CN1491924A - A kind of humic acid long-acting compound fertilizer and preparation method thereof - Google Patents
A kind of humic acid long-acting compound fertilizer and preparation method thereof Download PDFInfo
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- CN1491924A CN1491924A CNA021332770A CN02133277A CN1491924A CN 1491924 A CN1491924 A CN 1491924A CN A021332770 A CNA021332770 A CN A021332770A CN 02133277 A CN02133277 A CN 02133277A CN 1491924 A CN1491924 A CN 1491924A
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- humic acid
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- 239000004021 humic acid Substances 0.000 title claims abstract description 96
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003337 fertilizer Substances 0.000 title claims abstract description 76
- 150000001875 compounds Chemical class 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 93
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000004202 carbamide Substances 0.000 claims abstract description 58
- 239000000618 nitrogen fertilizer Substances 0.000 claims abstract description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229940072033 potash Drugs 0.000 claims abstract description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 12
- 239000002686 phosphate fertilizer Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 49
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 38
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 38
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 238000009833 condensation Methods 0.000 claims description 18
- 230000005494 condensation Effects 0.000 claims description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims description 18
- 239000011574 phosphorus Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 235000019270 ammonium chloride Nutrition 0.000 claims description 16
- 239000003415 peat Substances 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000005696 Diammonium phosphate Substances 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- -1 humic acid urea-formaldehyde complexes Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 4
- 239000011591 potassium Substances 0.000 claims 4
- 229910052700 potassium Inorganic materials 0.000 claims 4
- 239000001103 potassium chloride Substances 0.000 claims 2
- 235000011164 potassium chloride Nutrition 0.000 claims 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical group [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims 2
- 235000011151 potassium sulphates Nutrition 0.000 claims 2
- 238000007605 air drying Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 5
- 239000008098 formaldehyde solution Substances 0.000 abstract description 3
- 235000013399 edible fruits Nutrition 0.000 abstract description 2
- 235000013311 vegetables Nutrition 0.000 abstract description 2
- 235000013877 carbamide Nutrition 0.000 description 48
- 229960004279 formaldehyde Drugs 0.000 description 27
- 235000019256 formaldehyde Nutrition 0.000 description 27
- 238000000034 method Methods 0.000 description 19
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 208000006558 Dental Calculus Diseases 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 235000021049 nutrient content Nutrition 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 210000003608 fece Anatomy 0.000 description 3
- 239000010871 livestock manure Substances 0.000 description 3
- 238000013268 sustained release Methods 0.000 description 3
- 239000012730 sustained-release form Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004176 ammonification Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000001038 titanium pigment Substances 0.000 description 2
- 239000002601 urease inhibitor Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Fertilizers (AREA)
Abstract
The present invention relates to long-acting compound fertilizer, and is especially a kind of long-acting compound humic acid fertilizer. The long-acting compound humic acid fertilizer consists of composite of humic acid, urea and formaldehyde in 25-40 wt% and soluble nitrogen fertilizer, phosphate fertilizer and potash fertilizer 60-75 wt%. The composite of composite of humic acid, urea and formaldehyde consists of turf, urea, ammonium and formaldehyde solution; and the soluble nitrogen fertilizer, phosphate fertilizer and potash fertilizer are in the weight ratio of 12-25 to 30-40 to 10-20. The product is suitable for various soil, especially for growing green vegetable, flower and fruit tree.
Description
Technical field
The present invention relates to durable composite fertilizer, specifically a kind of humic acid long-acting compound fertilizer and preparation method thereof.
Background technology
In the prior art, conventional chemical nitrogenous fertilizer all has good water-solubility, execute in the soil after very easily the loss, fertilizer efficiency period only can be kept 20～60 days; And phosphate fertilizer is easy to be fixed by adsorption by soil after executing in the soil, becomes invalid attitude, especially in calcareous soil.Thereby development and production can be kept nitrogenous fertilizer long-acting, and to reduce phosphate fertilizer fixed sustained-controll-release fertiliser again very necessary.
Is the invention of great significance on the fertilizer manufacturing technology with humic acid for the feedstock production compoiste fertilizer.Humic acid is a unsettled porous, network poly structure, its structure 50%～55% by amino acid, biose amine, encircle aromatic proton more, contain the oxygen functional group and constitute, huge surface energy and sorptive power are arranged.Studies show that humic acid is strong to iron, aluminium, the isoionic avidity of calcium, by complexing or sequestering action, can significantly reduce quick-acting phosphorus fixations, simultaneously, humic acid has solublization to insoluble phosphorus and the phosphorus that has been fixed.In addition, humic acid fertilizer has the volatilization of minimizing ammonia and the function of loss, and humic acid and nitrogenous fertilizer compounding application can improve nitrogen use efficiency 10%～30%.Thereby humic acid is considered to best natural phosphate fertilizer release enhancing agent and nitrogen fertilizer potentiating agent.
At present, the conventional method of making humic acid fertilizer roughly can be divided three kinds.Method (1) is with the humic acid ammonification, comprises the direct ammoniation process of ammoniacal liquor, carbonated aqueous ammonia method, pile fermentation method and acid out ammoniation process; Method (2) is to make humic acid and urea generation complexing or condensation reaction, generates the UHA complex body; Method (3) is with humic acid or ammonium humate and the simple mixing granulation of other fertilizer.These three kinds of ammonium humates that method generated and humic acid urea only have faint slow-releasing in soil, the nitrogenous fertilizer that is discharged after once base is executed is not sufficient to satisfy the nitrogenous fertilizer needs of longer crop in vegetative period.It is reported that the fertilizer efficiency of ammonium humate and humic acid urea is approximately 60～80 days.Thereby the slow-releasing problem that solves humic acid nitrogenous fertilizer complex body is the key point of development humic acid long-acting compound fertilizer.
1964, the Japan clear 38-15916 of special permission bulletin has introduced a kind of manufacture method of humic acid urea formaldehyde complex body, at first humic acid is mixed with urea, under 130 ℃ of conditions, heating is merged, and generates the humic acid urea, adds formaldehyde solution then, generate humic acid urea formaldehyde complex body, this complex body is slow release fertilizer.The weak point of this invention is: one, and urea has the possibility that generates biuret under 130 ℃ of high temperature; Its two, the formaldehyde that is added can not be fully and humic acid urea generation polycondensation, wherein can react with other active group in the humic acid greatly, thereby cause the waste of formaldehyde.In addition, this patent further is not processed into composite fertilizer to this humic acid urea formaldehyde complex body.Calendar year 2001, Chinese patent CN1299794 and CN1298851 disclose a kind of manufacture method of humic acid long-acting compound fertilizer, promptly add urease inhibitors and nitrification inhibitor in common humic acid combined fertilizer.But it is doubtful that can employed urease inhibitors and nitrification inhibitor play a role, because their major parts will be adsorbed by humic acid and lose activity.Equally in calendar year 2001; Chinese patent CN1283600A discloses a kind of production method of coated UHA; this method is as core with urea; the self-control solution that with the principal constituent is sodium hydroxide, yellow soda ash and water glass is binding agent, is that the coating agent parcel that rolls in tablets press forms with the low level coal dust.Obviously, this coated UHA only has extremely limited sustained release performance, the formed humic acid integument of this method does not have water resistance, because humic acid is a unstable structure body, possess hydrophilic property, one run into water after, the humic acid integument is water-swelling immediately just, and loses sustained release performance.
Summary of the invention
For the not enough problem of sustained release performance that solves the humic acid combined fertilizer, the object of the present invention is to provide a kind of humic acid long-acting compound fertilizer, the long-lasting problem that this composite fertilizer can not only solve nitrogenous fertilizer can be taken into account the short of phosphate fertilizer simultaneously and release, and the fertilizer efficiency period of its nitrogenous fertilizer is regulatable; Another object of the present invention is to provide the preparation method of a kind of advantages of simple technological process, humic acid long-acting compound fertilizer that equipment cost is low.
To achieve these goals, technical solution of the present invention is: its composition by weight, be made up of 25～40 parts of humic acid urea formaldehyde complex bodys and 75～60 parts of solubility azophoska, wherein: the weight ratio between the solubility azophoska is 12～25: 30～40: 10～20; The raw material of described humic acid urea formaldehyde complex body is that 30% formaldehyde is formed by 15～30 parts of peat dusts, 31～46 parts of urea, 1～2 part of ammonium chloride and 36～42 parts of concentration by weight;
Described solubility nitrogenous fertilizer source is urea, ammonium chloride and ammonium sulfide, and the source of soluble phosphoric manure is monoammonium phosphate and diammonium phosphate, and the source of solubility potash fertilizer is vitriolate of tartar and Repone K;
Its preparation method can be operated as follows:
1) the described humic acid urea formaldehyde complex body of preparation:
1. at first 9～12 parts of urea and 36～42 parts of formaldehyde being mixed, is 7～8 with saturated NaOH solution with the mixing solutions pH regulator again, and condensation is 5～30 minutes under 50～95 ℃ of conditions;
2. add 1～2 part of ammonium chloride then, pH value of solution is transferred to 4～5; Add 22～34 parts of urea in this solution for continuous, keep solution temperature 65～85 ℃ 0.2～1 hour, make urea and formaldehyde continue condensation;
3. add 15～30 parts of 60～80 order peat dusts more slowly, and constantly stir, maintain the temperature at 50～90 ℃ 0.5～2 hour, product is the black viscous fluid, through air-dry, drying, pulverizing the back is greyish white or dark gray powder.
2) prepare described composite fertilizer:
Respectively the nitrogenous fertilizer of 12～25 parts of solubilities, 30～40 parts of soluble phosphoric manures and 10～20 parts of solubility potash fertilizer are pulverized, cross 60～80 mesh sieves, even with 25～40 parts of humic acid urea formaldehyde complex body powder mixes then, add in the tablets press, with 1.2～1.5 parts polyvinyl alcohol solutions is binding agent rolling granulation, gets product after screening, oven dry, cooling;
The mole molecular ratio of 1. middle urea of step and formaldehyde is 1: 2.0～2.5; The step 2. mole molecular ratio of urea and formaldehyde is 1.3～2.0: 1; Described polyvinyl alcohol solution concentration is 5%～10%; Described solubility nitrogenous fertilizer source is urea, ammonium chloride and ammonium sulfide, and the source of soluble phosphoric manure is monoammonium phosphate and diammonium phosphate, and the source of solubility potash fertilizer is vitriolate of tartar and Repone K.
The present invention compared with prior art has following advantage:
1. solved the long-acting problem of humic acid combined fertilizer.Adopt the humic acid combined fertilizer of the inventive method preparation, not only contain ammonium humate and humic acid urea composition, main is to contain longer urea formaldehyde of fertilizer efficiency period and humic acid urea formaldehyde, thereby there is longer fertilizer efficiency period humic acid combined fertilizer of the present invention, compare 60～80 days humic acid combined fertilizer with fertilizer efficiency period in the past, its fertilizer efficiency period was 100～180 days.
2. increased the fertilizer efficiency of phosphorus potash fertilizer.The humic acid combined fertilizer of the present invention's preparation can reduce quick-acting phosphorus fixations, simultaneously insoluble phosphorus is had certain solublization.In addition, the present invention is binding agent with the polyvinyl alcohol solution, and it can join with humic acid urea formaldehyde complex body generation glue, forms network structure.This can improve fertiliser granulates intensity on the one hand, reduce the fertiliser granulates percentage of damage; Can also seal on the other hand, absorbed portion titanium pigment potash fertilizer, it is slowly discharged in soil, and then reduces the fixed ratio of phosphorus potash fertilizer in soil, increase the fertilizer efficiency of phosphorus potash fertilizer.
3. advantages of simple technological process, equipment cost is low.Because production process of the present invention does not need high temperature more than 100 ℃, thereby is easy to control, and can avoids producing humic acid urea formaldehyde long-acting fertilizer in the past and need 130 ℃ high temperature, generate the problem of sour two ureas easily, and not need specific installation.
4. applied range.Product of the present invention is applicable to various soil, is particularly useful for green vegetables, flowers, fruit tree.
Description of drawings
Fig. 1 is one embodiment of the invention diadactic structure urea formaldehyde and humic acid condensation reaction.
Fig. 2 is one embodiment of the invention ternary structural urea formaldehyde and humic acid condensation reaction.
Fig. 3 is one embodiment of the invention urea and humic acid condensation reaction.
Fig. 4 is one embodiment of the invention humic acid urea formaldehyde complex body conversion process in soil.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail.
Embodiment 1
Humic acid long-acting compound fertilizer of the present invention, its composition are made up of 25～40 parts of humic acid urea formaldehyde complex bodys and 7560 parts of solubility azophoska by weight, and wherein: the weight ratio between the solubility azophoska is 12～25: 30～40: 10～20; The raw material of described humic acid urea formaldehyde complex body is that 30% formaldehyde is formed by 15～30 parts of peat dusts, 31～46 parts of urea, 1～2 part of ammonium chloride and 36～42 parts of concentration by weight.
The preparation of its humic acid nitrogenous fertilizer complex body:
With peat dust, urea, ammonium chloride and formaldehyde is raw material, at first makes urea and formaldehyde (mole a molecular ratio be 1: 2.0～2.5) condensation 5～30 minutes under 50～95 ℃ of conditions in basic solution (pH7～8);
Add ammonium chloride then, pH value of solution is transferred to 4～5; Adding urea in this solution for continuous, to make the mole molecular ratio of urea and formaldehyde be 1.3～2.0: 1, keep solution temperature 65～85 ℃ 0.2～1 hour, make urea and formaldehyde continuation condensation;
Then, slowly add peat dust (60～80 order), and constantly stir, its objective is and make urea formaldehyde diadactic structure (referring to Fig. 1) that urea and formaldehyde reaction generate and ternary structural (referring to Fig. 2) with the further condensation of the humic acid in the peat dust, make that the amido generation condensation in the carboxyl and urea-formaldehyde condensates forms bigger macromolecular compound in the humic acid, to increase the time of releasing of nitrogenous fertilizer in soil; Also make simultaneously remaining urea and the further condensation generation of the carboxyl of humic acid humic acid urea (referring to Fig. 3) in urea and the formaldehyde reaction process, or by other functional group's complexing in the humic acid; In addition, functional groups such as amino in the humic acid and hydroxyl also can further react with free formaldehyde, thereby can reduce the formaldehyde content in the humic acid nitrogenous fertilizer complex body;
Peat dust and urea formaldehyde solution reaction time are 0.5～2 hour, and temperature of reaction is 50～90 ℃, and the humic acid urea formaldehyde complex body that is generated is the black viscous fluid, and through air-dry, drying is pulverized the back and become greyish white or dark gray powder;
The release of nitrogen in soil of described humic acid urea formaldehyde complex body is the result (referring to Fig. 4) of ammonification, enzymolysis and nitrification associating; Its nitrogenous fertilizer dispose procedure is except that the character that depends on soil, temperature and microbic activity, more depend primarily on the condensation degree of self urea formaldehyde and the condensation level of urea formaldehyde, urea and humic acid, and these can be controlled by regulation and control material proportion, temperature of reaction and reaction times.
More than prepared humic acid urea formaldehyde complex body still be porous, network poly structure, be most carboxyls by carbonyl, the amino replacement, thereby still metal ion had stronger complexing and sequestering power, so still can reduce quick-acting phosphorus fixations.In addition, it is acid that humic acid nitrogenous fertilizer complex body still is after Ammonifying bacteria is decomposed, thereby insoluble phosphorus and the phosphorus that has been fixed are still had certain solublization.
Preparation composite fertilizer:
Behind above prepared humic acid urea formaldehyde complex body powder and the abundant mixing of solubility azophoska powder, be binding agent with the polyvinyl alcohol solution, the granulation of rolling in tablets press promptly gets humic acid long-acting compound fertilizer after screening, oven dry, cooling.
The benefit that with the polyvinyl alcohol solution is binding agent is that polyvinyl alcohol is a high polymer binder, can with humic acid nitrogenous fertilizer complex body generation glue connection, form network structure.This can improve fertiliser granulates intensity on the one hand, reduces the fertiliser granulates percentage of damage; On the other hand, formed network structure can be sealed, absorbed portion titanium pigment potash fertilizer, and it is slowly discharged in soil, and then reduces the fixed ratio of phosphorus potash fertilizer in soil, increases the fertilizer efficiency of fertilizer.
Concrete operations are as follows:
Have the electrically heated tracing system one, and in the iron case of temperature adjustable, the industrial formol (a mole molecular ratio is 1: 2.4) of 10 kilograms of urea and 40 kilogram 30% is mixed, be 8.0 with saturated NaOH solution with the mixing solutions pH regulator then, keeping solution temperature is 50～60 ℃, condensation 30 minutes; Add 1.5 kilograms of ammonium chlorides then, pH value of solution is transferred to 4～5; Add 27 kilograms of urea in this solution for continuous, this moment, the mole molecular ratio of urea and formaldehyde was 1.5: 1, kept solution temperature at 75～85 ℃, made urea and formaldehyde continue condensation 0.5 hour; Slowly add 21.5 kilograms of 80 order peat dusts then, and constantly stir, keep mixture temperature 50～60 ℃ 2 hours, product is the black viscous fluid, the black viscous fluid is inclined to, be tiled in the open container, locate air-dry 5～7 days the well-ventilated, put into drying plant then, the drying temperature scope is 85～100 ℃, makes humic acid nitrogenous fertilizer complex body lose free-water, pulverizes then, cross 60 mesh sieves, product is a dark gray powder.
28.7 kilograms of 30 kilograms of 25 kilograms in urea, diammonium phosphate and vitriolate of tartar with pulverizing and mistake 60 mesh sieves of humic acid urea formaldehyde complex body powder of above preparation are mixed for 15 kilograms, add in the tablets press then, with 1.3 kilograms of polyvinyl alcohol solutions (concentration is 5%) is binding agent rolling granulation, sieve out the fertiliser granulates that particle diameter is 2.8～4.0mm, put into the drying baker oven dry then; After cooling, get product.The nutrient content of its product is as follows: N, 21.3%; P
2O
5, 13.5%; K
2O, 6.8%; The insoluble N of cold water (25 ℃), 3.6%; Available phosphorus, 11.4%.After being manured into soil, its fertilizer efficiency period was 150～180 days.
Embodiment 2
The preparation flow of humic acid urea formaldehyde complex body is identical with embodiment 1, different is, at first the industrial formol (a mole molecular ratio is 1: 2.1) with 12 kilograms of urea and 42 kilogram 30% mixes, be 7.5 with saturated NaOH solution with the mixing solutions pH regulator then, at solution temperature is under 60～70 ℃ of conditions, condensation 20 minutes; Add 2 kilograms of ammonium chlorides then, pH value of solution is transferred to 4～5; Add 24 kilograms of urea in this solution for continuous, this moment, the mole molecular ratio of urea and formaldehyde was 1.4: 1, kept solution temperature at 65～75 ℃, made urea and formaldehyde continue condensation 0.2 hour; Slowly add 20 kilograms of 60 order peat dusts then, and constantly stir, keep mixture temperature 70～80 ℃ 1.5 hours, product is through air-dry, drying is pulverized the back and is crossed 80 mesh sieves, dark gray powder humic acid urea formaldehyde complex body.
33.5 kilograms of 35 kilograms of 12 kilograms of ammonium chlorides, monoammonium phosphates and vitriolate of tartar with pulverizing and mistake 60 mesh sieves of humic acid urea formaldehyde complex body powder of above preparation are mixed for 18 kilograms; add in the tablets press then; with 1.5 kilograms of polyvinyl alcohol solutions (concentration is 10%) is binding agent rolling granulation; through screening; oven dry gets product after the cooling.The nutrient content situation of its product is as follows: N, 12.0%; P
2O
5, 18.2%; K
2O, 8.1%; The insoluble N of cold water (25 ℃), 3.7%; Available phosphorus, 16.1%.After being manured into soil, its fertilizer efficiency period was 110～130 days.
Embodiment 3
It is identical with embodiment 1 that humic acid urea formaldehyde complex body prepares flow process, different is, at first the industrial formol (a mole molecular ratio is 1: 2.4) with 9 kilograms of urea and 36 kilogram 30% mixes, be 7.8 with saturated NaOH solution with the mixing solutions pH regulator then, at solution temperature is under 80～90 ℃ of conditions, condensation 10 minutes; Add 1 kilogram of ammonium chloride then, pH value of solution is transferred to 4～5; Add 24 kilograms of urea in this solution for continuous, this moment, the mole molecular ratio of urea and formaldehyde was 1.5: 1, kept solution temperature at 70～80 ℃, made urea and formaldehyde continue condensation 0.5 hour; Slowly add 30 kilograms of 60 order peat dusts then, and constantly stir, keep mixture temperature 80～90 ℃ 0.5 hour, product is through air-dry, drying is pulverized the back and is crossed 80 mesh sieves, dark gray powder humic acid urea formaldehyde complex body.
40 kilograms of 30 kilograms of 18.5 kilograms in ammonium sulfate, diammonium phosphate and Repone K with pulverizing and mistake 60 mesh sieves of humic acid urea formaldehyde complex body powder of above preparation are mixed for 10 kilograms; add in the tablets press then; with 1.5 kilograms of polyvinyl alcohol solutions (concentration is 6%) is binding agent rolling granulation; through screening; oven dry gets product after the cooling.The nutrient content situation of its product is as follows: N, 14.9%; P
2O
5, 13.5%; K
2O, 5.8%; The insoluble N of cold water (25 ℃), 4.2%; Available phosphorus, 11.4%.After being manured into soil, its fertilizer efficiency period was 130～150 days.
Embodiment 4
It is identical with embodiment 1 that humic acid urea formaldehyde complex body prepares flow process, different is, at first the industrial formol (a mole molecular ratio is 1: 2.5) with 9 kilograms of urea and 38 kilogram 30% mixes, be 7.0 with saturated NaOH solution with the mixing solutions pH regulator then, at solution temperature is under 85～95 ℃ of conditions, condensation 5 minutes; Add 1.8 kilograms of ammonium chlorides then, pH value of solution is transferred to 4～5; Add 36.2 kilograms of urea in this solution for continuous, this moment, the mole molecular ratio of urea and formaldehyde was 2.0: 1, kept solution temperature at 70～80 ℃, made urea and formaldehyde continue condensation 1 hour; Slowly add 15 kilograms of 80 order peat dusts then, and constantly stir, keep mixture temperature 60～70 ℃ 1.5 hours, product is through air-dry, drying is pulverized the back and is crossed 80 mesh sieves, dark gray powder humic acid urea formaldehyde complex body.
25 kilograms of 40 kilograms of 15 kilograms in urea, monoammonium phosphates and Repone K with pulverizing and mistake 60 mesh sieves of humic acid urea formaldehyde complex body powder of above preparation are mixed for 18.8 kilograms; add in the tablets press then; with 1.2 kilograms of polyvinyl alcohol solutions (concentration is 8%) is binding agent rolling granulation; through screening; oven dry gets product after the cooling.The nutrient content situation of its product is as follows: N, 16.2%; P
2O
5, 20.0%; K
2O, 10.9%; The insoluble N of cold water (25 ℃), 3.4%; Available phosphorus, 18.4%.After being manured into soil, its fertilizer efficiency period was 140～160 days.
Claims (7)
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| CN100381405C (en) * | 2005-06-15 | 2008-04-16 | 石河子市高新农业科学技术服务中心 | Fulvic acid complex liquid fertilizer and production method thereof |
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