CN117567197A - Synergistic diammonium phosphate and preparation method thereof - Google Patents
Synergistic diammonium phosphate and preparation method thereof Download PDFInfo
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- CN117567197A CN117567197A CN202311456574.5A CN202311456574A CN117567197A CN 117567197 A CN117567197 A CN 117567197A CN 202311456574 A CN202311456574 A CN 202311456574A CN 117567197 A CN117567197 A CN 117567197A
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- diammonium phosphate
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- 230000002195 synergetic effect Effects 0.000 title claims abstract description 241
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 235000019838 diammonium phosphate Nutrition 0.000 title claims abstract description 129
- 239000005696 Diammonium phosphate Substances 0.000 title claims abstract description 128
- 229910000388 diammonium phosphate Inorganic materials 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003223 protective agent Substances 0.000 claims abstract description 81
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical group C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 61
- 125000000524 functional group Chemical group 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 104
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 52
- 238000006243 chemical reaction Methods 0.000 claims description 50
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 150000002191 fatty alcohols Chemical class 0.000 claims description 19
- 239000003623 enhancer Substances 0.000 claims description 17
- 238000005728 strengthening Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004254 Ammonium phosphate Substances 0.000 claims description 15
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 15
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 150000003016 phosphoric acids Chemical class 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 14
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- 108010039918 Polylysine Proteins 0.000 claims description 14
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 14
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 8
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- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 7
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- 238000003306 harvesting Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000008979 phosphorus utilization Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Soil Sciences (AREA)
- Fertilizers (AREA)
Abstract
The invention provides synergistic diammonium phosphate and a preparation method thereof. The synergistic diammonium phosphate comprises: 88-97 parts by weight of diammonium phosphate, 1-5 parts by weight of synergistic carrier, 1-4 parts by weight of protective agent, 0.5-3 parts by weight of reinforcing agent and 0.5-1 part by weight of auxiliary agent, wherein the synergistic carrier is modified humic acid, the molecular weight of the modified humic acid is 80 kDa-150 kDa, the content of acidic functional groups is more than or equal to 20mmol/g, the content of carboxyl groups is more than or equal to 12mmol/g, the content of phenolic hydroxyl groups is more than or equal to 6mmol/g, O/C is more than or equal to 0.8, and E4/E6 is more than or equal to 4. Therefore, the synergistic diammonium phosphate has good product physical properties and yield increase and phosphorus reduction effects, and can further activate phosphorus and reduce the amount of fixed phosphorus in soil, thereby playing roles of improving the effectiveness of phosphorus and improving the utilization rate of phosphate fertilizer; in addition, the synergistic diammonium phosphate has positive stimulation to crops, can promote the growth of the crops and improve the yield of the crops.
Description
Technical Field
The invention relates to the technical field of fertilizers, in particular to synergistic diammonium phosphate and a preparation method thereof.
Background
The diammonium phosphate is a main agricultural phosphate fertilizer variety in China, is a high-concentration binary fertilizer for nitrogen and phosphorus, and is particularly suitable for crops happy with nitrogen and phosphorus. However, the apparent utilization rate of the phosphate fertilizer in China is only 10% -20%, the problems that the utilization rate of the phosphate fertilizer is low, the phosphate fertilizer is easy to fix, crops are difficult to absorb and utilize and the like exist, the phosphate fertilizer which cannot be utilized in the season is mainly fixed in soil in the form of low-efficiency phosphorus, and the phosphate fertilizer is equivalent to the fact that most of available phosphorus activated by industrial production of phosphate rock enters the soil in the form of fixed phosphorus which is difficult to be absorbed by crops, so that the phosphate rock resources and energy sources are wasted greatly, and the problems of environmental pollution and the like are caused.
The activity of the prior phosphate fertilizer still has great lifting potential, but the prior efficient synergistic technology of the phosphate fertilizer and the preparation method thereof still have a plurality of problems, for example, the synergistic carrier has poor stability in the industrial production process, is easily influenced by production conditions such as acid and alkali, high temperature and the like, and causes the problems of activity reduction or inactivation and the like, so that the synergistic carrier is difficult to exert the dephosphorization effect and the biological activity to the greatest extent. Therefore, the method has important significance on how to greatly improve the fertilizer efficiency of the phosphate fertilizer, realize the organic combination of the synergistic carrier and the phosphate fertilizer and the strengthening of the production process.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems:
in order to improve the effectiveness and biological activity of the common phosphate fertilizer, technicians at home and abroad form various efficient utilization technologies of the phosphate fertilizer by using physical, chemical, biological and other methods, such as a natural organic substance synergistic carrier technology, an inorganic substance synergistic carrier technology, a biological activation synergistic carrier technology and the like, and common products such as humic phosphate fertilizer, alginic acid phosphate fertilizer and the like. However, most of the efficient phosphorus utilization technologies cannot be popularized and applied on a large scale due to the limitations of technology application cost, synergistic effect, processing mode and the like; secondly, most of the phosphorus synergistic carrier is organic substances, and the stability is poor in the industrial production process, and the phosphorus synergistic carrier is easily influenced by production conditions such as acid and alkali, high temperature and the like, so that the problems of activity reduction or inactivation and the like are solved, and the synergistic carrier is difficult to exert the phosphorus dissolving effect and the biological activity to the greatest extent. Therefore, on the basis of developing a high-activity, environment-friendly and safe special synergistic carrier for the phosphate fertilizer, whether the activity loss of the synergistic carrier can be reduced in a production device and various application scenes is researched, the forward promotion effect of the biological activity of the synergistic carrier is exerted to the greatest extent, the fertilizer efficiency of the phosphate fertilizer is greatly improved, the organic combination of the synergistic carrier and the phosphate fertilizer is realized, the effect of the synergistic phosphate fertilizer is enhanced, and the breakthrough of the phosphorus synergistic technology is realized.
Through extensive research in the early stage, the inventor finds that the element composition, the molecular weight and the functional group content of humic acid can generate different influence effects on the phosphate fertilizer, for example, the modified humic acid has better phosphorus activation effect, which is provided with proper molecular weight, higher O content, higher O/C ratio, higher acid functional group and higher E4/E6 (E4/E6 can represent the aromaticity degree), and the modified humic acid is added into the phosphate fertilizer as a synergistic carrier, and is further combined with a protective agent and/or a reinforcing agent to realize the aim of reinforcing the high activity and the phosphorus removal effect of the synergistic carrier, thereby playing the roles of improving the phosphorus availability and the phosphate fertilizer utilization rate.
In view of this, in order to alleviate or solve at least one of the above mentioned problems to at least some extent, in one aspect of the present invention, the present invention provides a synergistic diammonium phosphate. According to an embodiment of the invention, the synergistic diammonium phosphate comprises: 88-97 parts by weight of diammonium phosphate, 1-5 parts by weight of synergistic carrier, 1-4 parts by weight of protective agent, 0.5-3 parts by weight of reinforcing agent and 0.5-1 part by weight of auxiliary agent, wherein the synergistic carrier is modified humic acid, the molecular weight of the modified humic acid is 80 kDa-150 kDa, the content of acidic functional groups is more than or equal to 20mmol/g, the content of carboxyl groups is more than or equal to 12mmol/g, the content of phenolic hydroxyl groups is more than or equal to 6mmol/g, O/C is more than or equal to 0.8, and E4/E6 is more than or equal to 4. The protective agent comprises at least one of organic acid, chelating agent, tert-butylhydroquinone, phytic acid and epsilon-polylysine hydrochloride; and the strengthening agent comprises at least one of higher fatty alcohol, ethylene glycol and p-toluenesulfonic acid. Therefore, the synergistic diammonium phosphate has good product physical properties and yield increase and phosphorus reduction effects, and can further activate phosphorus and reduce the fixation of phosphorus in soil, thereby playing roles of improving the effectiveness of the phosphorus and the utilization rate of the phosphorus fertilizer; in addition, the synergistic diammonium phosphate has positive stimulation to crops, can promote the growth of the crops and improve the yield of the crops. The addition of the auxiliary agent is beneficial to further improving the roundness and uniformity of the synergistic diammonium phosphate particles.
In addition, the synergistic diammonium phosphate according to the above embodiment of the present invention may further have the following additional technical features:
according to some embodiments of the invention, the protective agent satisfies at least one of the following conditions: the organic acid comprises at least one of citric acid, malic acid, gallic acid, glycine, alanine, lysine, methionine, acrylic acid and polyacrylic acid; the chelating agent comprises at least one of amino triacetic acid, disodium ethylenediamine tetraacetate, diethylenetriamine pentaacetic acid, hydroxyethyl tetraethylene diamine triacetic acid, tetrasodium iminodisuccinate, polyaspartic acid and alginic acid; based on 100 parts by weight of the protective agent, the content of the organic acid is 20-40 parts by weight, the content of the chelating agent is 20-40 parts by weight, the content of the tert-butylhydroquinone is 10-20 parts by weight, the content of the phytic acid is 5-10 parts by weight, and the content of the epsilon-polylysine hydrochloride is 5-10 parts by weight. Therefore, the protective agent has the functions of protecting and resisting oxidation on the activity of the synergistic carrier, and is beneficial to further improving the fertilizer efficiency of the synergistic diammonium phosphate.
According to some embodiments of the present invention, the higher fatty alcohol is contained in an amount of 50 to 80 parts by weight, the ethylene glycol is contained in an amount of 15 to 40 parts by weight, and the p-toluenesulfonic acid is contained in an amount of 5 to 10 parts by weight, based on 100 parts by weight of the enhancer. Therefore, the enhancer has an enhancing function on the activity of the synergistic carrier, and is beneficial to further improving the fertilizer efficiency of the synergistic diammonium phosphate.
According to some embodiments of the invention, the higher fatty alcohol comprises at least one of stearyl alcohol, cetyl alcohol, and dodecanol.
According to some embodiments of the invention, the adjuvant comprises at least one of sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium lignin sulfonate, sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, benzyl phenol polyoxyethylene ether, and phenethyl phenol polyoxyethylene ether. Thus, the overall physical properties of the synergistic diammonium phosphate are further improved.
In another aspect of the invention, the invention provides a method of preparing the synergistic diammonium phosphate described above. According to some embodiments of the invention, the method of preparing the synergistic diammonium phosphate described above comprises: (1) Adding at least one of a reinforcing agent and a protective agent, a synergistic carrier and an auxiliary agent into phosphoric acid, and heating to enable the mixture to react to obtain modified phosphoric acid containing the synergistic carrier; (2) Neutralizing the modified phosphoric acid and ammonia to form ammonium phosphate slurry; (3) Ammonifying and granulating the ammonium phosphate slurry to obtain a synergistic diammonium phosphate crude product; (4) And sequentially drying, screening and cooling the coarse product of the synergistic diammonium phosphate to obtain the synergistic diammonium phosphate. Therefore, the synergistic diammonium phosphate prepared by the method can effectively combine the synergistic carrier with phosphorus, further activate the phosphorus and improve the effectiveness of the phosphate fertilizer.
According to some embodiments of the invention, the method of preparing the synergistic diammonium phosphate described above satisfies at least one of the following conditions: adding higher fatty alcohol, glycol and p-toluenesulfonic acid into a reaction vessel, heating to 70-90 ℃, and stirring for 20-50 min to obtain the enhancer; in the step (1), heating to 100-120 ℃ and stirring for 1-3 h; in the step (1), adding a reinforcing agent, a protective agent, a synergistic carrier and an auxiliary agent into phosphoric acid for reaction; in the step (2), modified phosphoric acid and ammonia are introduced into a tubular reactor and a preneutralization reaction tank to perform neutralization reaction to respectively form ammonium phosphate slurry, and in the step (3), the ammonium phosphate slurry from the tubular reactor and the preneutralization reaction tank is respectively supplied into a granulator to further react with ammonia for ammonification granulation; the mass concentration of phosphoric acid is more than or equal to 45 percent. Therefore, the overall performance of the prepared synergistic diammonium phosphate fertilizer is improved.
According to some method embodiments of the invention, the synergistic carrier is modified humic acid, the molecular weight of the modified humic acid is 80 kDa-150 kDa, the content of acidic functional groups is more than or equal to 20mmol/g, the content of carboxyl groups is more than or equal to 12mmol/g, the content of phenolic hydroxyl groups is more than or equal to 6mmol/g, O/C is more than or equal to 0.8, and E4/E6 is more than or equal to 4.
According to some process embodiments of the present invention, the protectant comprises at least one of an organic acid, a chelating agent, tert-butylhydroquinone, phytic acid, epsilon-polylysine hydrochloride.
According to some method embodiments of the invention, the strengthening agent comprises at least one of a higher aliphatic alcohol, ethylene glycol, p-toluene sulfonic acid.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and is provided merely to illustrate the invention and is not to be construed as limiting the invention.
In one aspect of the invention, the invention provides synergistic diammonium phosphate. According to some embodiments of the invention, synergistic diammonium phosphate may include: 88 to 97 parts by weight of diammonium phosphate, 1 to 5 parts by weight of a synergistic carrier, 1 to 4 parts by weight of a protective agent, 0.5 to 3 parts by weight of a reinforcing agent and 0.5 to 1 part by weight of an auxiliary agent, for example, 88 parts by weight, 90 parts by weight, 92 parts by weight, 95 parts by weight or 97 parts by weight of diammonium phosphate, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight of a synergistic carrier, 1 part by weight, 2 parts by weight, 3 parts by weight or 4 parts by weight of a protective agent, 0.5 part by weight, 1 part by weight, 2 parts by weight or 3 parts by weight of a reinforcing agent, 0.5 part by weight, 0.6 part by weight, 0.8 part by weight or 1 part by weight of an auxiliary agent may be included in the synergistic diammonium phosphate.
According to some embodiments of the invention, the synergistic carrier may be modified humic acid, wherein the molecular weight of the modified humic acid is 80 kDa-150 kDa, the content of acidic functional groups is greater than or equal to 20mmol/g, the content of carboxyl groups is greater than or equal to 12mmol/g, the content of phenolic hydroxyl groups is greater than or equal to 6mmol/g, O/C is greater than or equal to 0.8, and E4/E6 is greater than or equal to 4. For example, the molecular weight of the modified humic acid may be 80kDa, 90kDa, 100kDa, 110kDa, 120kDa, 130kDa, 140kDa, 150kDa, etc.; the acidic functional group content of the modified humic acid may be 20mmol/g, 21mmol/g, 22mmol/g, 23mmol/g, 24mmol/g or more; the carboxyl group content of the modified humic acid may be 12mmol/g, 13mmol/g, 14mmol/g, 15mmol/g, 16mmol/g or more; the phenolic hydroxyl group content of the modified humic acid may be 6mmol/g, 7mmol/g, 8mmol/g, 9mmol/g, 10mmol/g or more; the O/C of the modified humic acid can be 0.8, 0.85, 0.9, 0.95, 1 and the like; the modified humic acid may have E4/E6 (indicating the degree of aromaticity) of 4, 4.5, 5, 5.5, 6 or the like. Therefore, the modified humic acid has a specific functional group structure, proper functional group content, proper O/C and E4/E6, and proper molecular weight distribution width, and the modified humic acid can play a good role in activating the phosphate fertilizer by being added into the phosphate fertilizer as a synergistic carrier.
In the invention, the special modified humic acid synergistic carrier for synergistic diammonium phosphate has a special phosphate-dissolving structure, the phosphate-dissolving effect is more outstanding, and the content of each component is in a proper range, the reinforcing agent and/or the protecting agent has protection and strengthening effects on the activity of the synergistic carrier, can prevent the synergistic carrier from being inactivated under the condition of acid and alkali or high temperature, prevent the functional groups from being denatured, strengthen the phosphate-dissolving effect of the synergistic carrier, reduce the fixation of soil phosphorus, improve the yield of phosphate-dissolving active substances, and further improve the phosphate-dissolving effect of the synergistic carrier. The synergistic diammonium phosphate can improve the effectiveness of phosphorus, has high fertilizer utilization rate, has forward stimulation effect on crops, can promote the growth of the crops, and can improve the crop yield.
In some embodiments of the invention, the modified humic acid can be prepared through oxidative decomposition, structural modification, ultrafiltration classification and other treatment steps.
The modified humic acid adopted in the invention can be prepared by the following steps:
(1) And mixing the humic acid precursor with an extracting agent to obtain a first mixture, and carrying out a first reaction on the first mixture at a first temperature.
Wherein the humic acid precursor may include at least one of weathered coal, lignite and peat.
Wherein the extractant may comprise at least one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium carbonate solution or a potassium carbonate solution, wherein the mass concentration of the solute in the extractant may be 2wt% to 6wt%.
Wherein, the mass ratio of the humic acid precursor to the extracting agent can be 1: (4-10).
Wherein the first temperature can be 80-120 ℃, and the first reaction time can be 1-2 h.
(2) Taking supernatant after the first reaction, adding an acid solution into the supernatant, standing, washing and precipitating to obtain the first humic acid.
Wherein the acid solution may include at least one of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and wherein the mass concentration of the solute in the acid solution is 5wt% to 30wt%.
Wherein, an acid solution can be added into the supernatant to ensure that the pH value of the supernatant is less than or equal to 1.
(3) And mixing the first humic acid with the oxidant solution to obtain a second mixture, and carrying out oxidative decomposition reaction on the second mixture at a second temperature to obtain a second humic acid solution.
Wherein the solute of the oxidizer solution may include at least one of hydrogen peroxide, sodium peroxide, and peracetic acid, and wherein the mass concentration of the solute in the oxidizer may be 3wt% to 8wt%.
Wherein, the mass ratio of the first humic acid to the oxidant solution can be 1: (0.5-1).
Wherein the pH of the second mixture may be 7 to 8.
Wherein the reaction temperature of the oxidative decomposition reaction can be 50-80 ℃, and the reaction time of the oxidative decomposition reaction can be 1-2 h.
(4) And modifying the functional group of the second humic acid to obtain a modified humic acid solution.
Wherein the modifying of the functional group of the second humic acid may comprise: adding water and a catalyst into the solution of the second humic acid to obtain a third mixture; adjusting the pH of the third mixture to 9-11; and adding a modifier into the third mixture to enable the second humic acid to generate functional group modification reaction.
Wherein the catalyst can comprise at least one of lithium chloride, phosphotungstic acid, N-dimethylacetamide, 2, 6-tetramethylpiperidine oxide and bipyridine propylene bisulfate ionic liquid; the modifier may include at least one of chloroacetic acid solution, acrylic acid solution, butenoic acid solution, glyoxylic acid solution, 3-hydroxybenzoic acid solution, 2, 4-dihydroxybenzoic acid solution, and the mass concentration of the solute in the modifier may be 5wt% to 10wt%.
Wherein the catalyst can be a mixture of lithium chloride, N-dimethylacetamide and 2, 6-tetramethylpiperidine oxide, and the mass ratio of the lithium chloride, the N, N-dimethylacetamide and the 2, 6-tetramethylpiperidine oxide in the catalyst is 1: (10-15): (0.1 to 0.2); or the catalyst can be a mixture of phosphotungstic acid, bipyridine propylene bisulfate ionic liquid and 2, 6-tetramethylpiperidine oxide, wherein the mass ratio of the phosphotungstic acid, the bipyridine propylene bisulfate ionic liquid to the 2, 6-tetramethylpiperidine oxide is 1: (5-12): (0.1-0.2).
Wherein, the mass ratio of the solution of the second humic acid, water, the catalyst and the modifier can be 1: (1-3): (0.02-0.04): (0.4-0.8).
(5) And intercepting the solution of the modified humic acid by adopting an ultrafiltration membrane, and drying the intercepted substances to obtain the modified humic acid.
The preparation specific embodiment of the modified humic acid of the invention is preferably as follows:
embodiment 1
200kg of crushed 100-mesh-sieve weathered coal and 1000kg of potassium hydroxide solution with the mass concentration of 5wt% are placed in a reaction kettle to be stirred uniformly, heated at the temperature of 100 ℃ for reaction for 1.5 hours, then the mixture is placed still for centrifugation, sediment is removed, supernatant fluid is taken, sulfuric acid solution with the mass concentration of 20wt% is added into the supernatant fluid to adjust the pH value of the solution to 1, and the mixture is placed still for centrifugation, and the sediment is washed by distilled water to obtain the first humic acid A1.
Adding 110kg of first humic acid A1 and 90kg of hydrogen peroxide solution with the mass concentration of 4wt% into a reaction kettle, stirring and mixing, adjusting the pH of the solution to 7.5, and heating and reacting for 1.5h at 70 ℃ to obtain a solution of second humic acid A2; then 400kg of water, 0.5kg of lithium chloride, 5.4kg of N, N-dimethylacetamide and 0.1kg of 2, 6-tetramethylpiperidine oxide are added into the reaction system, the pH value of the solution is regulated to 10 by using alkali solution, then 90kg of chloroacetic acid solution with the mass concentration of 9wt% is added, the temperature and the pH value of the solution are controlled to be unchanged during the period, the reaction time is 4 hours, and finally 4kg of absolute ethyl alcohol is added to terminate the reaction; and (3) passing the obtained modified humic acid solution through an ultrafiltration membrane with the pore diameter of 0.01 mu m, and spray-drying the entrapped modified humic acid to obtain the modified humic acid 1.
Embodiment 2
200kg of crushed 100-mesh-sieve weathered coal and 1200kg of potassium hydroxide solution with the mass concentration of 3wt% are placed in a reaction kettle to be stirred uniformly, heated at the temperature of 100 ℃ for 2 hours, then the mixture is placed still for centrifugation, sediment is removed, supernatant fluid is taken, sulfuric acid solution with the mass concentration of 20wt% is added into the supernatant fluid to adjust the pH value of the solution to 1, and the mixture is placed still for centrifugation, and the sediment is washed by distilled water to obtain the first humic acid B1.
120kg of first humic acid B1 and 80kg of hydrogen peroxide solution with the mass concentration of 7wt% are added into a reaction kettle, stirred and mixed, the pH value of the solution is regulated to 7.5, and the solution is heated and reacted for 1h at 70 ℃ to obtain a solution of second humic acid B2; then adding 500kg of water, 0.6kg of phosphotungstic acid, 5.3kg of bipyridine propylene bisulfate ionic liquid and 0.1kg of 2, 6-tetramethylpiperidine oxide into a reaction system, regulating the pH of the solution to 10 by using an alkali solution, then adding 140kg of acrylic acid solution with the mass concentration of 6wt%, controlling the temperature and the pH of the solution to be unchanged during the period, reacting for 5 hours, and finally adding 4kg of absolute ethyl alcohol to terminate the reaction; and (3) passing the obtained modified humic acid solution through an ultrafiltration membrane with the pore diameter of 0.01 mu m, and spray-drying the entrapped modified humic acid to obtain the modified humic acid 2.
Embodiment 3
200kg of lignite which is crushed and sieved by a 100-mesh sieve and 1200kg of potassium hydroxide solution with the mass concentration of 4wt% are placed in a reaction kettle to be uniformly stirred, heated and reacted for 1h at the temperature of 120 ℃, then the mixture is placed still for centrifugation, sediment is removed, supernatant fluid is taken, sulfuric acid solution with the mass concentration of 20wt% is added into the supernatant fluid to adjust the pH value of the solution to 1, and the mixture is placed still for centrifugation, and the sediment is washed by distilled water to obtain the first humic acid C1.
Adding 100kg of first humic acid C1 into a reaction kettle, stirring and mixing 100kg of hydrogen peroxide solution with the mass concentration of 5wt%, regulating the pH of the solution to 7.5, and heating at 70 ℃ for reaction for 1h to obtain a solution of second humic acid C2; then 600kg of water, 0.5kg of lithium chloride, 7.4kg of N, N-dimethylacetamide and 0.1kg of 2, 6-tetramethylpiperidine oxide are added into the reaction system, the pH value of the solution is regulated to 10 by using alkali solution, then 80kg of butenoic acid solution with the mass concentration of 8wt% is added, then 40kg of 2,4 dihydroxybenzoic acid solution with the mass concentration of 8wt% is added, the temperature and the pH value of the solution are controlled to be unchanged during the period, the reaction time is 4 hours, and finally 4kg of absolute ethyl alcohol is added to terminate the reaction; and (3) passing the obtained modified humic acid solution through an ultrafiltration membrane with the pore diameter of 0.01 mu m, and spray-drying the entrapped modified humic acid to obtain the modified humic acid 3.
Embodiment 4
200kg of weathered coal which is crushed and sieved by a 100-mesh sieve and 1000kg of potassium carbonate solution with the mass concentration of 6wt% are placed in a reaction kettle to be uniformly stirred, heated and reacted for 2 hours at the temperature of 100 ℃, then the mixture is placed still for centrifugation, sediment is removed, supernatant fluid is taken, sulfuric acid solution with the mass concentration of 20wt% is added into the supernatant fluid to adjust the pH value of the solution to 1, and the mixture is placed still for centrifugation, and the sediment is washed by distilled water to obtain the first humic acid D1.
Adding 120kg of first humic acid D1 and 80kg of sodium peroxide solution with the mass concentration of 8wt% into a reaction kettle, stirring and mixing, adjusting the pH of the solution to 7.5, and heating at 80 ℃ for reaction for 1h to obtain a solution of second humic acid D2; then adding 500kg of water, 0.5kg of lithium chloride, 6.2kg of N, N-dimethylacetamide and 0.1kg of 2, 6-tetramethylpiperidine oxide into the reaction system, regulating the pH of the solution to 10 by using an alkali solution, then adding 50kg of glyoxylate solution with the mass concentration of 10wt%, then adding 40kg of 3-hydroxybenzoic acid solution with the mass concentration of 10wt%, controlling the temperature and the pH of the solution to be unchanged during the period, controlling the reaction time to be 4 hours, and finally adding 4kg of absolute ethyl alcohol to terminate the reaction; and (3) passing the obtained modified humic acid solution through an ultrafiltration membrane with the pore diameter of 0.01 mu m, and spray-drying the entrapped modified humic acid to obtain the modified humic acid 4.
Embodiment 5
200kg of weathered coal which is crushed and sieved by a 100-mesh sieve and 1000kg of sodium hydroxide solution with the mass concentration of 2wt% are placed in a reaction kettle to be uniformly stirred, heated and reacted for 1.5 hours at the temperature of 100 ℃, then the mixture is placed still for centrifugation, sediment is removed, supernatant fluid is taken, sulfuric acid solution with the mass concentration of 20wt% is added into the supernatant fluid to adjust the pH value of the solution to 1, and the mixture is placed still for centrifugation, and the sediment is washed by distilled water to obtain the first humic acid E1.
Adding 100kg of first humic acid E1 and 100kg of hydrogen peroxide solution with the mass concentration of 4wt% into a reaction kettle, stirring and mixing, adjusting the pH of the solution to 7.5, and heating and reacting for 1.5h at 70 ℃ to obtain a solution of second humic acid E2; then 400kg of water, 0.5kg of lithium chloride, 5.4kg of N, N-dimethylacetamide and 0.1kg of 2, 6-tetramethylpiperidine oxide are added into the reaction system, the pH of the solution is regulated to 10 by using an alkali solution, then 30kg of chloroacetic acid solution with the mass concentration of 6wt%, 30kg of acrylic acid solution with the mass concentration of 6wt% and 40kg of butenic acid solution with the mass concentration of 6wt% are added, the temperature and the pH of the solution are controlled to be unchanged during the reaction, the reaction time is 4 hours, and finally 4kg of absolute ethyl alcohol is added for stopping the reaction; and (3) passing the obtained modified humic acid solution through an ultrafiltration membrane with the pore diameter of 0.01 mu m, and spray-drying the entrapped modified humic acid to obtain the modified humic acid 5.
According to some embodiments of the invention, the protective agent may include at least one of an organic acid, a chelating agent, tert-butylhydroquinone, phytic acid, epsilon-polylysine hydrochloride. In some embodiments of the invention, the protective agent may comprise one of the materials described above. In other embodiments of the present invention, the protective agent may include two or more of the above materials. The protective agent can protect and resist oxidation of the activity of the synergistic carrier, on one hand, the protective agent can prevent the functional groups and other characteristic structures of the synergistic carrier from being deactivated due to acid-base environment and high-temperature reaction conditions in the production process of the phosphate fertilizer, improve the antioxidation effect of the synergistic carrier, prevent the functional groups from being denatured, ensure the high activity of the synergistic carrier, and on the other hand, the protective agent can be chelated with metal elements such as magnesium, aluminum, iron and the like, and reduce the fixation of phosphorus by the elements such as magnesium, aluminum, iron and the like, thereby improving the effectiveness of the phosphorus.
According to some embodiments of the invention, the organic acid may include at least one of citric acid, malic acid, gallic acid, glycine, alanine, lysine, methionine, acrylic acid, polyacrylic acid.
According to some embodiments of the invention, the chelating agent may include at least one of aminotriacetic acid, disodium edetate, diethylenetriamine pentaacetic acid, hydroxyethyl-tethylenediamine triacetic acid, tetrasodium iminodisuccinate, polyaspartic acid, alginic acid.
According to some embodiments of the present invention, the organic acid may be contained in an amount of 20 to 40 parts by weight, the chelating agent may be contained in an amount of 20 to 40 parts by weight, the tertbutyl hydroquinone may be contained in an amount of 10 to 20 parts by weight, the phytic acid may be contained in an amount of 5 to 10 parts by weight, and the epsilon-polylysine hydrochloride may be contained in an amount of 5 to 10 parts by weight, based on 100 parts by weight of the protecting agent. For example, the organic acid may be contained in an amount of 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, the chelating agent may be contained in an amount of 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight, the tertbutyl hydroquinone may be contained in an amount of 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight or 20 parts by weight, the phytic acid may be contained in an amount of 5 parts by weight, 7 parts by weight, 9 parts by weight or 10 parts by weight, and the epsilon-polylysine hydrochloride may be contained in an amount of 5 parts by weight, 6 parts by weight, 8 parts by weight or 10 parts by weight, based on 100 parts by weight of the protecting agent.
According to some embodiments of the invention, the strengthening agent may include at least one of higher aliphatic alcohols, ethylene glycol, p-toluene sulfonic acid. The strengthening agent has strengthening function on the activity of the synergistic carrier, the synergistic carrier reacts with phosphoric acid to form phosphate substances, the phosphate substances can protect the phosphorus and reduce the fixation of the phosphorus, and the strengthening agent can further improve the yield of the phosphate dissolving substances (phosphate substances), so that the biological activity of the synergistic carrier is improved, and the effectiveness of the phosphorus is further improved.
According to some embodiments of the present invention, the reinforcing agent may include a higher fatty alcohol, ethylene glycol, and p-toluenesulfonic acid, the content of the higher fatty alcohol may be 50 to 80 parts by weight, the content of the ethylene glycol may be 15 to 40 parts by weight, and the content of the p-toluenesulfonic acid may be 5 to 10 parts by weight, based on 100 parts by weight of the reinforcing agent. The content of each component in the enhancer is within the above range, which is beneficial to improving the yield of the phosphate solubilizing substance generated by the enhancer in the synergistic carrier, thereby being beneficial to further improving the effectiveness of the fertilizer.
According to some embodiments of the invention, the higher fatty alcohol may comprise at least one of stearyl alcohol, cetyl alcohol, and dodecanol. For example, the higher fatty alcohol may be stearyl alcohol, cetyl alcohol or lauryl alcohol, and may also include two or three of stearyl alcohol, cetyl alcohol and lauryl alcohol.
According to some embodiments of the invention, the auxiliary agent may include at least one of sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium lignin sulfonate, sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, benzyl phenol polyoxyethylene ether, and phenethyl phenol polyoxyethylene ether. After the auxiliary agent is added, the synergistic carrier, the protective agent and the reinforcing agent can be quickly dissolved and uniformly distributed in the phosphoric acid, and in addition, the auxiliary agent can also improve the roundness and uniformity of finished granules of the synergistic diammonium phosphate.
In another aspect of the invention, the invention provides a method of preparing the synergistic diammonium phosphate described above. According to some embodiments of the present invention, a method of preparing the synergistic diammonium phosphate described above may include the steps of:
(1) At least one of the reinforcing agent and the protective agent, the synergistic carrier and the auxiliary agent are added into phosphoric acid, and the mixture is heated to react, so that the modified phosphoric acid containing the synergistic carrier is obtained.
According to some embodiments of the present invention, higher fatty alcohol, ethylene glycol, and p-toluenesulfonic acid may be charged into a reaction vessel (e.g., a reaction kettle), heated to 70-90 ℃, and stirred for 20-50 min to obtain a strengthening agent. For example, the reinforcing agent can be obtained by heating to 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, stirring for 20min, 25min, 30min, 40min or 50min, and uniformly mixing the higher fatty alcohol, ethylene glycol and p-toluenesulfonic acid.
According to some embodiments of the invention, in step (1), the strengthening agent, the protecting agent, the synergistic carrier and the auxiliary agent may be added to phosphoric acid to perform the reaction. According to some embodiments of the invention, in step (1), the enhancer, the protectant, the benefit carrier, and the adjuvant may be added sequentially to the phosphoric acid storage tank. Based on 100 weight parts of the prepared synergistic diammonium phosphate, 1 to 5 weight parts of synergistic carrier, 1 to 4 weight parts of protective agent, 0.5 to 3 weight parts of reinforcing agent and 0.5 to 1 weight part of auxiliary agent can be added, and the addition amount of phosphoric acid is calculated according to 88 to 97 weight parts of diammonium phosphate obtained after the phosphoric acid fully reacts. The relevant features of the synergistic carrier, the protective agent, the reinforcing agent and the auxiliary agent are described in detail above, and are not described in detail herein.
According to some embodiments of the invention, in step (1), the mixture may be heated to 100 ℃ to 120 ℃ and stirred for 1h to 3h to react to obtain the modified phosphoric acid containing the synergistic carrier. For example, the mixture may be heated to 100 ℃, 105 ℃, 110 ℃, 115 ℃, or 120 ℃ and stirred for 1h, 1.5h, 2h, 2.5h, or 3h to allow the mixture to react sufficiently to obtain modified phosphoric acid.
According to some embodiments of the invention, the mass concentration of phosphoric acid may be 45% or more, for example, the mass concentration of phosphoric acid may be 45%, 46%, 50%, 55%, etc. Therefore, the impurities such as aluminum, magnesium and the like in the phosphoric acid are less in the range, the produced diammonium phosphate product has good water solubility and high effective phosphorus content.
(2) And (3) carrying out a neutralization reaction on the modified phosphoric acid and ammonia to form ammonium phosphate slurry.
(3) Ammonifying and granulating the ammonium phosphate slurry to obtain a synergistic diammonium phosphate crude product.
According to some embodiments of the present invention, in step (2), modified phosphoric acid and ammonia may be introduced into the tubular reactor and the preneutralization reaction tank, so that the modified phosphoric acid and ammonia undergo a neutralization reaction, and an ammonium phosphate slurry is formed in the tubular reactor and the preneutralization reaction tank, respectively, and in step (3), the ammonium phosphate slurry from the tubular reactor and the preneutralization reaction tank is fed into a granulator to further react with ammonia for ammonification granulation, so as to obtain a synergistic diammonium phosphate crude product.
(4) And drying, screening and cooling the coarse product of the synergistic diammonium phosphate in sequence to obtain the synergistic diammonium phosphate.
In general, the preparation of synergistic diammonium phosphate by the method provided by the invention has at least the following advantages: (1) The modified humic acid synergistic carrier special for the synergistic diammonium phosphate has a special phosphate dissolving structure, the phosphate dissolving effect is more outstanding, and in the preparation process, the protective agent and/or the reinforcing agent has protection and reinforcing effects on the synergistic carrier, on one hand, the synergistic carrier can be prevented from being inactivated due to acid-base environment and high-temperature adverse reaction conditions in the phosphate fertilizer production process, and functional groups are prevented from being denatured, on the other hand, the reinforcing agent added by the process has reinforcing function on the activity of the synergistic carrier, the phosphate dissolving effect of the synergistic carrier can be enhanced, the phosphorus dissolving effect of soil is reduced, the yield of phosphorus dissolving active substances can be improved, and the phosphate dissolving effect of the synergistic carrier is further improved. (2) The synergistic carrier and the keep-alive technology are organically combined in the synergistic phosphate fertilizer production process, the purposes of high activity and enhanced phosphate dissolving effect of the synergistic carrier can be achieved, the effect of the original synergistic phosphate fertilizer can be achieved under the condition that the dosage of the synergistic carrier is small, the advantage of high efficiency is achieved, the prepared modified synergistic phosphate fertilizer can greatly reduce the amount of phosphorus fixed in soil, the phosphorus availability is improved, the phosphate fertilizer utilization rate is improved, and the modified synergistic phosphate fertilizer has a positive stimulation effect on crops, promotes growth and improves crop yield. (3) The preparation process of the synergistic diammonium phosphate can use the existing production device of common diammonium phosphate, or can be used for producing and preparing the synergistic diammonium phosphate by simple modification on the basis of the existing production device of common diammonium phosphate, does not influence the existing production process, and has the advantages of simple process, low cost, uniform mixing of synergistic carriers, full reaction and the like.
The invention is illustrated below by means of specific examples, which are given for illustrative purposes only and do not limit the scope of the invention in any way, as will be understood by those skilled in the art. In addition, in the examples below, materials and equipment used are commercially available unless otherwise specified. If in the following examples specific treatment conditions and treatment methods are not explicitly described, the treatment may be performed using conditions and methods well known in the art.
Example 1
And (3) preparation of a protective agent: based on 100 parts by weight of the protective agent, 40 parts by weight of citric acid, 40 parts by weight of disodium ethylenediamine tetraacetate, 10 parts by weight of tert-butylhydroquinone, 5 parts by weight of phytic acid and 5 parts by weight of epsilon-polylysine hydrochloride are sequentially added into a solid stirrer, and uniformly stirred to obtain the protective agent.
Preparing a reinforcing agent: based on 100 parts by weight of the reinforcing agent, 80 parts by weight of dodecanol, 15 parts by weight of ethylene glycol and 5 parts by weight of p-toluenesulfonic acid are put into a reaction kettle, heated to 80 ℃, and stirred for 30min to obtain the reinforcing agent.
4 parts by weight of a protective agent, 2 parts by weight of a reinforcing agent, 1 part by weight of sodium dodecyl benzene sulfonate and 5 parts by weight of modified humic acid (prepared according to the embodiment 1 above) are sequentially added into 143 parts by weight of 46% phosphoric acid, heated to 100 ℃, and stirred and reacted for 2 hours to obtain modified synergistic phosphoric acid 1 containing a synergistic carrier, the protective agent and the reinforcing agent.
The synergistic diammonium phosphate is prepared by the following steps:
(1) And (3) introducing the obtained modified synergistic phosphoric acid and liquid ammonia into the tubular reactor and the pre-neutralization reaction tank, and carrying out neutralization reaction to generate ammonium phosphate slurry.
(2) Spraying the ammonium phosphate slurry from the tubular reactor and the preneutralization tank onto a fine returning solid bed layer in a granulator, simultaneously supplying ammonia, enabling the ammonium phosphate slurry and the ammonia to further react in the granulator, carrying out ammoniation granulation, and enabling the neutralization degree to reach 1.9, thus obtaining the synergistic diammonium phosphate crude product.
(3) And drying, screening and cooling the coarse product of the synergistic diammonium phosphate in sequence to obtain the modified synergistic diammonium phosphate 1.
Example 2
And (3) preparation of a protective agent: based on 100 parts by weight of the protective agent, 35 parts by weight of acrylic acid, 30 parts by weight of polyaspartic acid, 20 parts by weight of tert-butylhydroquinone, 10 parts by weight of phytic acid and 5 parts by weight of epsilon-polylysine hydrochloride are sequentially added into a solid stirrer, and the protective agent is obtained after uniform stirring.
Preparing a reinforcing agent: based on 100 parts by weight of the reinforcing agent, 65 parts by weight of cetyl alcohol, 30 parts by weight of ethylene glycol and 5 parts by weight of p-toluenesulfonic acid were put into a reaction kettle, heated to 80 ℃ and stirred for 30min to obtain the reinforcing agent.
3 parts by weight of a protective agent, 1 part by weight of a reinforcing agent, 0.5 part by weight of fatty alcohol polyoxyethylene ether and 4 parts by weight of modified humic acid (prepared according to the embodiment 2 above) are sequentially added into 147 parts by weight of 46% phosphoric acid, heated to 100 ℃, and stirred and reacted for 2 hours to obtain modified synergistic phosphoric acid 2 containing a synergistic carrier, the protective agent and the reinforcing agent.
Modified synergistic diammonium phosphate 2 is prepared according to the production process method of the synergistic diammonium phosphate of the embodiment 1.
Example 3
And (3) preparation of a protective agent: based on 100 parts by weight of the protective agent, 15 parts by weight of citric acid, 5 parts by weight of gallic acid, 30 parts by weight of disodium ethylenediamine tetraacetate, 10 parts by weight of alginic acid, 20 parts by weight of tert-butylhydroquinone, 10 parts by weight of phytic acid and 10 parts by weight of epsilon-polylysine hydrochloride are sequentially added into a solid stirrer, and uniformly stirred to obtain the protective agent.
Preparing a reinforcing agent: based on 100 parts by weight of the reinforcing agent, 50 parts by weight of stearyl alcohol, 40 parts by weight of ethylene glycol and 10 parts by weight of p-toluenesulfonic acid are put into a reaction kettle, heated to 80 ℃ and stirred for 30min, so as to obtain the reinforcing agent.
Sequentially adding 1 part by weight of a protective agent, 0.5 part by weight of a reinforcing agent, 0.5 part by weight of sodium dodecyl benzene sulfonate and 1 part by weight of modified humic acid (prepared according to the embodiment 3 above) into 156 parts by weight of 46% phosphoric acid, heating to 100 ℃, and stirring and reacting for 2 hours to obtain modified synergistic phosphoric acid 3 containing a synergistic carrier, the protective agent and the reinforcing agent.
Modified synergistic diammonium phosphate 3 is prepared according to the production process method of the synergistic diammonium phosphate of the embodiment 1.
Comparative example 1
4 parts by weight of modified humic acid (prepared according to the above embodiment 4) was added to 150 parts by weight of 46% mass concentration phosphoric acid, heated to 100℃and stirred for 2 hours to obtain synergistic phosphoric acid containing only synergistic carrier.
The production process of the synergistic diammonium phosphate of the embodiment 1 is used for preparing common synergistic diammonium phosphate which only contains the synergistic carrier and does not contain the protective agent and the strengthening agent.
Comparative example 2
And (3) preparation of a protective agent: based on 100 parts by weight of the protective agent, 15 parts by weight of citric acid, 5 parts by weight of gallic acid, 40 parts by weight of disodium ethylenediamine tetraacetate, 20 parts by weight of tert-butylhydroquinone, 10 parts by weight of phytic acid and 10 parts by weight of epsilon-polylysine hydrochloride are sequentially added into a solid stirrer, and the protective agent is obtained after uniform stirring.
Preparing a reinforcing agent: based on 100 parts by weight of the reinforcing agent, 50 parts by weight of stearyl alcohol, 40 parts by weight of ethylene glycol and 10 parts by weight of p-toluenesulfonic acid are put into a reaction kettle, heated to 80 ℃ and stirred for 30min, so as to obtain the reinforcing agent.
Sequentially adding 1 part by weight of a protective agent, 0.5 part by weight of a reinforcing agent and 0.5 part by weight of sodium dodecyl benzene sulfonate into 158 parts by weight of phosphoric acid with the mass concentration of 46%, heating to 100 ℃, and stirring and reacting for 2 hours to obtain modified phosphoric acid only containing the protective agent and the reinforcing agent.
According to the production process method of the synergistic diammonium phosphate of the embodiment 1, common modified diammonium phosphate only containing a protective agent and a reinforcing agent is prepared.
Comparative example 3
Ordinary phosphoric acid is used to prepare ordinary diammonium phosphate without synergistic carrier, protective agent and reinforcing agent according to the production process method of diammonium phosphate of example 1.
Comparative example 4
And (3) preparation of a protective agent: based on 100 parts by weight of the protective agent, 35 parts by weight of citric acid, 30 parts by weight of disodium ethylenediamine tetraacetate, 20 parts by weight of tert-butylhydroquinone, 10 parts by weight of phytic acid and 5 parts by weight of epsilon-polylysine hydrochloride are sequentially added into a solid stirrer, and uniformly stirred to obtain the protective agent.
3 parts by weight of a protective agent, 0.5 part by weight of sodium dodecyl benzene sulfonate and 4 parts by weight of modified humic acid (prepared according to the embodiment 4 above) are sequentially added into 150 parts by weight of phosphoric acid with 46% mass concentration, heated to 100 ℃, and stirred and reacted for 2 hours to obtain modified synergistic phosphoric acid 4 containing a synergistic carrier and the protective agent.
According to the production process method of the synergistic diammonium phosphate of the embodiment 1, modified synergistic diammonium phosphate 4 containing a synergistic carrier, a protective agent and no strengthening agent is prepared.
Comparative example 5
Preparing a reinforcing agent: based on 100 parts by weight of the reinforcing agent, 65 parts by weight of stearyl alcohol, 30 parts by weight of ethylene glycol and 5 parts by weight of p-toluenesulfonic acid are put into a reaction kettle, heated to 80 ℃ and stirred for 30min, so as to obtain the reinforcing agent.
3 parts by weight of a reinforcing agent, 0.5 part by weight of sodium dodecyl benzene sulfonate and 4 parts by weight of modified humic acid (prepared according to the embodiment 5 above) are sequentially added into 150 parts by weight of phosphoric acid with 46% mass concentration, heated to 100 ℃, and stirred and reacted for 2 hours to obtain modified synergistic phosphoric acid 5 containing a synergistic carrier and the reinforcing agent.
According to the production process method of the synergistic diammonium phosphate of the embodiment 1, modified synergistic diammonium phosphate 5 containing a synergistic carrier, a reinforcing agent and no protective agent is prepared.
Fertilizer efficiency test of diammonium phosphate fertilizer of each of examples and comparative examples on winter wheat.
The test design is as follows:
test wheat variety: jimai 22
Test site: shandong Linyi
Test time: 2022, 10, 25, 2023, 6, 10
Test fertilizer: the common diammonium phosphate of comparative example 3, the common synergistic diammonium phosphate of comparative example 1, the common modified diammonium phosphate of comparative example 2, the modified synergistic diammonium phosphate 4 containing a synergistic carrier and a protective agent and no strengthening agent, the modified synergistic diammonium phosphate 5 containing a synergistic carrier and a strengthening agent and no protective agent, and the three modified synergistic diammonium phosphates of examples 1, 2 and 3.
The fertilizer efficiency verification of the synergistic phosphate fertilizer is carried out in a field, the test comprises 9 treatments, wherein the treatment 1 is that no phosphate fertilizer is applied, the treatment 2 is that the common diammonium phosphate is obtained in the comparative example 3, and the treatment 3 is that the phosphoric acid is obtained in the comparative example 1 Diammonium phosphate, treatment 4 is the diammonium phosphate obtained in comparative example 2, treatment 5 is the modified synergistic diammonium phosphate 1 obtained in example 1, treatment 6 is the modified synergistic diammonium phosphate 2 obtained in example 2, treatment 7 is the modified synergistic diammonium phosphate 3 obtained in example 3, treatment 8 is the modified synergistic diammonium phosphate 4 obtained in comparative example 4, and treatment 9 is the modified synergistic diammonium phosphate 5 obtained in comparative example 5. Each treatment area is 1 mu, the phosphorus fertilizer for test is applied according to the same phosphorus amount (except treatment 1), and the phosphorus amount (P) 2 O 5 ) 10 kg/mu, and all the nitrogen and potassium fertilizers are respectively urea and potassium chloride, and the nitrogen and potassium amounts of each treatment and the like are applied. Management of the growth period of wheat is carried out according to a local conventional cultivation technology, and the yield and phosphorus absorption of each treatment are measured after harvest.
The test results are shown in table 1:
TABLE 1
| Numbering device | Treatment of | Wheat yield (kg/mu) | Apparent utilization rate of phosphate fertilizer (%) |
| Process 1 | No phosphate fertilizer is applied | 457.3 | - |
| Process 2 | Ordinary diammonium phosphate | 601.5 | 18.0 |
| Process 3 | Common synergistic diammonium phosphate | 646.9 | 21.5 |
| Process 4 | Ordinary modified diammonium phosphate | 638.1 | 22.8 |
| Process 5 | Modified synergistic diammonium phosphate 1 | 676.7 | 26.7 |
| Process 6 | Modified synergistic diammonium phosphate 2 | 670.1 | 26.3 |
| Process 7 | Modified synergistic diammonium phosphate 3 | 680.3 | 27.8 |
| Process 8 | Modified synergistic diammonium phosphate 4 | 657.5 | 25.4 |
| Process 9 | Modified synergistic diammonium phosphate 5 | 654.3 | 25.1 |
The results in Table 1 show that, compared with the common diammonium phosphate treated by 2, the wheat yield of the modified synergistic diammonium phosphate treated by 3-9 is increased by 6.08-13.10%, and the apparent utilization rate of the phosphate fertilizer is increased by 3.5-9.8%. Compared with the common synergistic diammonium phosphate with the synergistic carrier added in the treatment of 3, the wheat yield of the modified synergistic diammonium phosphate with the synergistic carrier added in the treatment of 5-7 and the protective agent, the reinforcing agent and the synergistic carrier added in the treatment of 1-3 is increased by 3.59% -5.16%, and the apparent utilization rate of the phosphate fertilizer is increased by 4.8% -6.3%; compared with the common synergistic diammonium phosphate treated by the method 3, the wheat yield of the modified diammonium phosphate without the synergistic carrier is reduced by 1.36% by adding the protective agent and the reinforcing agent in the treatment 4, and the apparent utilization rate of the phosphate fertilizer is improved by 1.3%. As can be seen from Table 1, after the synergistic carrier is added in the production of the diammonium phosphate, the synergistic carrier has good synergistic effect on the diammonium phosphate, has the effects of stimulating the growth of crops, reducing the fixation of phosphorus, improving the effectiveness of phosphate fertilizer and improving the phosphorus absorption of crops, and can improve the yield of crops and the utilization rate of phosphate fertilizer. And after the protective agent and the reinforcing agent are added, the synergistic carrier effect is further reinforced: firstly, the protective agent has protective and antioxidation effects on the synergistic carrier, can prevent characteristic structures such as functional groups of the synergistic carrier from being deactivated due to acid-base environment and high-temperature reaction conditions in the production process of the phosphate fertilizer, improves the antioxidation effect of the synergistic carrier, prevents the functional groups from being denatured, ensures high activity of the synergistic carrier, and secondly, the protective agent can be chelated with metal elements such as magnesium, aluminum, iron and the like, reduces fixation of phosphorus by the elements such as magnesium, aluminum, iron and the like, improves the effectiveness of phosphorus, and has a certain activation effect on the phosphorus in soil after being applied to the soil; the enhancer can increase the yield of the phosphate dissolving active substance, further improve the bioavailability of phosphorus in the phosphate fertilizer and improve the fertilizer efficiency of diammonium phosphate; only the addition of the protective agent and the reinforcing agent has the protective effect on the phosphorus of the phosphate fertilizer, has better effect on improving the effectiveness of the phosphate fertilizer, but has general effect on the yield increase of crops. Meanwhile, the modified synergistic diammonium phosphate 4 without the enhancer and the modified synergistic diammonium phosphate 5 without the protectant have better yield increasing effect than the common synergistic diammonium phosphate in the treatment 3, but the treatment 8 and the treatment 9 have poorer effects than the modified treatment 5-7 with the synergistic carrier, the protectant and the enhancer, which means that the protectant or the enhancer has better enhancement effect on the synergistic carrier when being singly used, and the synergistic carrier and the enhancer are better when being matched for use.
And (3) testing the water-soluble phosphorus fixation rate of the synergistic diammonium phosphate.
Weighing about 1g (0.0001 g) of a sample with a 0.50mm sieve, putting two parts of the sample into 200mL leaching bottles, adding 100mL of water (A solution) into one part, adding 80mL of water and 20mL of 100g/L calcium chloride solution (B solution), screwing up a bottle cap, oscillating for 30min in a constant-temperature oscillating machine with the oscillating speed of 180 times/min, filtering, respectively measuring the water-soluble phosphorus content in each sample filtrate, wherein phosphorus in the filtrate A is the water-soluble phosphorus content, and subtracting the water-soluble phosphorus content in the filtrate B from the water-soluble phosphorus content in the filtrate A is the water-soluble phosphorus content fixed by calcium ions, wherein the proportion of the water-soluble phosphorus content in the filtrate A is the water-soluble phosphorus fixation rate. And comparing the water-soluble phosphorus content and the water-soluble phosphorus fixation rate in the synergistic diammonium phosphate by taking the common diammonium phosphate as a reference. The test is 8 treatments, wherein the treatment 1 is common diammonium phosphate obtained in the comparative example 3, the treatment 2 is common synergistic diammonium phosphate obtained in the comparative example 1, the treatment 3 is common modified diammonium phosphate obtained in the comparative example 2, the treatment 4 is modified synergistic diammonium phosphate 1 obtained in the example 1, the treatment 5 is modified synergistic diammonium phosphate 2 obtained in the example 2, the treatment 6 is modified synergistic diammonium phosphate 3 obtained in the example 3, the treatment 7 is modified synergistic diammonium phosphate 4 obtained in the comparative example 4, and the treatment 8 is modified synergistic diammonium phosphate 5 obtained in the comparative example 5.
The test results are shown in table 2:
TABLE 2
The results in Table 2 show that, compared with the common diammonium phosphate in treatment 1, the modified and synergistic diammonium phosphate in treatment 2-8 can reduce the fixation of phosphorus by calcium ions, and the water-soluble phosphorus fixation rate is reduced by 13.93-24.11 percent. Compared with the common synergistic diammonium phosphate with 2 synergistic carriers, the modified synergistic diammonium phosphate with 4-6 synergistic carriers and the protective agent, the reinforcing agent and the synergistic carriers simultaneously has the advantages that the water-soluble phosphorus fixation rate of 1-3 synergistic diammonium phosphate is reduced by 9.84-10.18 percent; compared with the common synergistic diammonium phosphate of the treatment 2, the water-soluble phosphorus fixation rate of the modified diammonium phosphate without the synergistic carrier is reduced by 5.95 percent by adding the protective agent and the reinforcing agent in the treatment 3. As can be seen from table 2, the synergistic carrier can reduce phosphorus fixation, improve the effectiveness of the phosphate fertilizer, and has a strengthening effect on the synergistic carrier effect after the protective agent and the strengthening agent are added, further improves the effectiveness of the diammonium phosphate, and reduces the phosphorus fixation amount; and the addition of only the protective agent and the reinforcing agent has the same effect of improving the effectiveness of the phosphate fertilizer. Meanwhile, as can be seen from table 2, treatment 7 contains synergistic carrier and protective agent, and treatment 8 contains synergistic carrier and enhancer, and the modified synergistic diammonium phosphate 5 without protective agent has better anti-fixing effect on phosphorus than the common synergistic diammonium phosphate in treatment 2, but treatment 7 and treatment 8 have poorer effects than modified synergistic diammonium phosphate 1-3 in treatment 4-6 containing synergistic carrier, protective agent and enhancer, which means that the protective agent or enhancer has better effect on synergistic carrier when used alone, and the synergistic effect is better when used together.
In order to clearly add the synergistic carrier, the protective agent and the reinforcing agent, the chemical reaction in phosphoric acid is changed, modified synergistic phosphoric acid 1-5 in examples 1-3 and comparative examples 4-5, synergistic phosphoric acid in comparative example 1, modified phosphoric acid in comparative example 2 and ordinary phosphoric acid in comparative example 3 are taken, and the detection by using a gas chromatography-mass spectrometry (GC-MS) shows that no orthophosphoric monoester exists in the ordinary phosphoric acid, and the orthophosphoric monoester can be generated in phosphoric acid after the synergistic carrier is added, and the test results are shown in table 3:
TABLE 3 Table 3
| Numbering device | Mass fraction of orthophosphoric monoester (%) |
| Ordinary phosphoric acid | 0 |
| Synergistic phosphoric acid | 0.53 |
| Modified phosphoric acid | 1.22 |
| Modified synergistic phosphoric acid 1 | 1.54 |
| Modified synergistic phosphoric acid 2 | 1.36 |
| Modified synergistic phosphoric acid 3 | 1.32 |
| Modified synergistic phosphoric acid 4 | 0.57 |
| Modified synergistic phosphoric acid 5 | 1.38 |
As shown in Table 3, the content of the orthophosphoric monoester in the modified synergistic phosphoric acid 1-3 is improved by 149.1% -190.6% compared with the synergistic phosphoric acid. Only a protective agent is added in the modified synergistic phosphoric acid 4, no reinforcing agent is added, the content of orthophosphoric monoester in phosphoric acid is not obviously influenced, the protective agent has a protective effect on a synergistic carrier, and the yield of a phosphate-dissolving active substance is not obviously improved; only the reinforcing agent is added into the modified synergistic phosphoric acid 5, the content of orthophosphoric monoester of a phosphorus-dissolving substance in the phosphoric acid is further improved, which indicates that the reinforcing agent has a reinforcing function on the activity of the synergistic carrier, the reinforcing agent can further improve the yield of the phosphorus-dissolving substance, the biological activity of the synergistic carrier and the phosphorus effectiveness. The research shows that the phosphate structure has higher phosphorus activity, and the addition of the reinforcing agent such as higher fatty alcohol, glycol, p-toluenesulfonic acid and the like can further improve the yield of the phosphate dissolving substance, improve the biological activity of the synergistic carrier and further improve the phosphorus effectiveness.
In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "other embodiments," "some particular embodiments," and the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. A synergistic diammonium phosphate, comprising: 88 to 97 weight portions of diammonium phosphate, 1 to 5 weight portions of synergistic carrier, 1 to 4 weight portions of protective agent, 0.5 to 3 weight portions of reinforcing agent and 0.5 to 1 weight portion of auxiliary agent,
the synergistic carrier is modified humic acid, the molecular weight of the modified humic acid is 80 kDa-150 kDa, the content of acidic functional groups is more than or equal to 20mmol/g, the content of carboxyl is more than or equal to 12mmol/g, the content of phenolic hydroxyl is more than or equal to 6mmol/g, O/C is more than or equal to 0.8, and E4/E6 is more than or equal to 4;
the protective agent comprises at least one of organic acid, chelating agent, tert-butyl hydroquinone, phytic acid and epsilon-polylysine hydrochloride; and
the enhancer comprises at least one of higher fatty alcohol, ethylene glycol and p-toluenesulfonic acid.
2. The synergistic diammonium phosphate as claimed in claim 1, wherein the protectant satisfies at least one of the following conditions:
the organic acid comprises at least one of citric acid, malic acid, gallic acid, glycine, alanine, lysine, methionine, acrylic acid and polyacrylic acid;
the chelating agent comprises at least one of amino triacetic acid, disodium ethylenediamine tetraacetate, diethylenetriamine pentaacetic acid, hydroxyethyl tetraethylene diamine triacetic acid, tetrasodium iminodisuccinate, polyaspartic acid and alginic acid;
Based on 100 parts by weight of the protective agent, the content of the organic acid is 20-40 parts by weight, the content of the chelating agent is 20-40 parts by weight, the content of the tert-butylhydroquinone is 10-20 parts by weight, the content of the phytic acid is 5-10 parts by weight, and the content of the epsilon-polylysine hydrochloride is 5-10 parts by weight.
3. The synergistic diammonium phosphate as claimed in claim 1, wherein the content of higher fatty alcohol is 50 to 80 parts by weight, the content of ethylene glycol is 15 to 40 parts by weight, and the content of p-toluenesulfonic acid is 5 to 10 parts by weight based on 100 parts by weight of the enhancer.
4. A synergistic diammonium phosphate as claimed in claim 3, characterized in that the higher fatty alcohol comprises at least one of stearyl alcohol, cetyl alcohol, dodecanol.
5. The synergistic diammonium phosphate as claimed in claim 1, wherein the adjuvant comprises at least one of sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium lignin sulfonate, sodium dodecyl sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, benzyl phenol polyoxyethylene ether, phenethyl phenol polyoxyethylene ether.
6. A method of preparing a synergistic diammonium phosphate as claimed in any one of claims 1 to 5, comprising:
(1) Adding at least one of a reinforcing agent and a protective agent, a synergistic carrier and an auxiliary agent into phosphoric acid, and heating to enable the mixture to react to obtain modified phosphoric acid containing the synergistic carrier;
(2) Neutralizing the modified phosphoric acid and ammonia to form ammonium phosphate slurry;
(3) Ammonifying and granulating the ammonium phosphate slurry to obtain a synergistic diammonium phosphate crude product;
(4) And sequentially drying, screening and cooling the coarse product of the synergistic diammonium phosphate to obtain the synergistic diammonium phosphate.
7. The method of claim 6, wherein at least one of the following conditions is satisfied:
adding higher fatty alcohol, glycol and p-toluenesulfonic acid into a reaction vessel, heating to 70-90 ℃, and stirring for 20-50 min to obtain the enhancer;
in the step (1), heating to 100-120 ℃ and stirring for 1-3 h;
in the step (1), adding a reinforcing agent, a protective agent, a synergistic carrier and an auxiliary agent into phosphoric acid for reaction;
in the step (2), modified phosphoric acid and ammonia are introduced into a tubular reactor and a preneutralization reaction tank to perform neutralization reaction to respectively form ammonium phosphate slurry, and in the step (3), the ammonium phosphate slurry from the tubular reactor and the preneutralization reaction tank is supplied into a granulator to further react with ammonia for ammonification granulation;
The mass concentration of the phosphoric acid is more than or equal to 45 percent.
8. The method of claim 6, wherein the synergistic carrier is modified humic acid with a molecular weight of 80 kDa-150 kDa, an acidic functional group content of 20mmol/g or more, a carboxyl content of 12mmol/g or more, a phenolic hydroxyl content of 6mmol/g or more, an O/C of 0.8 or more, and an E4/E6 of 4 or more.
9. The method of claim 6, wherein the protective agent comprises at least one of an organic acid, a chelating agent, tert-butylhydroquinone, phytic acid, epsilon-polylysine hydrochloride.
10. The method of claim 6, wherein the strengthening agent comprises at least one of higher aliphatic alcohols, ethylene glycol, and p-toluene sulfonic acid.
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