CN1114578C - Process for preparing efficient phosphorous fertilizer without raw acid - Google Patents

Abstract

A method for producing high-efficiency phosphate fertilizer without raw material acid. It is characterized in that it uses organic and inorganic activators to add a certain proportion to the phosphate rock powder under certain process conditions, which can significantly improve the effectiveness of phosphorus. Phosphate rock powder is activated and then added a certain proportion of ordinary calcium superphosphate or calcium magnesium phosphate fertilizer to obtain raw material acid-free high-efficiency phosphate fertilizer. The fertilizer effect is equivalent to or slightly better than ordinary calcium superphosphate or calcium magnesium phosphate fertilizer. Its production does not require special equipment such as mixing and chemical conversion of phosphate rock powder and sulfuric acid, but only ordinary mixing equipment, which is conducive to the processing and production of existing compound fertilizer plants and the efficient utilization of medium and low-grade phosphate rock.

Description

Production method of raw material-free acid phosphate fertilizer

The invention belongs to the field of fertilizer manufacture, in particular to the production of phosphate fertilizer.

Superphosphate or calcium magnesium phosphate fertilizer produced by the reaction of sulfuric acid and phosphate rock powder is the traditional production method of phosphate fertilizer. Its production needs to consume a lot of sulfuric acid, and the strong acidity of the finished phosphate fertilizer is not good for acidic soil, and it is also not conducive to the production of compound fertilizer. . In addition, one of the biggest disadvantages of superphosphate or calcium magnesium phosphate fertilizer and other phosphate fertilizers, including ammonium phosphate, heavy calcium, nitrophosphate fertilizer, calcium magnesium phosphate fertilizer, etc., is that they are quickly fixed into slow-acting or ineffective phosphorus after being applied to the soil, which is harmful to crops. The effectiveness is not high. Generally, the utilization rate in the current season is only about 20%. How to improve the production process of phosphate fertilizer, reduce the cost, and improve the effectiveness of phosphate fertilizer has always been a hot spot in agricultural science and technology. The present invention aims at these problems after many years of research, using organic and inorganic activators to activate phosphate rock powder and adding a certain proportion of common calcium superphosphate or calcium magnesium phosphate fertilizers to obtain obvious results. Invented a process for producing high-efficiency phosphate fertilizer without raw material acid.

The purpose of the present invention is to improve the existing production process of phosphate fertilizer by the use of activator to prepare phosphate fertilizer by reacting sulfuric acid and phosphate rock powder, reducing equipment investment and loss, low production cost, strong resistance to soil fixation, and high bioavailability. It is an acid-free and high-efficiency phosphate fertilizer with good economic benefits and environmental friendliness.

The invention includes crushing, grinding, raw material mixing and stirring, drying and other processes of phosphate rock. Features of this method: activators are added during the production process of raw material-free acid phosphate fertilizers. There are two ways to add activators according to equipment and raw material conditions. 1. Add organic or inorganic activators to phosphate rock powder, mix well and add An appropriate amount of water is ground in a grinder, and the activator fully contacts with the phosphate rock powder during the grinding process to activate the phosphate rock. Add calcium superphosphate or calcium magnesium phosphate fertilizer accounting for 5-99% (weight) of the product phosphate fertilizer to the activated phosphate rock powder coming out of the grinder, stir evenly, and dry to become the product. 2. Add an appropriate amount of water to the phosphate rock powder and calcium superphosphate or calcium magnesium phosphate fertilizer accounting for 5-99% (weight) of the product phosphate fertilizer and mix evenly, then add an organic or inorganic activator, stir evenly, stack and activate, and become the product after drying .

Said inorganic activator is zeolite, bentonite, vermiculite, ammonized zeolite, ammonized bentonite, ammonized vermiculite, acidified zeolite, acidified bentonite, acidified vermiculite. Wherein zeolite, bentonite, and vermiculite are natural inorganic minerals; ammonized zeolite, ammonized bentonite, and ammonized vermiculite are ammonium saturates of zeolite, bentonite, and vermiculite respectively; acidified zeolite, acidified bentonite, and acidified vermiculite are respectively zeolite, Acid saturates of bentonite and vermiculite.

Said organic activator refers to lignin (including alkali lignin and lignosulfonate), monosodium glutamate waste liquid, alcohol waste liquid. Lignin (including alkali lignin and lignin sulfonate) is a commodity, monosodium glutamate waste liquid is obtained by concentrating waste liquid from monosodium glutamate plant, and alcohol waste liquid is obtained by concentrating waste liquid from alcohol factory. One or more of the above-mentioned organic or inorganic activators can be selected when adding organic or inorganic activators to activate phosphate rock powder to produce high-efficiency phosphate fertilizers without raw materials. When adding multiple activators, the total amount should not exceed one of them. The maximum amount that should be added. The addition of activator: the addition of zeolite accounts for 2-60% (weight) of product phosphate fertilizer, the addition of bentonite accounts for 2-60% (weight) of product phosphate fertilizer, the addition of vermiculite accounts for 2-60% (weight) of product phosphate fertilizer ), the addition of ammonium zeolite accounts for 2-60% (weight) of the product phosphate fertilizer, the addition of ammonium bentonite accounts for 2-60% (weight) of the product phosphate fertilizer, and the addition of ammonium vermiculite accounts for 2-60% of the product phosphate fertilizer (weight), acidified zeolite add-on accounts for 2-60% (weight) of product phosphate fertilizer, acidified bentonite add-on accounts for 2-60% (weight) of product phosphate fertilizer, acidified vermiculite add-on accounts for 2-60% (weight) of product phosphate fertilizer weight), lignin addition accounts for 2-50% (weight) of product phosphate fertilizer, monosodium glutamate waste liquid addition accounts for 10-75% (weight) of product phosphate fertilizer, alcohol waste liquid adds and accounts for 10-75% (weight) of product phosphate fertilizer ). Among the above activators, the ideal addition amount of zeolite, bentonite, vermiculite, ammonized zeolite, ammonized bentonite, ammonized vermiculite, acidified zeolite, acidified bentonite, and acidified vermiculite accounts for 15-25% of the product phosphate fertilizer. The ideal addition amount accounts for 4-8% of the product phosphate fertilizer. .

Different types of phosphate rock powder have different available phosphorus and total phosphorus contents, the total phosphorus content is 25-33% (P ₂ O ₅ %), and the available phosphorus is 4-8% (P ₂ O ₅ %) phosphate rock Powder such as China Kaiyang phosphate rock powder, the addition of various activators accounted for 10-30% of the weight of the product phosphate fertilizer can obtain obvious fertilizer efficiency and economic benefits. For phosphate rock powder with total phosphorus content of 22-30% (P ₂ O ₅ %) and available phosphorus less than 2% (P ₂ O ₅ %), such as Chinese Kunyang phosphate rock powder, the amount of various activators accounted for 12-45% of the weight of the product phosphate fertilizer is advisable.

In the production process of raw material-free acid high-efficiency phosphate fertilizer, the addition of calcium superphosphate or calcium magnesium phosphate fertilizer can choose one or both of them to mix in any proportion. When mixing and adding, the ratio of calcium superphosphate and calcium magnesium phosphate fertilizer is 3/7 (weight) is ideal. The addition amount of superphosphate or calcium magnesium phosphate fertilizer varies according to the type of phosphate rock powder and activator and the effective phosphorus content of superphosphate or calcium magnesium phosphate fertilizer. It is adjusted according to the requirements for the effective phosphorus and fertilizer efficiency of the product phosphate fertilizer. 5-99% (weight), the ideal addition is 15-30% (weight).

The implementation process of the present invention can take one of the following two processes according to equipment and raw material conditions: one, the phosphate rock is pulverized through an 80-200 mesh sieve, and one or more of the above-mentioned activators are added in proportion to the phosphate rock powder Various, after mixing evenly, add an appropriate amount of liquid to fully stir and grind, use a ball mill or a stirring mixer to grind into a homogeneous slurry, and place it for more than 1 hour to activate the phosphate rock powder. Then add calcium superphosphate or calcium magnesium phosphate fertilizer that accounts for 5-99% of the product phosphate fertilizer weight, stir evenly, and dry to become the product; Mix 99% superphosphate or calcium magnesium phosphate fertilizer with appropriate amount of liquid, then add the organic or inorganic activator in the above ratio, stir evenly, stack and activate for 1-7 days, and become the product after drying.

The inorganic activator zeolite, bentonite, and vermiculite added to the phosphate rock powder in the present invention have a special structure and a large ion exchange capacity, and after mixing treatment, they have a strong activation effect on the phosphate rock powder and can reduce the concentration of phosphorus in the soil. The fixation effect in . Adding organic activator lignin and monosodium glutamate waste liquid itself contains a large number of active groups such as hydroxyl, carboxyl and amine groups, which can activate phosphorus in phosphate rock powder after mixing treatment. On the basis of this activation, according to the principle of "vertical balance" (dynamic balance of fertilizer supply and fertilizer demand), it is combined with an appropriate amount of superphosphate or calcium magnesium phosphate fertilizer to produce a vertical composite effect, so that this product has quick-acting, long-acting, Efficient outstanding performance.

Quality inspection of this product: 1. Structural analysis: use X-ray diffraction technology to determine its crystal structure, and use infrared spectroscopy to analyze its bond formation. 2. Chemical analysis: use the molybdenum blue colorimetric method to determine the content of water-soluble phosphorus and available phosphorus. 3. Determination of anti-fixation ability in soil: Add 0.5g of acid-saving high-efficiency phosphate fertilizer to 400g of soil, add appropriate amount of water to keep the soil in the water state of field water holding capacity and cultivate for 2-5 days, then add 800ml of water to shake for 6 hours, filter, Measure the phosphorus content in the filtrate and the available phosphorus and water-soluble phosphorus content in the filtered soil. Determination of CK (common calcium superphosphate or calcium magnesium phosphate fertilizer) according to the above steps, and compare the resistance of the two to phosphorus fixation. Compared with CK, the phosphorus content in the filtrate of raw acid-free high-efficiency phosphate fertilizer and the content of available phosphorus and water-soluble phosphorus in the soil are higher.

Product Features:

The general fertilizer effect characteristics of the raw material-free acid high-efficiency phosphate fertilizer are strong resistance to soil fixation, quick-acting and long-acting, high fertilizer utilization rate, and high bioavailability. According to experiments, under the same amount of fertilization conditions, the raw acid-free high-efficiency phosphate fertilizer increases the yield by 8-35% compared with ordinary phosphate fertilizer, and significantly increases the phosphorus uptake of the aboveground part of corn on the red soil corn in the south.

The chemical analysis results of raw acid-free high-efficiency phosphate fertilizers show that compared with ordinary calcium superphosphate or calcium magnesium phosphate fertilizers, the proportion of water-soluble phosphorus in its effective phosphorus decreases, but the content of CaHPO ₄ .2H ₂ O in soluble phosphorus does not decrease, and The reduction of crystallinity is beneficial to improve the dynamic balance between nutrient supply and crop demand. The anti-fixation ability of non-raw acid high-efficiency phosphate fertilizer is significantly better than that of ordinary calcium superphosphate or calcium magnesium phosphate fertilizer. Under the condition of equal weight, the fertilizer effect of this product is usually better than ordinary calcium superphosphate or calcium magnesium phosphate fertilizer. Advantages of the present invention:

1. It has opened up a new technical approach for the industrialized large-scale multi-channel and efficient utilization of phosphate rock powder;

2. Reduced equipment investment for phosphate fertilizer production, enabling compound fertilizer plants or new phosphate fertilizer plants to produce phosphate fertilizers with a small amount of equipment investment;

3. There is no mixing process of sulfuric acid and phosphate rock powder in production, which greatly reduces the loss caused by equipment corrosion and is conducive to the use of low-grade phosphate rock, thus significantly reducing the production cost of phosphate fertilizer;

4. Phosphate fertilizer products have strong resistance to soil fixation, the fertilizer supply and crop fertilizer requirements are more coordinated, the utilization rate is high, the fertilizer effect is good, and it can increase production and significantly improve crop quality, significantly reduce leaching loss, and help prevent and control eutrophication in water bodies It has obvious environmental and economic benefits.

Implementation example: embodiment 1: with 100 tons of phosphate rock shown in table 1, the production process of producing no raw material acid high-efficiency phosphate fertilizer:

Table 1 Basic chemical composition of a phosphate rock composition Total P ₂ O ₅ Effective P ₂ O ₅ CaO MgO CO ₂ f _{Fe2O3 _} Al ₂ O ₃ acid insoluble matter %(quality) 34.18 6.2 46.47 0.20 1.23 3.21 1.11 1.03 10.87 1. The phosphate rock is crushed through a 80-100 mesh sieve; 2. Add 15-30 tons of ammonium bentonite activator, mix it with the phosphate rock powder, add a small amount of liquid (water in this case), and grind it into a slurry in a grinder 3. Add 12-35 tons of superphosphate or calcium magnesium phosphate fertilizer to the slurry coming out of the grinder, and stir evenly; 4. Dry to become the product. Embodiment 2: With 100 tons of phosphate rock shown in the above table 1, the production process of producing no raw material acid high-efficiency phosphate fertilizer: 1. the phosphate rock is pulverized through an 80-100 mesh sieve; 2. in the phosphate rock powder, add 12-35 3. Add 15-30 tons of ammonium bentonite activator, stir evenly with the mixture of phosphate rock powder and calcium phosphate or calcium magnesium phosphate fertilizer, stack 1-5 days; 4. Drying becomes the product. Embodiment 3: with 100 tons of phosphate rocks shown in table 2, produce the production process of raw material-free acid high-efficiency phosphate fertilizer:

Table 2 Basic chemical composition of a phosphate rock composition Total P ₂ O ₅ Effective P ₂ O ₅ CaO MgO CO ₂ f _{Fe2O3 _} Al ₂ O ₃ acid insoluble matter %(quality) 28.28 1.3 50.47 0.20 1.23 2.81 1.12 1.03 12.87 1. The ore is crushed through a 80-100 mesh sieve; 2. Add 3-12 tons of lignin activator, mix with phosphate rock powder, add a small amount of liquid, grind it into a slurry in a grinder, and place it for 1-5 hours; 3. .Add 15-40 tons of calcium superphosphate or calcium magnesium phosphate fertilizer to the slurry coming out of the grinder, and stir evenly; 4. Dry to become a product.

Claims (1)

1. The production method of raw material-free acid phosphate fertilizer: including the crushing, grinding, mixing and stirring of raw materials, drying and other processes of phosphate rock powder. Grind into a homogenate, add superphosphate or calcium magnesium phosphate fertilizer accounting for 15-30% (weight) of the product's phosphate fertilizer weight in the homogenate, stir evenly, and dry to become a product; After -30% (weight) calcium superphosphate or calcium magnesium phosphate fertilizer mixture is added an appropriate amount of water and mixed evenly, add organic or inorganic activator, stir evenly, pile up activation ripening, become product after drying; The addition amount of above-mentioned inorganic activator It is 15-25% of product phosphate fertilizer weight, and said inorganic activator is: one or more of zeolite, bentonite, vermiculite, ammonized zeolite, ammonized bentonite, ammonized vermiculite, when adding multiple activators , its total addition should not exceed the maximum value of one of the additions, the above-mentioned organic activator is lignin, and its addition accounts for 4-8% of the product phosphate fertilizer. The addition of the calcium superphosphate or calcium magnesium phosphate fertilizer can be selected one of them or can be mixed arbitrarily. The mixing ratio of calcium superphosphate or calcium magnesium phosphate fertilizer is calcium superphosphate; calcium magnesium phosphate fertilizer is 3:7 (by weight).