, and the sodium ion adsorption ratio in the soil is also significantly reduced, and the soil sodium ion adsorption ratio is reduced by 60.72% after treatment, sodium The ion adsorption ratio is one of the indicators indicating the degree of alkalization of the soil. In addition, the pH of the soil is significantly reduced, so that the fertilizer prepared according to the formulation of the present invention also has a significant improvement effect on the saline-alkali soil.

实施例 14 Example 14

其中步骤（1) (2) 同实施例 1，所不同的是步骤 (3)，具体为： Step (1) (2) is the same as step 1, except that step (3) is specifically:

稀黑液中加入磷酸二氢铵，重量百分比含量分别为 98%和 2%，即得可作为冲施肥的肥料。所述的可作为冲施肥的肥料中氮的重量百分比含量为 3%，磷的重量百分比以 P₂0₅计为 3%，黄腐酸重量百分比 5%。 Ammonium dihydrogen phosphate is added to the dilute black liquor, and the weight percentages are 98% and 2%, respectively, which means that it can be used as a fertilizer for flushing fertilizer. The weight percentage of nitrogen in the fertilizer which can be used as a fertilizer is 3%, the weight percentage of phosphorus is 3% in terms of P ₂ 0 ₅ , and the weight percentage of fulvic acid is 5%.

实施例 15 Example 15

步骤（1) (2) 同实施例 2，所不同的是步骤（3)，具体为： Step (1) (2) Same as Embodiment 2, except that step (3) is specifically:

将亚铵法稀黑液和蒽醌 -烧碱法稀黑液按照体积比 1: 100的比例混合，得到混合草浆稀黑液，将混合稀草浆黑液直接蒸发浓缩至固含量为 30%，波美度为 18，得到混合浓黑液，其 pH=ll，将混合浓黑液中加入磷酸二氢铵，重量百分比含量分别为 98%和 2%，并调 pH为 10，即得可作为冲施肥的肥料。可作为冲施肥的肥料中氮的重量百分比含量为 3%，磷的重量百分比以 P₂0₅计为 3%，黄腐酸重量百分比 15%。 Mixing the ammonium imide black liquor and the bismuth-caustic black liquor in a ratio of 1:100 by volume to obtain a mixed straw black liquor, and directly concentrating the mixed straw black liquor to a solid content of 30%. , Baume degree is 18, the mixed concentrated black liquor is obtained, its pH=11, the mixed concentrated black liquor is added with ammonium dihydrogen phosphate, the weight percentage is 98% and 2%, respectively, and the pH is adjusted to 10, that is, As a fertilizer for fertilization. The weight percentage of nitrogen in the fertilizer which can be used as a fertilizer is 3%, the weight percentage of phosphorus is 3% in terms of P ₂ 0 ₅ , and the weight percentage of fulvic acid is 15%.

实施例 16 Example 16

步骤（1) (2) 同实施例 3，所不同的是步骤（3)，具体为： Step (1) (2) Same as Embodiment 3, except that step (3) is specifically:

将亚铵法稀黑液和蒽醌一烧碱法稀草浆黑液按照体积比 100: 1的比例混合，得到混合草浆稀黑液，将混合草浆黑液直接蒸发浓缩至固含量为 65%，波美度为 40，得到混合浓黑液， pH=5，将混合浓黑液中加入磷酸氢二铵和硫酸钾，各组分重量百分比含量依次为 20%、 60%和 20%，并调 pH为 6，即得可作为冲施肥的肥料。可作为冲施肥的肥料中氮的重量百分比含量为 25%，磷的重量百分比以 P₂0₅计为 25%，钾的重量百分比以 K₂0计为 3%，黄腐酸重量百分比 7%。实施例 17 The ammonium imide black liquor and the samarium caustic soda pulp black liquor are mixed according to a volume ratio of 100:1 to obtain a mixed straw pulp black liquor, and the mixed straw pulp black liquor is directly evaporated to a solid content of 65. %, Baume degree is 40, the mixed concentrated black liquor is obtained, pH=5, and the mixed concentrated black liquor is added with diammonium hydrogen phosphate and potassium sulfate, and the weight percentage of each component is 20%, 60% and 20%, respectively. and Adjusting the pH to 6, it can be used as a fertilizer for fertilizer application. The weight percentage of nitrogen in the fertiliser fertilizer is 25%, the weight percentage of phosphorus is 25% in terms of P ₂ 0 ₅ , the weight percentage of potassium is 3% in K ₂ 0 , and the weight percentage of fulvic acid is 7%. . Example 17

步骤（1) (2) 同实施例 4，所不同的是步骤（3)，具体为： Step (1) (2) Same as Embodiment 4, except that step (3) is specifically:

稀黑液首先蒸发浓缩至固含量 15.1%，波美度 9，得到浓黑液，然后加入尿素、硫酸铵、磷酸二氢铵和氯化钾，各组分重量百分比含量依次为 30%、 30%、 8%、 30%、 2%；调节 pH到 8，即得可作为冲施肥的肥料。可作为冲施肥的肥料中氮的重量百分比含量为 20%，磷的重量百分比以 Ρ₂0₅计为 10%，钾的重量百分比以 Κ₂0计为 3%，黄腐酸重量百分比 5%。 The diluted black liquor is first evaporated to a solid content of 15.1%, Baume degree 9, to obtain a concentrated black liquor, and then added urea, ammonium sulfate, ammonium dihydrogen phosphate and potassium chloride, the weight percentage of each component is 30%, 30 %, 8%, 30%, 2%; Adjusting the pH to 8, it can be used as a fertilizer for flushing fertilizer. As a percentage by weight content of fertilization of fertilizer nitrogen is 20% by weight of phosphorus percentages Ρ ₂ 0 ₅ is 10% by weight of potassium percentages Κ ₂ 0 in terms of 3%, fulvic acid weight percentage 5% .

实施例 18 Example 18

步骤（1) (2) 同实施例 5，所不同的是步骤 (3)，具体为： Step (1) (2) Same as Embodiment 5, except that step (3) is specifically:

将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 1: 4的比例混合，得到混合草浆稀黑液，将混合草浆黑液采用五效蒸发，得到的混合浓黑液其固含量为 40%，波美度为 20， ρΗ=6，在混合浓黑液中加入磷酸二氢铵、碳酸氢铵、氯化钾和硫酸钾，各组分重量百分比含量依次为 60%、 20 %、 10%、 2%和 8%，即得可作为冲施肥的肥料，无须额外调整 ρΗ。可作为冲施肥的肥料中氮的重量百分比含量为 14%，磷的重量百分比以 Ρ₂0₅计为 8%，钾的重量百分比以 Κ₂0计为 6%，黄腐酸重量百分比 15%。 The ammonium imide black liquor and the sulfate black liquor are mixed according to a volume ratio of 1:4 to obtain a mixed straw black liquor, and the mixed straw black liquor is subjected to five-effect evaporation to obtain a mixed concentrated black liquor. The solid content is 40%, the Baume degree is 20, ρΗ=6, and ammonium dihydrogen phosphate, ammonium hydrogencarbonate, potassium chloride and potassium sulfate are added to the mixed concentrated black liquor, and the weight percentage of each component is 60%, 20%, 10%, 2% and 8%, that is, can be used as fertilizer for fertilizer application, no need to adjust ρΗ. The weight percentage of nitrogen in the fertiliser fertilizer is 14%, the weight percentage of phosphorus is 8% in terms of Ρ ₂ _{5 5} , the weight percentage of potassium is 6% in terms of Κ ₂₀ , and the weight percentage of fulvic acid is 15%. .

实施例 19 Example 19

步骤（1) (2) 同实施例 6，所不同的是步骤 (3)，具体为： Step (1) (2) The difference from the embodiment 6 is the step (3), which is specifically:

将亚铵法稀黑液和蒽醌一烧碱法稀黑液按照体积比 4: 1的比例混合，得到混合草浆稀黑液，将混合草浆稀黑液采用五效蒸发，得到的混合浓黑液其固含量为 47%，波美度为 29， ρΗ=6，将混合浓黑液中加入尿素、磷酸二氢铵和氯化钾，各组分重量百分比含量依次为 80%、 Ί%、 8%、 5%, 即得可作为冲施肥的肥料。可作为冲施肥的肥料中氮的重量百分比含量为 10%，磷的重量百分比以 Ρ₂0₅计为 4%，钾的重量百分比以 Κ₂0计为 6%，黄腐酸重量百分比 40%。 Mixing the ammonium imide black liquor and the sulphuric acid caustic black liquor in a ratio of 4:1 by volume to obtain a mixed straw pulp black liquor, and mixing the straw pulp black liquor with a five-effect evaporation to obtain a mixed concentration The black liquor has a solid content of 47%, a Baume degree of 29, and ρΗ=6. The mixed concentrated black liquor is added with urea, ammonium dihydrogen phosphate and potassium chloride, and the weight percentage of each component is 80%, Ί%. 8%, 5%, that is, can be used as fertilizer for fertilizer application. The weight percentage of nitrogen in the fertiliser fertilizer is 10%, the weight percentage of phosphorus is 4% in terms of Ρ ₂ _{5 5} , the weight percentage of potassium is 6% in terms of Κ ₂₀ , and the weight percentage of fulvic acid is 40%. .

实施例 20 Example 20

步骤（1) (2) 同实施例 7，所不同的是步骤 (3)，具体为： Step (1) (2) The difference from the embodiment 7 is the step (3), which is specifically:

将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 3: 1的比例混合，得到混合草浆稀黑液；将混合草浆稀黑液采用五效蒸发，得到的混合浓黑液其固含量为 45%，波美度为 28， ρΗ=7，将混合浓黑液中加入尿素和氯化钾，各组分重量百分比含量依次为 70%、 10%和 20%，即得可作为冲施肥的肥料，无须调整 ρΗ。所述的可作为冲施肥的肥料中氮的重量百分比含量为 8%，钾的重量百分比以 Κ₂0计为 7%，黄腐酸重量百分比 32%。 Mixing the ammonium imide black liquor and the sulfate black liquor in a ratio of 3:1 by volume to obtain a mixed straw black liquor; and mixing the straw black liquor with a five-effect evaporation to obtain a mixed concentrated black liquor The solid content is 45%, the Baume degree is 28, ρΗ=7, and the mixed concentrated black liquor is added with urea and potassium chloride, and the weight percentage of each component is 70%, 10% and 20%, respectively. As a fertilizer for fertilizing, there is no need to adjust ρΗ. The weight percentage of nitrogen in the fertilizer which can be used as a fertilizer is 8%, the weight percentage of potassium is 7% in terms of Κ ₂₀ , and the weight percentage of fulvic acid is 32%.

实施例 21 Example 21

步骤（1) (2) 同实施例 19，所不同的是步骤 (3)，具体为： Step (1) (2) Same as Embodiment 19, except that step (3) is specifically:

其它条件同实施例 19，亚铵法稀黑液和蒽醌一烧碱稀黑液体积比 10: 1，混合草浓黑液固含量 50%，波美度为 31，其中加入磷酸二氢钾，重量百分比含量依次为 50%、 50%, 即得可作为冲施肥的肥料，不需要额外调整 pH。可作为冲施肥的肥料中钾的重量百分比以 K₂0计为 25%，磷的重量百分比以 Ρ₂0₅计为 25 %，黄腐酸重量百分比 30 %。 Other conditions are the same as those in the embodiment 19, the volume ratio of the ammonium imide black liquor and the niobium caustic black liquor is 10:1, the mixed grass black liquor has a solid content of 50%, and the Baume degree is 31, wherein potassium dihydrogen phosphate is added. The weight percentage content is 50%, 50%, which is Fertilizer fertilizer does not require additional pH adjustment. The weight percentage of potassium in the fertilizer which can be used as a fertilizer is 25% in terms of K ₂ 0, the weight percentage of phosphorus is 25% in terms of Ρ ₂ 0 ₅ , and the weight percentage of fulvic acid is 30%.

实施例 22 Example 22

步骤（1) (2) 同实施例 20，所不同的是步骤（3)，具体为： Step (1) (2) Same as Embodiment 20, except that step (3) is specifically:

其它条件同实施例 18，亚铵法稀黑液和硫酸盐法稀黑液体积比 1: 10，混合浓黑液固含量 30 Other conditions are the same as those in the embodiment 18, the volume ratio of the ammonium black solution and the sulfuric acid black liquor 1: 10, the mixed black liquor solid content 30

%, 波美度为 17，其中加入尿素、硫酸铵、磷酸二氢铵和氯化钾，各组分重量百分比含量分别为 30%、 30%、 8%、 30%和 2%，调 ρΗ为 8，即得可作为冲施肥的肥料。可作为冲施肥的肥料中氮的重量百分比含量为 20%，磷的重量百分比以 Ρ₂0₅计为 10%，钾的重量百分比以 Κ₂0计为 3 %, 黄腐酸重量百分比 8% %, Baume degree is 17, which is added with urea, ammonium sulfate, ammonium dihydrogen phosphate and potassium chloride, the weight percentage of each component is 30%, 30%, 8%, 30% and 2%, respectively. 8, that is, can be used as fertilizer for fertilizer application. The weight percentage of nitrogen in the fertiliser fertilizer is 20%, the weight percentage of phosphorus is 10% in terms of Ρ ₂ _{5 5} , the weight percentage of potassium is 3% in terms of Κ ₂₀ , and the weight percentage of fulvic acid is 8%.

实施例 23 Example 23

步骤（1) (2) 同实施例 12，其余条件同实施例 17，所得的可作为冲施肥的肥料中氮的重量百分比含量为 19%，磷的重量百分比以 Ρ₂0₅计为 11%，钾的重量百分比以 Κ₂0计为 4%，黄腐酸重量百分比 6%。 Step (1) (2) in Example 12, Example 17 remaining conditions being the same, the weight percentage content of the resulting may be nitrogen as fertilization of fertilizer was 19% by weight of phosphorus percentages Ρ ₂ 0 ₅ Total 11% The weight percentage of potassium is 4% in terms of Κ _{20 and} 6% by weight of fulvic acid.

实施例 24 Example 24

步骤（1) (2) 同实施例 13，其余条件同实施例 17，所得的可作为冲施肥的肥料中氮的重量百分比含量为 18%，磷的重量百分比以 Ρ₂0₅计为 10%，钾的重量百分比以 Κ₂0计为 4%，黄腐酸重量百分比 5.4%。 Step (1) (2) in Example 13, Example 17 remaining conditions being the same, resulting as a percentage by weight content of fertilization of fertilizer nitrogen is 18% by weight of phosphorus percentages Ρ ₂ 0 ₅ 10% or The weight percentage of potassium is 4% in terms of Κ _{20 and} the weight percentage of fulvic acid is 5.4%.

实验例 6 Experimental example 6

该实验例为本发明可作为冲施肥的肥料在青菜上的肥效试验。 This experimental example is a fertilizer effect test of the invention as a fertilizer for flushing fertilizer on green vegetables.

试验在农田中进行，供试品种为四倍体苏州青，农田划分为多个小区，每个小区为 20m2，空白组为不做任何处理，对照组为栽种后 10天施用 "心实"有机冲施肥 I号（总养分 4%，有机质 20%，江苏心实肥料有限公司） 600kg/hm2 冲施，其它为施用本发明实施例组，用量同对照组，采收期为第 70天。 The test was carried out in farmland. The tested variety was tetraploid Suzhou blue, and the farmland was divided into multiple plots, each plot was 20 m2. The blank group was not treated. The control group was applied for 10 days after planting. The application of the fertilizer No. I (total nutrient 4%, organic matter 20%, Jiangsu Xinshi Fertilizer Co., Ltd.) 600kg/hm2, the other application group of the present invention, the dosage is the same as the control group, and the harvesting period is the 70th day.

结果如表 5所示： The results are shown in Table 5:

表 5不同处理的青菜性状和产量 Table 5: Characteristics and yield of differently processed green vegetables

处理株高 cm 叶片数叶总重 g 叶片光泽度小区平均产量 kg 空白组 17.62 13.8 67.8 一般 42.58 Treatment plant height cm number of leaves total leaf weight g leaf gloss area average yield kg blank group 17.62 13.8 67.8 general 42.58

对照组 19.02 14.2 71.9 较好 45.60 Control group 19.02 14.2 71.9 Good 45.60

实施例 14 19.80 15.0 74.8 较好 48.26 Example 14 19.80 15.0 74.8 is better 48.26

实施例 17 20.12 15.8 78.2 好 51.68 Example 17 20.12 15.8 78.2 Good 51.68

实施例 19 20.09 15.9 77.9 好 51.23 Example 19 20.09 15.9 77.9 Good 51.23

实验例 7 Experimental example 7

该实验例为本发明可作为冲施肥的肥料在黄瓜上的肥效试验。 This experimental example is a fertilizer effect test of the invention as a fertilizer for flushing fertilizer on cucumber.

试验在农用大棚中进行，供试品种为京优 3号，农田划分为多个小区，每个小区为 20m²，空白组为不做任何处理，其它为施用本发明实施例组，用量为 600kg/hm²，施用时间为黄瓜株高 90 一 100cm时。 The test was carried out in an agricultural greenhouse. The test variety was Jingyou No. 3. The farmland was divided into several plots, each plot was 20 m ² , empty The white group was left without any treatment, and the others were applied to the group of the present invention in an amount of 600 kg/hm ² and the application time was when the plant height of the cucumber was 90 to 100 cm.

试验结果如表 6 The test results are shown in Table 6.

表 6不同处理的黄瓜性状和产量 Table 6 Cucumber traits and yield of different treatments

处理株高 cm ~~ 5株大果数(>20(^) 病株率％产量 (kg/667m²) ~ 空白组 Ϊ2 0 06 ΪΑ6 2586.3 实施例 15 142.8 3.6 5.8 3321.6 实施例 20 145.6 4.0 4.6 3403.8 Treatment plant height cm ~~ 5 large fruit counts (>20 (^) disease plant rate % yield (kg/667m ² ) ~ blank group Ϊ2 0 06 ΪΑ6 2586.3 Example 15 142.8 3.6 5.8 3321.6 Example 20 145.6 4.0 4.6 3403.8

由上可见，本发明可作为冲施肥的肥料施用后养分容易被吸收，不易被土壤固定，不板结土壤，无毒害残留；施用方便，省工省力；营养成分多而全面，肥效快，有利于作物增产。在作物生长旺盛季节，避免了普通肥料追肥肥料养分释放转化慢、肥效迟缓、影响作物产量和品质的缺实施例 25 It can be seen from the above that the nutrient can be easily absorbed as a fertilized fertilizer after application, is not easy to be fixed by soil, does not bind soil, has no toxic residue; is convenient to apply, saves labor and labor; nutrient composition is comprehensive and comprehensive, and fertilizer efficiency is fast, which is beneficial to Crop yield increase. In the season of vigorous crop growth, the lack of conversion of common fertilizer topdressing fertilizer nutrient release, slow fertilizer efficiency, and affecting crop yield and quality are avoided.

步骤（1) (2) 同实施例 1，所不同的是步骤（3)，具体为： Step (1) (2) The difference from the first embodiment is the step (3), which is specifically:

在稀黑液中按每 1000ml加入 O.lg硫酸亚铁和 20g硫酸锌，用 H₃P0₄将 pH调节为 10; 即得可作为叶面肥的肥料，黄腐酸重量百分比含量为 5%，适用于大田作物。 Add O.lg ferrous sulfate and 20g zinc sulfate per 1000ml in the diluted black liquor, and adjust the pH to 10 with H ₃ P0 ₄ ; that is, it can be used as a fertilizer for foliar fertilizer, and the content of fulvic acid is 5% by weight. , suitable for field crops.

实施例 26 Example 26

步骤（1) (2) 同实施例 2，所不同的是步骤 (3)，具体为： Step (1) (2) Same as Embodiment 2, except that step (3) is specifically:

将亚铵法稀黑液和蒽醌 -烧碱法稀黑液按照体积比 1: 100的比例混合，得到混合草浆稀黑液，将混合稀草浆黑液直接蒸发浓缩至固含量为 30%，波美度为 18，得到混合浓黑液，其 pH=ll，在混合浓草浆黑液中按每 1000ml加入 O.lg硼砂、 15g硫酸亚铁和 20g硫酸锌，用 H₃P0₄将 pH调节为 8; 即得可作为叶面肥的肥料，黄腐酸重量百分比 8%，适用于果树。 Mixing the ammonium imide black liquor and the bismuth-caustic black liquor in a ratio of 1:100 by volume to obtain a mixed straw black liquor, and directly concentrating the mixed straw black liquor to a solid content of 30%. , Baume degree is 18, the mixed concentrated black liquor is obtained, its pH=11, O.lg borax, 15g ferrous sulfate and 20g zinc sulfate are added per 1000ml in the mixed concentrated black liquor, and H ₃ P0 ₄ will be used. The pH is adjusted to 8; that is, it can be used as a fertilizer for foliar fertilizer, and the percentage of fulvic acid is 8%, which is suitable for fruit trees.

实施例 27 Example 27

步骤（1) (2) 同实施例 3，所不同的是步骤 (3)，具体为： Step (1) (2) Same as Embodiment 3, except that step (3) is specifically:

将亚铵法稀黑液和蒽醌一烧碱法稀草浆黑液按照体积比 100: 1的比例混合，得到混合草浆稀黑液，将混合草浆黑液直接蒸发浓缩至固含量为 65%，波美度为 40，得到混合浓黑液， pH=5，在混合浓黑液中按每 1000ml加入 15g硼酸和 O.lg硫酸锌，用 HN0₃调整 pH为 6，即得可作为叶面肥的肥料，黄腐酸重量百分比 40%，适用于蔬菜。 The ammonium imide black liquor and the samarium caustic soda pulp black liquor are mixed according to a volume ratio of 100:1 to obtain a mixed straw pulp black liquor, and the mixed straw pulp black liquor is directly evaporated to a solid content of 65. %, Baume degree is 40, the mixed concentrated black liquor is obtained, pH=5, 15g of boric acid and O.lg zinc sulfate are added per 1000ml in the mixed concentrated black liquor, and the pH is adjusted to 6 by HN0 ₃ Fertilizer for face fertilizer, 40% by weight of fulvic acid, suitable for vegetables.

实施例 28 Example 28

步骤（1) (2)同实施例 4，所不同的是步骤 (3)，具体为：稀黑液首先蒸发浓缩至固含量 15.1 %, 波美度 9，得到浓黑液，在浓黑液中按每 1000ml加入 O.lg硫酸亚铁和 20g硫酸锌，用 H₃P0₄ 将 pH调节为 10; 即得可作为叶面肥的肥料，黄腐酸重量百分比含量为 5%，适用于大田作物。实施例 29 Step (1) (2) Same as Example 4, except that step (3) is specifically as follows: The diluted black liquor is first evaporated to a solid content of 15.1%, Baume degree 9, to obtain a concentrated black liquor, in concentrated black liquor Adding O.lg ferrous sulfate and 20g of zinc sulphate per 1000ml, adjusting the pH to 10 with H ₃ P0 ₄ ; that is, it can be used as a fertilizer for foliar fertilizer, the content of fulvic acid is 5% by weight, suitable for Daejeon crop. Example 29

步骤（1) (2) 同实施例 5，所不同的是步骤（3)，具体为：将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 1: 4的比例混合，得到混合草浆稀黑液，将混合草浆黑液采用五效蒸发，得到的混合浓黑液其固含量为 40%，波美度为 20， pH=6，在混合浓黑液中按每 1000ml加入 O.lg硼酸和 20g氯化锌，不需要额外调整 pH，即得可作为叶面肥的肥料，黄腐酸重量百分比 15%，适用于蔬菜。 Step (1) (2) Same as Example 5, except that the step (3) is specifically as follows: the ammonium black and the sulfate method are black The liquid is mixed according to the ratio of volume ratio of 1:4 to obtain a mixed black liquor of straw pulp, and the mixed liquor black liquor is subjected to five-effect evaporation, and the obtained concentrated black liquor has a solid content of 40%, a Baume degree of 20, and a pH. =6, O.lg boric acid and 20g zinc chloride are added per 1000ml in the mixed concentrated black liquor. No additional pH adjustment is required, so that it can be used as a fertilizer for foliar fertilizer. The percentage of fulvic acid is 15%, suitable for vegetables. .

实施例 30 Example 30

步骤（1) (2) 同实施例 6，所不同的是步骤（3)，具体为：将亚铵法稀黑液和蒽醌一烧碱法稀黑液按照体积比 4: 1的比例混合，得到混合草浆稀黑液，将混合草浆稀黑液采用五效蒸发，得到的混合浓黑液其固含量为 47%，波美度为 29， pH=6，在混合浓黑液中按每 1000ml加入 15g 硼砂、 O.lg硫酸亚铁和 O.lg硫酸锌，不需要额外调整 pH ；即得可作为叶面肥的肥料，黄腐酸重量百分比 30%适用于果树。 Step (1) (2) Same as in Example 6, except that the step (3) is specifically: mixing the ammonium imide black liquor and the sulphuric acid caustic black liquor in a ratio of 4:1 by volume. The mixed straw black liquor is obtained, and the mixed straw black liquor is subjected to five-effect evaporation, and the obtained concentrated black liquor has a solid content of 47%, a Baume degree of 29, and a pH=6, and is pressed in the mixed concentrated black liquor. 15g borax, O.lg ferrous sulfate and O.lg zinc sulphate are added per 1000ml, no additional pH adjustment is required; that is, it can be used as a fertilizer for foliar fertilizer, and 30% by weight of fulvic acid is suitable for fruit trees.

实施例 31 Example 31

步骤（1) (2) 同实施例 7，所不同的是步骤（3)，具体为：将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 3: 1的比例混合，得到混合草浆稀黑液；将混合草浆稀黑液采用五效蒸发，得到的混合浓黑液其固含量为 45%，波美度为 28， pH=7，在混合浓黑液中按每 1000ml加入 15g硫酸亚铁和 O.lg氯化锌，不需要额外调整 pH; 即得可作为叶面肥的肥料，黄腐酸重量百分比 35%，适用于大田作物。 Step (1) (2) Same as in Example 7, except that the step (3) is specifically: mixing the ammonium imide black liquor and the sulfate black liquor in a ratio of 3:1 by volume to obtain a mixture. Straw black liquor; the mixed straw black liquor is evaporated by five effects, and the obtained concentrated black liquor has a solid content of 45%, Baume degree of 28, pH=7, and per 1000 ml of mixed concentrated black liquor. Adding 15g of ferrous sulfate and O.lg zinc chloride does not require additional pH adjustment; it can be used as a fertilizer for foliar fertilizer, and the percentage of fulvic acid is 35%, which is suitable for field crops.

实施例 32 Example 32

步骤（1) (2) 同实施例 30，所不同的是步骤（3)，具体为：其它条件同实施例 30，亚铵法稀黑液和蒽醌一烧碱稀黑液体积比 10: 1，在混合浓黑液中按每 1000ml加入 O.lg硼酸和 15g硫酸锌，不需要额外调整 pH，即得可作为叶面肥的肥料，黄腐酸重量百分比 37%，适用于蔬菜。实施例 33 Step (1) (2) Same as Example 30, except that the step (3) is specifically as follows: other conditions are the same as those in the embodiment 30, the volume ratio of the immigrant black liquor and the niobium caustic black liquor is 10:1. O.lg boric acid and 15g zinc sulfate are added per 1000ml in the mixed concentrated black liquor. No additional pH adjustment is required, so that it can be used as a fertilizer for foliar fertilizer, and the percentage of fulvic acid is 37%, which is suitable for vegetables. Example 33

步骤（1) (2) 同实施例 31，所不同的是步骤（3)，具体为：其它条件同实施例 29，亚铵法稀黑液和硫酸盐法稀黑液体积比 1: 10，在碱法和亚铵法混合浓缩草浆黑液中按每 1000ml加入 15g 硼砂、 O.lg硫酸亚铁和 O.lg硫酸锌，不需要额外调整 pH ；即得可作为叶面肥的肥料，黄腐酸重量百分比 30%，适用于果树。 Step (1) (2) Same as Example 31, except that step (3) is specifically: other conditions are the same as those in Example 29, and the volume ratio of the ammonium black solution and the sulfuric acid black liquor is 1:10. Add 15g borax, O.lg ferrous sulfate and O.lg zinc sulphate per 1000ml in the alkali liquor and ammonium imide mixed concentrated straw black liquor. No additional pH adjustment is required; that is, it can be used as a fertilizer for foliar fertilizer. The percentage of fulvic acid is 30%, which is suitable for fruit trees.

实施例 34、 Example 34

其它条件同实施例 31，所不同的是在混合浓黑液中按每 1000ml加入 5g硼砂、 10g硫酸亚铁和 6g硫酸锌，不需要额外调整 pH ；即得可作为叶面肥的肥料，黄腐酸重量百分比 25%，适用于果树。 Other conditions are the same as in Example 31, except that 5 g of borax, 10 g of ferrous sulfate and 6 g of zinc sulfate are added per 1000 ml in the mixed concentrated black liquor, and no additional pH adjustment is required; that is, a fertilizer which can be used as a foliar fertilizer, yellow The percentage of humic acid is 25% by weight and is suitable for fruit trees.

实施例 35 Example 35

其它条件同实施例 30，所不同的是在混合浓黑液中按每 1000ml加入 9g硫酸亚铁和 3g硫酸锌，用 H₃P0₄将 pH调节为 10; 即得可作为叶面肥的肥料，黄腐酸重量百分比 28%，适用于大田作物。 Other conditions are the same as in Example 30, except that 9 g of ferrous sulfate and 3 g of zinc sulfate are added per 1000 ml in the mixed concentrated black liquor, and the pH is adjusted to 10 with H ₃ P0 ₄ ; that is, a fertilizer which can be used as a foliar fertilizer , fulvic acid weight percentage of 28%, suitable for field crops.

实施例 36 其它条件同实施例 31，所不同的是在混合浓黑液中按每 1000ml加入 10g硼酸和 13g硫酸锌，用 HN0₃调整 pH为 6，即得可作为叶面肥的肥料，黄腐酸重量百分比 26 %，适用于蔬菜。 Example 36 Other conditions are the same as those in Example 31 except that 10 g of boric acid and 13 g of zinc sulfate are added per 1000 ml in the mixed concentrated black liquor, and the pH is adjusted to 6 with HN0 ₃ to obtain a fertilizer which can be used as a foliar fertilizer, and the weight of the fulvic acid Percentage 26% for vegetables.

实施例 37 Example 37

步骤（1 ) (2 ) 同实施例 13，其余条件同实施例 28，所不同的是在浓黑液中按每 1000ml加入 12g硼砂、 l lg硫酸亚铁和 7g硫酸锌，用 H₃P0₄将 pH调节为 8 ; 即得可作为叶面肥的肥料，黄腐酸重量百分比 8 %，适用于果树。 Step (1) (2) Same as Example 13, the other conditions are the same as those in Example 28, except that 12 g of borax, 1 lg of ferrous sulfate and 7 g of zinc sulfate are added per 1000 ml in concentrated black liquor, and H ₃ P0 _{4 is used.} Adjust the pH to 8; that is, it can be used as a fertilizer for foliar fertilizer. The percentage of fulvic acid is 8% by weight, which is suitable for fruit trees.

实施例 38 Example 38

步骤（1 ) (2 ) 同实施例 14，其余条件同实施例 28，所不同的是在浓黑液中按每 1000ml加入 6g硼砂、 7g硫酸亚铁和 5g硫酸锌，用 H₃P0₄将 pH调节为 8 ; 即得可作为叶面肥的肥料，黄腐酸重量百分比 7 %，适用于果树。 Step (1) (2) Same as Example 14, the other conditions are the same as in Example 28, except that 6 g of borax, 7 g of ferrous sulfate and 5 g of zinc sulfate are added per 1000 ml in concentrated black liquor, and H ₃ P0 _{4 is} used. The pH is adjusted to 8; that is, it can be used as a fertilizer for foliar fertilizer, and the percentage of fulvic acid is 7% by weight, which is suitable for fruit trees.

实验例 8 Experimental example 8

1、试验材料与方法：试验采用大区对比法，每示范试验区面积 2.0 hm² 。试验共设 3个处理, 处理 1 2 在常规施肥的基础上,分别在苗期、花前期用实施例 25和 28 得到的可作为叶面肥的肥料 1000 倍液叶面喷洒，每公顷用量 450g ;处理 3 为对照，在常规施肥的基础上,分别在苗期、花前期用等量清水叶面喷洒。供试水稻品种为空育 131 1. Test materials and methods: The test uses a large area comparison method with an area of 2.0 hm ² per demonstration area. A total of 3 treatments were carried out in the test. Treatment 1 2 On the basis of conventional fertilization, the 1000-fold liquid foliar spray of the fertilizer obtained as the foliar fertilizer obtained in Examples 25 and 28 at the seedling stage and the pre-flowering stage was sprayed at 450 g per hectare. Treatment 3 was used as a control. On the basis of conventional fertilization, the same amount of clear water was sprayed on the seedling stage and the pre-flowering stage. The tested rice variety is Kong Yu 131

2、产量测定结果 2. Yield measurement results

表 7 Table 7

株 1¾ 千粒重 Λ里处理平方米穗数穗实粒数 Plant 13⁄4 thousand grain weight Λ里 processing square rice spike number

cm cm g Kg/hm² 实施例 25 540. 4 79. 1 15. 2 51. 6 23. 9 7318. 5 实施例 28 582. 4 80. 2 15. 6 52. 2 24. 3 7644. 0 对照 511. 2 77. 9 14. 6 48. 3 23. 4 6183. 5 试验结果表明，施用本发明产品的水稻的平方米穗数、株高、穗长、穗实粒数、千粒重、产量较对照组相比，均有显著的增加。其中，实施例 25组较对照每公顷增产 1135. 0kg，增产 18. 4 % , 实施例 28组较对照每公顷增产 1460. 5，增产 23. 6 %，经济效益显著。 Cm cm g Kg/hm ² Example 25 540. 4 79. 1 15. 2 51. 6 23. 9 7318. 5 Example 28 582. 4 80. 2 15. 6 52. 2 24. 3 7644. 0 Control 511. 2 77. 9 14. 6 48. 3 23. 4 6183. 5 The test results show that the rice panicle number, plant height, ear length, grain number per panicle, 1000-grain weight, and yield of rice to which the product of the present invention is applied are compared with the control. Compared with the group, there was a significant increase. The increase in production of 1135. 0kg per hectare was increased by 18.4%, and the increase of 14.60% per hectare was compared with that of the control group. The yield increased by 23.6%, and the economic benefit was significant.

实验例 9 Experimental example 9

1、供试品种美国 8号苹果，为美国选育的优良品种 1. Test variety US No. 8 apple, an excellent variety for breeding in the United States

2、试验设计与方法本试验设 4个不同的施用处理，前三组分别用实施例 26 30 33的叶面肥稀释 1000倍叶面喷施，另外设一组对照喷施清水。小区面积 60m² (长 30m，宽 2m)。每小区有苹果树 10株。叶面施肥在晴天上午的 10时左右进行。 2. Test design and method Four different application treatments were set up in this test. The first three groups were diluted with 1000% foliar application of the foliar fertilizer of Example 26 30 33, and a set of control sprayed water was set. The area of the plot is 60 m ² (length 30 m, width 2 m). There are 10 apple trees in each plot. Foliar fertilization is carried out at around 10 am on a sunny day.

3、试验结果 3. Test results

表 8 Table 8

龍 I II III 平均折亩产实施例 26 87. 6 89. 0 87. 2 87. 93 967. 23 实施例 30 91.3 92.2 92.6 92.03 1012.23 实施例 33 91.7 91.5 91.9 91.70 1008.70 对照 81.7 82.4 82.2 82.0 902.0 Dragon I II III Average yield per mu Example 26 87. 6 89. 0 87. 2 87. 93 967. 23 Example 30 91.3 92.2 92.6 92.03 1012.23 Example 33 91.7 91.5 91.9 91.70 1008.70 Control 81.7 82.4 82.2 82.0 902.0

可见，施用实施例 26、 30、 33得到的可作为叶面肥的肥料的苹果较对照分别增产 7.23%、 12.22%, 11.83%, 经济效益显著。 It can be seen that the apples which can be used as fertilizers for foliar fertilizers obtained in Examples 26, 30 and 33 have an increase of 7.23%, 12.22% and 11.83%, respectively, and the economic benefits are remarkable.

实验例 10 Experimental example 10

1、供试材料（1) 供试肥料：惠满丰有机腐殖酸液肥 4000mg/kg，主要含腐殖酸及各种植物所需的大量元素和微量元素；本发明实施例 27和 29所得可作为叶面肥的肥料； 1. Test materials (1) Test fertilizer: Huimanfeng organic humic acid liquid fertilizer 4000mg/kg, mainly containing humic acid and a large number of elements and trace elements required by various plants; obtained in Examples 27 and 29 of the present invention Can be used as a fertilizer for foliar fertilizers;

(2) 供试品种苏椒五号辣椒，江苏省农科院蔬菜研究所研制。 (2) The test variety Sujiao No. 5 pepper was developed by the Vegetable Research Institute of Jiangsu Academy of Agricultural Sciences.

2、试验方法试验于 2005— 2006年大棚中进行。 2006年 10月 20日大棚内育苗， 11月 30 日假植于营养钵， 2月 5 日定植，大行距 65cm，小行距 35cm，株距 33cm，深沟高畦。小区定苗 30株。于门椒开花时进行第 1次叶面喷施处理，门椒直经 2cm时进行第 2次叶面喷施处理，门椒采收时进行第 3次叶面喷施处理，以清水为对照。采收始期为 4月 25日，采收终期为 7月 2日，共 68天。 2. Test method The test was carried out in a greenhouse from 2005 to 2006. On October 20, 2006, the seedlings were planted in the greenhouse. On November 30, they were planted in the nutrient bowl. They were planted on February 5, with a line spacing of 65 cm, a small row spacing of 35 cm, and a plant spacing of 33 cm. There are 30 seedlings in the community. The first foliar spray treatment was carried out when the pepper was flowering, and the second foliar spray treatment was carried out when the door pepper was 2 cm straight, and the third foliar spray treatment was carried out when the pepper was harvested. . The harvesting period is April 25th, and the final harvesting period is July 2nd, a total of 68 days.

3、试验结果 3. Test results

表 9不同处理的总产量 Table 9 Total yield of different treatments

处理亩产 kg 增产％ Treatment yield per mu increase in production

惠满丰 2878.2 9~52 Hui Manfeng 2878.2 9~52

实施例 27 2952.0 12.33 Example 27 2952.0 12.33

实施例 29 3175.2 20.82 Example 29 3175.2 20.82

对照 2628.0 Comparison 2628.0

可见，施用本发明实施例 27和 29的可作为叶面肥的肥料增产效果显著。 It can be seen that the fertilizers which can be used as foliar fertilizers of Examples 27 and 29 of the present invention have a remarkable effect of increasing yield.

实施例 39 Example 39

步骤（1) (2) 同实施例 1，所不同的是步骤 (3)，具体为：用甲酸将稀黑液的 pH调节到 5，析出木质素，加入黑液重量 2ppm的聚合硫酸铁，静置，然后将黑液过滤，得到的滤液即为肥料前产品。将滤液干燥，得到固体肥料。 Step (1) (2) Same as Example 1, except that step (3) is specifically: adjusting the pH of the diluted black liquor to 5 with formic acid, precipitating lignin, adding 2 ppm of polyferric sulfate of black liquor, After standing, the black liquor was filtered, and the obtained filtrate was a pre-fertilizer product. The filtrate was dried to give a solid fertilizer.

实施例 40 Example 40

将亚铵法稀黑液和蒽醌 -烧碱法稀黑液按照体积比 1: 100的比例混合，得到混合草浆稀黑液，将混合稀草浆黑液直接蒸发浓缩至固含量为 30%，波美度为 18，得到混合浓黑液，其 pH=ll，用乙酸将浓黑液的 pH调节到 2，析出木质素，加入黑液重量 50ppm的碱式氯化铝，静置，然后将黑液过滤，得到的滤液即为肥料前产品。 Mixing the ammonium imide black liquor and the bismuth-caustic black liquor in a ratio of 1:100 by volume to obtain a mixed straw black liquor, and directly concentrating the mixed straw black liquor to a solid content of 30%. , Baume degree is 18, the mixed concentrated black liquor is obtained, the pH is ll, the pH of the concentrated black liquor is adjusted to 2 with acetic acid, the lignin is precipitated, the basic aluminum chloride having a black liquor weight of 50 ppm is added, and then allowed to stand, then The black liquor was filtered, and the obtained filtrate was a pre-fertilizer product.

将滤液进行干燥，得到固体肥料。 The filtrate was dried to obtain a solid fertilizer.

实施例 41 步骤（1 ) (2 ) 同实施例 3，所不同的是步骤（3)，具体为： Example 41 Step (1) (2) Same as Embodiment 3, except that step (3) is specifically:

将亚铵法稀黑液和蒽醌一烧碱法稀草浆黑液按照体积比 100: 1的比例混合，得到混合草浆稀黑液，将混合草浆黑液直接蒸发浓缩至固含量为 65 %，波美度为 40，得到混合浓黑液， pH=5，用丙酸将浓黑液的 pH调节到 4，析出木质素，加入黑液重量 5ppm的聚丙烯酸铵，静置，然后将黑液过滤，得到的滤液即为肥料前产品。 The ammonium imide black liquor and the samarium caustic soda pulp black liquor are mixed according to a volume ratio of 100:1 to obtain a mixed straw pulp black liquor, and the mixed straw pulp black liquor is directly evaporated to a solid content of 65. %, Baume degree is 40, the mixed concentrated black liquor is obtained, pH=5, the pH of the concentrated black liquor is adjusted to 4 with propionic acid, lignin is precipitated, ammonium polyacrylate having a black liquor weight of 5 ppm is added, and it is allowed to stand, then The black liquor is filtered, and the obtained filtrate is the pre-fertilizer product.

将滤液用中国专利 CN01141835.4所描述的方法用超临界 C0₂提取，即得高纯黄腐酸。实施例 42 The filtrate was extracted with supercritical CO ₂ by the method described in Chinese Patent No. CN11141835.4, that is, high purity fulvic acid was obtained. Example 42

步骤（1 ) (2 ) 同实施例 4，所不同的是步骤 (3)，具体为： Step (1) (2) Same as Embodiment 4, except that step (3) is specifically:

稀黑液首先蒸发浓缩至固含量 15.1 %，波美度 9，得到浓黑液，用苯甲酸将浓黑液的 pH调节到 3.5，析出木质素，加入黑液重量 15ppm的聚丙烯酸铵，静置，然后将黑液过滤，得到的滤液即为肥料前产品。将滤液用中国专利 CN01141835.4所描述的方法用超临界 C0₂提取，即得高纯黄腐酸。 The diluted black liquor was first concentrated by evaporation to a solid content of 15.1%, Baume degree of 9, to obtain a concentrated black liquor, the pH of the concentrated black liquor was adjusted to 3.5 with benzoic acid, lignin was precipitated, and ammonium polyacrylate having a black liquor weight of 15 ppm was added. The black liquor is then filtered, and the obtained filtrate is the pre-fertilizer product. The filtrate was extracted with supercritical CO ₂ by the method described in Chinese Patent No. CN11141835.4, that is, high purity fulvic acid was obtained.

实施例 43 Example 43

步骤（1 ) (2 ) 同实施例 5，所不同的是步骤（3 )，具体为： Step (1) (2) Same as Embodiment 5, except that step (3) is specifically:

将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 1 : 4的比例混合，得到混合草浆稀黑液，将混合草浆黑液采用五效蒸发，得到的混合浓黑液其固含量为 40 %，波美度为 20， pH=6，用盐酸将浓黑液的 pH调节到 3.7，析出木质素，加入黑液重量 lOppm的碱式氯化铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 The ammonium imide black liquor and the sulfate black liquor are mixed according to a ratio of volume ratio of 1:4 to obtain a mixed straw black liquor, and the mixed straw black liquor is subjected to five-effect evaporation to obtain a mixed concentrated black liquor. The solid content is 40%, the Baume degree is 20, pH=6, the pH of the concentrated black liquor is adjusted to 3.7 with hydrochloric acid, the lignin is precipitated, and the basic aluminum chloride having a weight of 10 ppm of black liquor is added, allowed to stand, and then blackened. The liquid was filtered to obtain a filtrate, that is, a pre-fertilizer product.

将滤液用中国专利 CN01141835.4所描述的方法用超临界 C0₂提取，即得高纯黄腐酸。实施例 44 The filtrate was extracted with supercritical CO ₂ by the method described in Chinese Patent No. CN11141835.4, that is, high purity fulvic acid was obtained. Example 44

步骤（1 ) (2 ) 同实施例 6，所不同的是步骤（3 )，具体为： Step (1) (2) The difference from the embodiment 6 is the step (3), which is specifically:

将亚铵法稀黑液和蒽醌一烧碱法稀黑液按照体积比 4: 1的比例混合，得到混合草浆稀黑液，将混合草浆稀黑液采用五效蒸发，得到的混合浓黑液其固含量为 47 %，波美度为 29， pH=6，用硫酸将浓黑液的 pH调节到 4.5，析出木质素，加入黑液重量 30ppm的碱式氯化铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 Mixing the ammonium imide black liquor and the sulphuric acid caustic black liquor in a ratio of 4:1 by volume to obtain a mixed straw pulp black liquor, and mixing the straw pulp black liquor with a five-effect evaporation to obtain a mixed concentration The black liquor has a solid content of 47%, a Baume degree of 29, and a pH=6. The pH of the concentrated black liquor is adjusted to 4.5 with sulfuric acid to precipitate lignin, and the basic aluminum chloride having a black liquor weight of 30 ppm is added and allowed to stand. The black liquor is then filtered to obtain a filtrate, i.e., a pre-fertilizer product.

将肥料前产品进行干燥即得固体肥料。 Drying the pre-fertilizer product yields a solid fertilizer.

实施例 45 Example 45

步骤（1 ) (2) 同实施例 7，所不同的是步骤（3 )，具体为： Step (1) (2) The difference from the embodiment 7 is the step (3), which is specifically:

将亚铵法稀黑液和硫酸盐法稀黑液按照体积比 3 : 1的比例混合，得到混合草浆稀黑液；将混合草浆稀黑液采用五效蒸发，得到的混合浓黑液其固含量为 45 %，波美度为 28， pH=7，用硝酸将浓黑液的 pH调节到 2.5，析出木质素，加入黑液重量 7ppm的碱式氯化铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 Mixing the ammonium imide black liquor and the sulfate black liquor in a ratio of 3:1 by volume to obtain a mixed straw black liquor; and mixing the straw black liquor with a five-effect evaporation to obtain a mixed concentrated black liquor The solid content is 45%, the Baume degree is 28, pH=7, the pH of the concentrated black liquor is adjusted to 2.5 with nitric acid, the lignin is precipitated, the basic aluminum chloride with a black liquor weight of 7 ppm is added, and the mixture is allowed to stand. The black liquor was filtered to obtain a filtrate, that is, a pre-fertilizer product.

实施例 46 步骤（1 ) (2 ) 同实施例 44，所不同的是步骤（3 )，具体为：亚铵法稀黑液和蒽醌一烧碱稀黑液体积比 10: 1，用硝酸将浓黑液的 pH调节到 2.8，析出木质素，加入黑液重量 8ppm的碱式氯化铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 Example 46 Step (1) (2) Same as in Example 44, except that the step (3) is specifically: the volume ratio of the ammonium blackish solution and the sulphuric acid caustic black liquor is 10:1, and the concentrated black liquor is made with nitric acid. The pH was adjusted to 2.8, lignin was precipitated, and basic aluminum chloride having a black liquor weight of 8 ppm was added thereto, allowed to stand, and then the black liquor was filtered to obtain a filtrate, that is, a pre-fertilizer product.

实施例 47 Example 47

步骤（1 ) (2 ) 同实施例 7，其它条件同实施例 5，所不同的是，亚铵法稀黑液和硫酸盐法稀黑液体积比 1 : 10，用硝酸将浓黑液的 pH调节到 2.1，析出木质素，加入黑液重量 9ppm的聚丙烯酸铵，静置，然后将黑液过滤，得到滤液即肥料前产品。 Step (1) (2) Same as in Example 7, the other conditions are the same as those in Example 5, except that the volume ratio of the ammonium black and the sulfate black liquor is 1:10, and the black liquor is concentrated with nitric acid. The pH was adjusted to 2.1, lignin was precipitated, ammonium polyacrylate having a black liquor weight of 9 ppm was added, and the mixture was allowed to stand, and then the black liquor was filtered to obtain a filtrate, that is, a pre-fertilizer product.

实施例 48、 Example 48.

其它条件同实施例 7，所不同的是用磷酸将浓黑液的 pH调节到 1，析出木质素，加入黑液重量 14ppm的聚合硫酸铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 The other conditions were the same as those in Example 7, except that the pH of the concentrated black liquor was adjusted to 1 with phosphoric acid, lignin was precipitated, and 14 ppm of polyaluminum sulphate was added, and the black liquor was allowed to stand, and then the black liquor was filtered to obtain a filtrate, that is, a fertilizer. Former product.

实施例 49 Example 49

其它条件同实施例 6，所不同的是：用磷酸将浓黑液的 pH调节到 1.5，析出木质素，加入黑液重量 20ppm的聚合硫酸铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 Other conditions were the same as those in Example 6. The pH of the concentrated black liquor was adjusted to 1.5 with phosphoric acid, lignin was precipitated, and the polyaluminum sulfate having a black liquor weight of 20 ppm was added thereto, allowed to stand, and then the black liquor was filtered to obtain a filtrate. Pre-fertilizer products.

将滤液用中国专利 CN01141835.4所描述的方法用超临界 C0₂提取，即得高纯黄腐酸。实施例 50 The filtrate was extracted with supercritical CO ₂ by the method described in Chinese Patent No. CN11141835.4, that is, high purity fulvic acid was obtained. Example 50

其它条件同实施例 7，所不同的是：用磷酸将浓黑液的 pH调节到 2.8，析出木质素，加入黑液重量 18ppm的聚合硫酸铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 Other conditions were the same as those in Example 7, except that the pH of the concentrated black liquor was adjusted to 2.8 with phosphoric acid, lignin was precipitated, and polyaluminum sulphate having a black liquor weight of 18 ppm was added thereto, allowed to stand, and then the black liquor was filtered to obtain a filtrate. Pre-fertilizer products.

实施例 51 Example 51

步骤（1 ) (2 ) 同实施例 13，其余条件同实施例 4，所不同的是用磷酸将浓黑液的 pH调节到 3.2，析出木质素，加入黑液重量 l lppm的聚合硫酸铝，静置，然后将黑液过滤，得到滤液，即为肥料前产品，将肥料前产品进行干燥即得固体肥料。 Step (1) (2) Same as Example 13, the other conditions are the same as those in Example 4, except that the pH of the concentrated black liquor is adjusted to 3.2 with phosphoric acid, lignin is precipitated, and polyaluminum sulfate having a weight of l1 ppm of black liquor is added. After standing, the black liquor is filtered to obtain a filtrate, which is a pre-fertilizer product, and the pre-fertilizer product is dried to obtain a solid fertilizer.

实施例 52 Example 52

步骤（1 ) (2 ) 同实施例 14，其余条件同实施例 4，所不同的是：用硝酸将浓黑液的 pH调节到 2.7，析出木质素，加入黑液重量 6ppm的聚合硫酸铝，静置，然后将黑液过滤，得到滤液。将滤液用中国专利 CN01141835.4所描述的方法用超临界 C0₂提取，即得高纯黄腐酸。 Step (1) (2) Same as Example 14, the other conditions are the same as those in Example 4, except that: the pH of the concentrated black liquor is adjusted to 2.7 with nitric acid, lignin is precipitated, and the polyaluminum sulfate having a black liquor weight of 6 ppm is added. After standing, the black liquor was filtered to obtain a filtrate. The filtrate was extracted with supercritical CO ₂ by the method described in Chinese Patent No. CN11141835.4, that is, high purity fulvic acid was obtained.

实施例 53 Example 53

( 1 ) 亚铵法蒸煮 (1) Ammonium cooking

在稻草秸秆中加入蒸煮药液，其中亚硫酸铵的用量为绝干原料量 11%，液比为 1 : 2，通入蒸汽进行加热，加热升温至温度为 100°C时保温 20分钟，进行小放汽，继续加热升温至 165°C，保温 60分钟，得到浓度为 8 %的浆，浆的硬度为高锰酸钾值 16。 (2 ) 高硬度浆后处理得到稀黑液 The cooking liquor is added to the straw straw, wherein the amount of ammonium sulfite is 11% of the absolute dry material, the liquid ratio is 1:2, heated by steam, and heated to a temperature of 100 ° C for 20 minutes. The small steam is continuously heated to 165 ° C and kept for 60 minutes to obtain a slurry having a concentration of 8 %. The hardness of the slurry is 16 potassium permanganate. (2) High-hardness pulp post-treatment to obtain a dilute black liquor

浆从挤浆机的入口进入，挤出黑液，挤出黑液之后，得到固含量为 15 %，波美度为 9的稀黑液， pH为 10。 The slurry enters from the inlet of the extruder, extrudes the black liquor, and after extruding the black liquor, a dilute black liquor having a solid content of 15% and a Baume degree of 9 is obtained, and the pH is 10.

( 3 ) 稀黑液进行处理 (3) Treatment of diluted black liquor

将步骤（2 )所得的稀黑液用磷酸将浓黑液的 pH调节到 2.8，析出木质素，加入黑液重量 18ppm 的聚合硫酸铝，静置，然后将黑液过滤，得到滤液即肥料前产品。 The diluted black liquor obtained in the step (2) was adjusted to pH 2.8 with phosphoric acid, and lignin was precipitated, and polyaluminum sulfate having a black liquor weight of 18 ppm was added thereto, allowed to stand, and then the black liquor was filtered to obtain a filtrate before the fertilizer. product.

实验例 11 Experimental example 11

对实施例 7的固态肥料测定，结果如下： The solid fertilizer of Example 7 was measured and the results were as follows:

(1)、结构特征 (1), structural characteristics

1、元素组成： C 54.82% ； H 2.29% ； 0 41.14% ； N 0.66% ； S 1.09%。 1. Elemental composition: C 54.82%; H 2.29%; 0 41.14%; N 0.66%; S 1.09%.

2、功能团含量：总酸基 8.76毫克当量 /克（羚基 6.12毫克当量 /克，酚羟基 2.64毫克当量 /克）. 2. Functional group content: total acid group 8.76 meq/g (antelope 6.12 meq/g, phenolic hydroxyl 2.64 meq/g).

3、数均分子量： Mn=1032 。 3. Number average molecular weight: Mn=1032.

(2)、产品质量标准黄腐酸固体为深棕色、味酸、无臭、易溶于水、乙醇。稀酸、稀碱和含水丙酮。 (2), product quality standard fulvic acid solid is dark brown, sour, odorless, soluble in water, ethanol. Dilute acid, dilute alkali and aqueous acetone.

1、黄腐酸含量≥95% ； 2、 10%水溶液 PH 2.5— 3 ； 1, fulvic acid content ≥ 95%; 2, 10% aqueous solution PH 2.5-3;

3、重金属 <20PPM； 4、砷盐 <2PPM ； 3, heavy metals <20PPM; 4, arsenic salt <2PPM;

5、 E4 //E6比值在 10— 15之间。 5. E4 //E6 ratio is between 10 and 15.

Claims

Claim

A method for comprehensively utilizing straw straws, characterized in that it comprises:

(1) The grass straw is steamed to obtain a high hardness pulp having a hardness of potassium permanganate of 16-28; a high hardness pulp having a hardness of 18-27 is preferred; the hardness is preferably permanganic acid. High hardness pulp with a potassium value of 20-25;

(2) squeezing the high-hardness slurry to obtain a slurry after slurrying and a thin black liquor;

(3) Separating the diluted black liquor into solid and liquid, discarding the solid, and obtaining the filtrate as the pre-fertilizer product; or first evaporating and diluting the diluted black liquor to obtain a concentrated black liquor, then performing solid-liquid separation, discarding the solid, and obtaining The filtrate is the pre-fertilizer product.

2. A pre-fertilizer product, characterized in that the preparation method of the pre-fertilizer product comprises:

(3) The solid black liquor is subjected to solid-liquid separation, and the solid is discarded, and the obtained filtrate is obtained as the pre-fertilizer product; or the diluted black liquor is first concentrated by evaporation to obtain a concentrated black liquor, and then solid-liquid separation is performed, and the solid is discarded. The obtained filtrate obtained the pre-fertilizer product.

The method of comprehensive utilization according to claim 1 or the pre-fertilizer product according to claim 2, wherein the grass comprises wheat grass, straw, cotton stalk, bagasse, arundo donax or reed One or a mixture of two or more; the cooking method includes one or more combinations of an ammonium iodide method, a caustic soda method, a sulfate method, or an alkaline method. The sodium sulphate method, preferably the ammonium imide process is:

1 Adding cooking liquor to the grass straw raw materials, wherein the amount of ammonium sulfite is 9-13% of the amount of dry raw materials, and the amount of sodium hydroxide is 0-8% of the amount of dry raw materials, and the liquid ratio is 1 : 2-4;

2 It is heated by steam, heated to a temperature of 165-173 ° C, heating, small venting, and heat preservation for 160-210 minutes;

Preferably, the barium-soda cooking is:

1 Adding cooking liquor to the grass straw raw material, wherein the alkali amount is 9-15% of the absolute dry material, and the liquid ratio is 1:2-4, and the amount of the rhodium is the absolute dry material. 0. 5-0. 8%。 The amount of 0. 5-0. 8%. ;

2 is heated by steam, heated to a temperature of 160-165 ° C, heating, small venting, heat preservation time of 140-190 minutes;

Preferably, the kraft cooking is:

1 adding a cooking liquid to the grass straw raw material, wherein the amount of the dry raw material is 8-11%, the liquid ratio is 1:2-4, and the degree of sulfurization is 5-8%; 2 steaming to heat, heating to a temperature of 165-173 ° C, heating, small deflation, heat preservation time of 150-200 minutes;

Preferably, the alkaline sodium solution cooking comprises:

The sulphuric acid is added in an amount of 9 to 15% by weight of the dry raw material, the sodium sulfite is 2 to 6%, and the hydrazine is 0. 04 - 0. 08%, cooking. The liquid ratio is 1: 3-4;

2 Heated by steam, heated to a temperature of 160-165 ° C, heating, small venting, heat preservation time of 140-190 minutes.

The method according to claim 1 or the pre-fertilizer product according to claim 2, wherein the dilute black liquor is separately cooked by an ammonium imide method and an alkali method, and then squeezed to obtain an ammonium imide method. The black liquor and the alkali black liquor are mixed, and then the mixed ammonium and alkali processes are mixed with the diluted black liquor; or the diluted black liquor is the diluted black liquor obtained by the ammonium imitation process.

The comprehensive utilization method or the pre-fertilizer product according to claim 4, wherein the mixing ratio of the ammonium imide black liquor and the alkali black liquor in the ammonium black and alkali mixed black liquor Is 1: 100-100: 1, preferably 1: 10- 10: 1, more preferably 1: 4-4: 1, the ammonium imide black liquor Baume 2-9, solid content 4-15 %, pH is 7-10; The alkaline black liquor has a Baume degree of 2-9, a solid content of 4-15%, and a pH of 9-13.

The solid content of the concentrated black liquor is 15.1-65%, and the Baume degree is 9-1. The solid content of the concentrated black liquor is 15.1-65%. 40; Preferably, the solid content is 30-65%, the Baume degree is 18-40, more preferably the solid content is 40-47%, the Baume degree is 25-29, and the pH of the concentrated black liquor is preferably 5-11; More preferably, the pH is 6-8.

7. The method of comprehensive utilization according to claim 1 or the pre-fermenter product according to claim 2, wherein the solid-liquid separation comprises adding an acid to the diluted black liquor or the concentrated black liquor to adjust the pH to 5 or less, then a flocculant is added, and the lignin solid is removed by filtration to obtain a filtrate.

8. The comprehensive utilization method or pre-fertilizer product according to claim 7, wherein the acid comprises an organic acid and an inorganic acid, and preferably the organic acid comprises one of formic acid, acetic acid, propionic acid or benzoic acid. One or more; preferred inorganic acids are one or more of hydrochloric acid, sulfuric acid, nitric acid or pity acid, and the pH is adjusted to 2-4.

The method of comprehensive utilization or the pre-fertilizer product according to claim 7, wherein the flocculant is added in an amount of 2 to 50 ppm by weight of the black liquor; preferably 5 to 15 ppm, most preferably 5 ppm; The agent includes one of polymeric ferric sulfate, basic aluminum chloride or ammonium polyacrylate.

The method of comprehensive utilization according to claim 1 or the pre-fermenter product according to claim 2, wherein the evaporation concentration is multi-effect evaporation, preferably six-effect evaporation, and more preferably the six-effect evaporation process is Countercurrent six-effect evaporation, mixed straw black liquor flows from VI effect, heating steam flows from I effect, and the mixed straw black liquor after flashing passes through VI effect, V effect, After the IV effect and the III effect heating and evaporation, it becomes a semi-concentrated black liquor, and the semi-concentrated black liquor is then subjected to the II effect and the I effect heating to evaporate, and then becomes a concentrated black liquor, that is, the alkali method and the ammonium imide method are mixed and concentrated. liquid.

The comprehensive utilization method according to claim 1 or the pre-fertilizer product according to claim 2, wherein the six-effect evaporation effect temperature is: I effect 100-110 ° C, II effect 90- 100 ° C, III effect 80-90 ° C, IV effect 70-80 ° C, V effect 60-70 ° C, VI effect 50-6 CTC; each effect black liquor wave beauty is: VI effect 5-8, V effect 7-10, IV effect 9-12, III effect 11-14; After II effect and I effect, II effect 14-17, I effect 18-21; The pressure of each effect is: I effect 20 -38 kPa , II effect 10 ~ - 10kPa, III effect - 20 ~ - 30 kPa, IV effect - 50 ~ - 60kPa, V effect - 60 ~ - 70kPa, VI effect a 75 ^ ^ - 85kPa, all pressures in the text are relative pressure, Relative to atmospheric pressure.

A fertilizer characterized in that the fertilizer comprises spray-drying or spray-granulating the concentrated black liquor described in claim 1, preferably after spray granulation.

The fertilizer according to claim 12, wherein the spray granulation head temperature is 550 to 600, the tail temperature is 47-55 ° C, and the return amount is 50%.

The fertilizer according to claim 12 or 13, wherein the fertilizer comprises mixing the concentrated black liquor, lignin and humic acid according to claim 1 and then performing spray drying or spray granulation. Preferably, after the spray granulation is obtained; or the concentrated black liquor, lignin and humic acid according to claim 1 are respectively spray-dried or spray-granulated, preferably after spray granulation and mixing;

When mixing, the weight percentage of each component is: 30-80% of concentrated black liquor; 1-4% of lignin; 1-25% of humic acid; preferably the weight percentage of each component is: 50-60% of concentrated black liquor Lignin 15-35 %; humic acid 10-15%.

The fertilizer according to claim 12, wherein the concentrated black liquor has a solid content of 15.1-65%, a Baume degree of 9-40, and a preferred solid content of 30-65%, Baume degree. More preferably, the solid content is from 40 to 47%, the Baume degree is from 25 to 29, and the pH of the concentrated black liquor is preferably from 5 to 11; more preferably, the pH is from 6 to 8.

The fertilizer according to claim 12, wherein the fertilizer comprises mixing the concentrated black liquor according to claim 1 and a soluble large amount of element fertilizer, followed by spray drying or spray granulation, preferably spray coating. After the granules are obtained; or the concentrated black liquor and the soluble large amount of the elemental fertilizer according to claim 1 are respectively spray-dried or spray-granulated, preferably after spray granulation, and mixed; the weight percentage of each component during mixing is: Black liquor 20-98%; soluble large element fertilizer 2 - 80%; preferably the weight percentage of each component is: concentrated black liquor 50-90%; soluble large element fertilizer 10-50%.

The fertilizer according to claim 16, wherein the soluble large amount of element fertilizer is one or more of soluble nitrogen fertilizer, soluble peat fertilizer and soluble potassium fertilizer; preferably soluble nitrogen fertilizer and soluble potassium fertilizer are added.

18. A fertilizer, characterized in that the fertilizer comprises dilute black liquor or concentrated black liquor, lignin and humic acid, and the weight percentage of each component is: 30-80% of diluted black liquor or concentrated black liquor; Lignin 1 -45 %; humic acid 1 - 25%; preferably each The weight percentage of the components is: dilute black liquor or concentrated black liquor 50-60%; lignin 15-35%; humic acid 10-15%; the diluted black liquor is solid content of 4-15%, wave The black liquor having a degree of 2-9; the concentrated black liquor is a black liquor obtained by evaporating and concentrating the above diluted black liquor to remove a part of water.

The fertilizer according to claim 18, wherein the diluted black liquor is black liquor produced by cooking grass straw, and the cooking comprises one of an ammonium imide method and an alkali method. Or a combination of more than one, the alkaline method comprising a sulphuric acid caustic method, a sulphate method or an alkaline sodium sulphate method.

The fertilizer according to claim 18, wherein the diluted black liquor is preferably pulped by an ammonium imide method and an alkali method to obtain an ammonium imide black liquor and an alkali black liquor, and then mixed to form a black liquor. The iminium method and the alkali method are mixed with the dilute black liquor; the mixed ratio of the iminium black method and the alkaline method diluted black liquor in the iminium method and the alkali method is 1:100-100:1. Preferably, 1:10-10: 1, more preferably 1:4-4: 1, the ammonium imide black liquor Baume 2-9, the solid content is 4-15%, the pH is 7-10; The basic method of dilute black liquor Baume 2-9, solid content of 4-15%, pH of 9-13.

The fertilizer according to claim 18, wherein the concentrated black liquor has a solid content of 15.1-65%, a Baume degree of 9-40, and a preferred solid content of 30-65%, Baume degree. More preferably, the solid content is from 40 to 47%, the Baume degree is from 25 to 29, and the pH of the concentrated black liquor is preferably from 5 to 11; more preferably, the pH is from 6 to 8.

22. A fertilizer, characterized in that the fertilizer comprises dilute black liquor or concentrated black liquor, soluble large amount of element fertilizer, and the weight percentage of each component is: diluted black liquor or concentrated black liquor 20-98%; Soluble large amount of elemental fertilizer 2 - 80%; preferably the weight percentage of each component is: diluted black liquor or concentrated black liquor 50 - 90%; soluble large amount of elemental fertilizer 10 - 50%; said diluted black liquor is solid content of 4 a 15%, Baume degree is 2-9 black liquor;

The concentrated black liquor is a black liquor obtained by evaporating and concentrating the diluted black liquor to remove a part of water.

The fertilizer according to claim 22, wherein the soluble large amount of element fertilizer is one or more of soluble nitrogen fertilizer, soluble peat fertilizer and soluble potassium fertilizer; preferably soluble nitrogen fertilizer and soluble potassium fertilizer are added.

The fertilizer according to claim 22, wherein the diluted black liquor or concentrated black liquor may also be added with sludge and/or pity gypsum; the weight percentage is sludge: 3-45%; pity Gypsum: 3-30%; preferred weight percentage is sludge: 10-20%; pity gypsum: 5-15%; the sludge is biochemical sludge produced by papermaking sewage treatment process, and the organic matter content is 50% or more.

The fertilizer according to claim 22, wherein an inorganic auxiliary material is added to the diluted black liquor or concentrated black liquor, and the inorganic auxiliary material is an inorganic salt containing N, P or K, or 2 of them The above mixture, preferably KC1, is added in an amount such that the total amount of N, P ₂ 0 ₅ and K ₂ 0 is 4 to 30% by mass, preferably 5 to 10% by mass based on the total dry weight of each component.

The fertilizer according to claim 23, wherein the soluble nitrogen fertilizer is urea, ammonium hydrogencarbonate, sulfuric acid a combination of one or more of ammonium, ammonium chloride, dihydro ammonium dihydrogen or dihydrogen diammonium hydroxide, preferably urea, and the soluble nitrogen fertilizer is in the range of 2 - 60% by weight of the fulvic acid fertilizer, preferably 2 - 30%; the soluble peat is a combination of one or more of dihydro ammonium dihydrogen ammonium, dihydro acid diammonium, dihydro potassium dihydrogen or dihydrogen potassium dihydrogen, preferably dihydro ammonium dihydrogen, The soluble peat is 2 to 60% by weight, preferably 2 to 30% by weight of the total weight of the fertilizer product; the soluble potassium salt is potassium sulfate, potassium chloride, potassium dihydrogen or dihydrogen One or a combination of potassium, preferably potassium chloride, has a soluble potassium salt content of from 2 to 50% by weight, preferably from 2 to 30% by weight.

27. A fertilizer, characterized in that the fertilizer comprises a dilute black liquor or a concentrated black liquor, a soluble trace element fertilizer; the trace element comprises one of iron, copper, boron, zinc or magnesium or One or more combinations.

The fertilizer according to claim 27, wherein the fertilizer has a fulvic acid content of 5-40% by weight, and further comprises a nitrogen content of 2-35% by weight and/or a weight percentage to P. _₂₀₅ in terms of pity 3-25% and / or K ₂ 0 percentage by weight calculated as 3-25% potassium.

The fertilizer according to claim 27, wherein a soluble trace element fertilizer is added to the diluted black liquor or concentrated black liquor, and the volume-to-weight ratio of the diluted black liquor or the concentrated black liquor to the soluble trace element fertilizer is 1000ml: 0.2-45g.

The fertilizer according to claim 27, wherein the soluble trace element fertilizer is a ferrous salt and a zinc salt, and the amount thereof is added separately per 1000 ml of the alkali and ammonium ammonium mixed straw black liquor. 0. l-15g and 0. 1-20g, can be used as field fertilizer for field crops; or the soluble trace element fertilizer is boron fertilizer and zinc salt, which is added per 1000ml alkali and ammonium The lint black liquor is added with 0.1-15 g and 0.1-20 g, respectively, and can be used as vegetable foliar fertilizer; or the soluble trace element fertilizer is boron salt, zinc salt and ferrous salt, and the amount of addition is per l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l l

The fertilizer according to claim 30, wherein the ferrous salt is ferrous sulfate; the zinc salt is zinc sulfate and/or zinc chloride, preferably zinc sulfate; Boric acid and/or borax, preferably borax.

The fertilizer according to claim 28, wherein the fertilizer has a pH of 6 to 10 and a fulvic acid weight of 5 to 40%.