CN107827548A - A kind of Controlled Release Fertilizer and preparation method and application - Google Patents
A kind of Controlled Release Fertilizer and preparation method and application Download PDFInfo
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- CN107827548A CN107827548A CN201711072223.9A CN201711072223A CN107827548A CN 107827548 A CN107827548 A CN 107827548A CN 201711072223 A CN201711072223 A CN 201711072223A CN 107827548 A CN107827548 A CN 107827548A
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- controlled release
- release fertilizer
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- 239000003337 fertilizer Substances 0.000 title claims abstract description 75
- 238000013270 controlled release Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 86
- 239000010902 straw Substances 0.000 claims abstract description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 20
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 10
- 239000000872 buffer Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 150000001879 copper Chemical class 0.000 claims description 16
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 15
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 15
- 229940106681 chloroacetic acid Drugs 0.000 claims description 15
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001694 spray drying Methods 0.000 claims description 11
- 239000006172 buffering agent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 241000209140 Triticum Species 0.000 claims description 6
- 235000021307 Triticum Nutrition 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 240000008042 Zea mays Species 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 235000005822 corn Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 4
- 229940099427 potassium bisulfite Drugs 0.000 claims description 4
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 4
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 4
- 235000019252 potassium sulphite Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 230000003113 alkalizing effect Effects 0.000 claims description 2
- 230000021523 carboxylation Effects 0.000 claims description 2
- 238000006473 carboxylation reaction Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 abstract description 47
- 230000000694 effects Effects 0.000 abstract description 10
- 235000015097 nutrients Nutrition 0.000 abstract description 9
- 229920002678 cellulose Polymers 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000013268 sustained release Methods 0.000 abstract description 3
- 210000003608 fece Anatomy 0.000 abstract 1
- 239000010871 livestock manure Substances 0.000 abstract 1
- 238000004080 punching Methods 0.000 abstract 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 abstract 1
- 239000012730 sustained-release form Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 241000196324 Embryophyta Species 0.000 description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 description 11
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 10
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 7
- 241000227653 Lycopersicon Species 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Fertilizers (AREA)
Abstract
The present invention relates to a kind of Controlled Release Fertilizer and preparation method and application.The Controlled Release Fertilizer is using powder of straw as raw material, and sulfonation processing is carried out in the presence of sulphite, buffer, anthraquinone, mantoquita, is then handled through sodium hydroxide alkalization, most handles and is made through monoxone afterwards.The present invention also provides preparation method and the application of the Controlled Release Fertilizer.Lignin molecule amount is small in Controlled Release Fertilizer prepared by the present invention, and sulphonation rate is high, and the lignin in straw and cellulose are made full use of.The Controlled Release Fertilizer adds water punching to apply or applied as base manure or top dressing, had good sustained release effect, can effectively control the release of nutrient.
Description
Technical Field
The invention relates to a controlled release fertilizer and a preparation method and application thereof, belonging to the field of fertilizer preparation.
Background
Chemical fertilizers are important agricultural production data, play an irreplaceable role in promoting grain and agricultural production development, but the problems of excessive application, blind application and the like of chemical fertilizers exist at present, so that the cost is increased and the environment is polluted.
Cellulose and lignin are widely present in plant straws and belong to the most abundant organic renewable resources in the world. As a big agricultural country, China has 6 to 8 hundred million tons of straw resources which are abundant. The straws contain huge nutrient resources, and nearly half of the nutrients absorbed by the crops are retained in the straws. However, the straws as a kind of resources are not fully and reasonably utilized for a long time, and a large amount of straws are discarded and burnt, which not only causes the waste of resources, but also pollutes the environment. How to fully utilize the plant straws is a problem to be solved urgently in reality. Chinese patent document CN105885058A discloses a method for preparing sodium lignosulfonate from crop straws, which comprises the following steps: washing, drying and crushing crop straws; adding ionic liquid, a solvent and crop straw particles into a reaction kettle for reaction; filtering the mixture after reaction, and recovering the solvent; adding deionized water into the filtrate to precipitate lignin, separating and drying; preparing the obtained lignin into a suspension, adjusting the pH value, adding sodium sulfite, reacting and filtering; and concentrating and spray-drying the filtrate to obtain sodium lignosulfonate. In the method, the lignin is sulfonated only by using sodium sulfite, and the obtained sodium lignosulfonate has a large molecular weight, is not easy to be absorbed and utilized by crops and cannot be used as a lignin fertilizer.
On the other hand, although lignin with small molecular weight and good water solubility is beneficial to the absorption of crops, the lignin with small molecular weight and good water solubility also has some problems, for example, lignin fertilizer loss is easily caused in the fertilization and irrigation processes, and the utilization efficiency is reduced. At present, no report of directly utilizing lignin to prepare a slow-control fertilizer is found.
Disclosure of Invention
Aiming at the defects of the prior art and improving the utilization rate of the lignin fertilizer, the invention provides a controlled release fertilizer prepared by utilizing plant straws and a preparation method thereof. The prepared controlled release fertilizer has good slow release effect, can effectively control the release of nutrients, and achieves the aims of long acting and high efficiency; and the lignin has small molecular weight, high sulfonation rate and good water solubility of the fertilizer, and is beneficial to crop absorption.
The straw powder described in the specification is plant straw powder, in particular crop straw; the plant straw is pretreated in a manner known in the art, for example, by washing, drying, chopping, etc., to form a raw material.
The technical scheme of the invention is as follows:
a controlled-release fertilizer is prepared from straw powder through sulfonating in the presence of sulfite, buffering agent, anthraquinone and copper salt, alkalizing with sodium hydroxide, and treating with chloroacetic acid.
A preparation method of a controlled release fertilizer comprises the following steps: in an aqueous system, performing sulfonation treatment on straw powder in the presence of sulfite, a buffering agent, anthraquinone and copper salt; a spray drying step after sulfonation treatment; dispersing the spray-dried solid powder in an ethanol aqueous solution for alkalization; adding chloroacetic acid to perform carboxylation; wherein,
adding 10-40 parts of sulfite, 2-10 parts of a buffering agent, 0.1-0.5 part of anthraquinone and 0.5-2 parts of copper salt by 100 parts of straw powder.
Preferably, the straw powder is one or a combination of corn straw powder, wheat straw powder, rice straw powder, rape straw powder and cotton straw powder.
Preferably, the sulfite is one or a combination of potassium sulfite, potassium bisulfite, ammonium sulfite and ammonium bisulfite.
Preferably, the buffer is one or a combination of urea and ammonia.
Preferably, the copper salt is one or a combination of copper sulfate, copper chloride and copper nitrate.
Preferably, the mass ratio of the chloroacetic acid to the solid powder is 0.5-1.2: 1.
According to the invention, a preferred embodiment is: a preparation method of a controlled release fertilizer comprises the following steps:
(1) adding straw powder and water into a high-pressure reaction device, stirring, adding sulfite, a buffering agent, anthraquinone and copper salt, uniformly stirring, sealing the high-pressure reaction device, heating to 100-200 ℃, stirring for reaction for 1-10 h, and spray drying to obtain solid powder.
(2) Taking the solid powder obtained in the step (1), stirring and dispersing the solid powder in an ethanol water solution, adding sodium hydroxide, heating to 20-60 ℃, and stirring for reacting for 20-90 min;
(3) and (3) after the reaction is finished, adding chloroacetic acid into the reactant in the step (2), heating to 50-90 ℃, stirring for reaction for 1-7 h, cooling to room temperature, neutralizing with acid until the pH value is 7-8, centrifuging, and centrifugally drying to obtain the controlled release fertilizer.
According to the invention, preferably, the mass ratio of the straw powder to the water in the step (1) is 0.05-0.5: 1; further preferably, the mass ratio of the straw powder to water is 0.1-0.3: 1.
according to the invention, the straw powder in the step (1) is preferably one or a combination of corn straw powder, wheat straw powder, rice straw powder, rape straw powder and cotton straw powder.
According to the invention, preferably, the mass ratio of the sulfite to the straw powder in the step (1) is 0.1-0.4: 1. Preferably, the sulfite is one or a combination of potassium sulfite, potassium bisulfite, ammonium sulfite and ammonium bisulfite.
According to the invention, preferably, the mass ratio of the buffering agent to the straw powder in the step (1) is 0.02-0.1: 1. Preferably, the buffer is one or a combination of urea and ammonia. And (4) stabilizing the pH value of the solution.
According to the invention, preferably, the mass ratio of the anthraquinone to the straw powder in the step (1) is 0.001-0.005: 1.
According to the invention, preferably, the mass ratio of the copper salt to the straw powder in the step (1) is 0.005-0.02: 1. Preferably, the copper salt is one or a combination of copper sulfate, copper chloride and copper nitrate.
According to the invention, the reaction temperature in the step (1) is preferably 100-220 ℃, and the reaction temperature is further preferably 130-180 ℃. The preferable reaction time is 3-8 h.
According to the invention, the mass ratio of the solid powder to the ethanol water solution in the step (2) is preferably 0.05-0.5: 1; further preferably 0.06 to 0.15: 1.
According to the invention, preferably, the mass fraction of ethanol in the ethanol aqueous solution in the step (2) is 50-90%; more preferably, the mass fraction of ethanol in the ethanol aqueous solution is 65% to 80%.
According to the invention, the mass ratio of the sodium hydroxide to the solid powder in the step (2) is preferably 0.4-1.2: 1. More preferably, the mass ratio of the sodium hydroxide to the solid powder is 0.5-1: 1.
According to the invention, the reaction temperature in the step (2) is preferably 30-50 ℃, and the reaction time is preferably 30-60 min.
According to the invention, the mass ratio of the chloroacetic acid in the step (3) to the solid powder in the step (2) is preferably 0.5-1.2: 1, and more preferably 0.65-1: 1;
according to the present invention, it is preferable that the acid for neutralization in step (3) is hydrochloric acid, sulfuric acid or nitric acid.
According to the invention, the washing in the step (3) is washing with an ethanol water solution for 2-3 times; the mass fraction of ethanol in the ethanol water solution is 40-95%; more preferably, the mass fraction of ethanol in the ethanol aqueous solution is 50-85%.
According to the invention, the reaction temperature in the step (3) is preferably 60-80 ℃; the preferable reaction time is 1.5-4 h.
The above-mentioned processes for the preparation of the invention, which are not specifically described, are in accordance with the prior art.
The controlled release fertilizer prepared by the invention achieves the effect of sustained and controlled release by the adsorption effect of the carboxymethyl cellulose on lignin and other nutrients, can slowly release the lignin, improves the utilization efficiency of crops on the nutrients, and has the advantages of long acting and high efficiency
The controlled release fertilizer prepared by the method has the content of 40-60% of sodium carboxymethylcellulose and 10-20% of lignin. The release cycle of the nutrients of the controlled release fertilizer is that the release rate in 20 days is 70-85%.
The application of the controlled release fertilizer can be realized by adding water to flush the controlled release fertilizer, and can also be directly applied to soil as a base fertilizer or an additional fertilizer.
The application of the controlled release fertilizer of the invention is to dilute the prepared controlled release fertilizer by water by 1000 times (mass times) and to flush the fertilizer.
The invention has the technical characteristics and excellent effects that:
1. in the preparation process of the controlled release fertilizer, anthraquinone and copper salt are added, and have a synergistic effect, so that the separation of lignin from plant straws is accelerated, and the content of water-soluble lignin is increased. Wherein, the anthraquinone is an oxidation-reduction cycle process in the lignin extraction process, so that macromolecular lignin is rapidly decomposed into micromolecular lignin, and the lignin is an aromatic natural high molecular polymer with a complex structure and has a three-dimensional reticular space structure; the inventor finds that the copper salt complexation can accelerate the sulfonation reaction of lignin and improve the sulfonation efficiency of sulfite. In the invention, the synergistic effect of anthraquinone and copper salt realizes the purposes of small lignin molecular weight and high sulfonation rate in the prepared controlled release fertilizer.
2. The preparation method of the invention fully utilizes lignin and cellulose in the plant straws, and has the characteristics of novel preparation method, low price of raw materials, wide sources and the like. The full utilization of the plant straws firstly considers that the utilization rate of the plant straws reaches the highest, and only one of the plant straws can not be taken, but the rest is wasted; secondly, the value of the product is increased, and the added value is increased. The highest content of the contemporary cellulose and lignin in the plant straws. The lignin is an aromatic natural high molecular polymer with a complex structure and contains various functional groups, the cellulose is macromolecular polysaccharide consisting of glucose, carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose (CMCNa) is obtained after carboxymethylation of the cellulose, and the aqueous solution of the cellulose has the effects of thickening, film forming, adhesion, water retention, colloid protection, emulsification, suspension and the like, and can play a role in sustained and controlled release when used in fertilizers.
3. The lignin in the controlled release fertilizer prepared by the invention has small molecular weight (the weight average molecular weight is about 2500-4500), high sulfonation rate, good water solubility and favorable absorption and utilization of plants, and can be mixed with water in any proportion. The controlled release fertilizer prepared by the invention has good slow release effect, can effectively control the release of nutrients (the release rate is about 80 percent in 20 days of the release period), and achieves the aims of long acting and high efficiency.
4. In the controlled release fertilizer prepared by the method, lignin improves the stress resistance of crops, sulfite can provide potassium element or nitrogen element, anthraquinone can play a role in bacteriostasis, and copper element is also one of medium and trace elements required by crops, so that the controlled release fertilizer is a comprehensive high-efficiency fertilizer.
Drawings
Fig. 1 is a lignin release curve of the controlled release fertilizer prepared in example 1, wherein the abscissa is the number of days released in units of: d; the ordinate is the release rate, in units: % of the total weight of the composition.
Detailed Description
The present invention will be further described with reference to the following examples, but is not limited thereto.
Example 1:
a controlled release fertilizer and a preparation method thereof comprise the following steps:
(1) adding 2Kg of wheat straw powder into 20Kg of water, and stirring at normal temperature to obtain a straw powder aqueous solution; sequentially adding 0.8Kg of potassium sulfite, 0.04Kg of urea, 1g of anthraquinone and 3g of copper nitrate into the straw powder aqueous solution while stirring; sealing the high-pressure reaction device, heating to 160 ℃, stirring for reaction for 3 hours, and spray drying to obtain 2.81Kg of solid powder;
(2) dispersing the solid powder obtained in the step (1) into 42Kg of ethanol aqueous solution (60%) by stirring, adding 2Kg of sodium hydroxide, heating to 55 ℃, and reacting for 30min by stirring; after the reaction is finished, adding 2.5Kg of chloroacetic acid into the reactant solution, heating to 80 ℃, stirring for reaction for 3h, cooling to room temperature, neutralizing with sulfuric acid until the pH value is 7-8, centrifuging, washing with 50% ethanol water solution for 2-3 times, centrifuging and drying to obtain the controlled release fertilizer, wherein the content of sodium carboxymethylcellulose is 40.4%, and the content of lignin is 13.6%.
Release experiment of lignin of controlled release fertilizer:
dissolving 1g of controlled release fertilizer product in 15mL of water, transferring the product into a molecular weight MW8000 dialysis bag, sealing the bag, putting the bag into 2L of deionized water, leaching the bag in water at 25 ℃, and measuring the mass fraction of the nutrient content in the water in the total nutrient; the lignin release profile of the resulting controlled release fertilizer is shown in figure 1.
Example 2:
a controlled release fertilizer and a preparation method thereof comprise the following steps:
(1) adding 3Kg of corn straw powder into 20Kg of water, and stirring at normal temperature to obtain a straw powder aqueous solution; and adding 0.8Kg of ammonium sulfite, 0.18Kg of urea, 9g of anthraquinone and 30g of copper sulfate into the straw powder aqueous solution in sequence by stirring. And sealing the high-pressure reaction device, heating to 150 ℃, stirring for reaction for 5 hours, and spray-drying to obtain 4Kg of solid powder.
(2) Stirring and dispersing the solid powder obtained in the step (1) in 45Kg of ethanol aqueous solution (75%), adding 3Kg of sodium hydroxide, heating to 35 ℃, and stirring and reacting for 60 min; after the reaction is finished, adding 3Kg of chloroacetic acid into the reactant solution, heating to 70 ℃, stirring for reaction for 5h, cooling to room temperature, neutralizing with nitric acid until the pH value is 7-8, centrifuging, washing with 70% ethanol water solution for 2-3 times, centrifuging and drying to obtain the controlled release fertilizer, wherein the content of sodium carboxymethylcellulose is 47.7%, and the content of lignin is 12.1%.
Example 3:
a controlled release fertilizer and a preparation method thereof comprise the following steps:
(1) adding 2Kg of rice straw powder and 2Kg of cotton straw powder into 20Kg of water, and stirring at normal temperature to obtain a straw powder aqueous solution; sequentially adding 1.5Kg of potassium bisulfite, 0.6Kg of ammonia water, 30g of anthraquinone and 100g of copper chloride into the straw powder aqueous solution under stirring; and sealing the high-pressure reaction device, heating to 130 ℃, stirring for reaction for 7 hours, and spray-drying to obtain 5.6Kg of solid powder.
(2) Dispersing the solid powder obtained in the step (1) in 60Kg of ethanol aqueous solution (80%) by stirring, adding 3Kg of sodium hydroxide, heating to 40 ℃, and reacting for 90min by stirring; after the reaction is finished, adding 4Kg of chloroacetic acid into the reactant solution, heating to 75 ℃, stirring for reaction for 2h, cooling to room temperature, neutralizing with sulfuric acid until the pH value is 7-8, centrifuging, washing with 60% ethanol water solution for 2-3 times, and centrifuging and drying to obtain the controlled release fertilizer, wherein the content of sodium carboxymethylcellulose is 53.4% and the lignin is 11.8%.
Example 4:
a controlled release fertilizer and a preparation method thereof comprise the following steps:
(1) adding 1Kg of wheat straw powder into 20Kg of water, and stirring at normal temperature to obtain a straw powder aqueous solution; adding 0.15Kg of ammonium bisulfite, 0.04Kg of urea, 0.06Kg of ammonia water, 3g of anthraquinone, 10g of copper chloride and 10g of copper sulfate into the straw powder aqueous solution in turn by stirring; sealing the high-pressure reaction device, heating to 190 ℃, stirring for reaction for 2 hours, and spray drying to obtain 1.2Kg of solid powder.
(2) Dispersing the solid powder obtained in the step (1) into 20Kg of ethanol aqueous solution (65%) by stirring, adding 1Kg of sodium hydroxide, heating to 50 ℃, and reacting for 40min by stirring; after the reaction is finished, adding 1Kg of chloroacetic acid into the prepared reactant solution, heating to 85 ℃, stirring for reaction for 1h, cooling to room temperature, neutralizing with hydrochloric acid until the pH value is 7-8, centrifuging, washing with 80% ethanol water solution for 2-3 times, and centrifuging and drying to obtain the controlled release fertilizer, wherein the content of sodium carboxymethylcellulose is 41.9%, and the content of lignin is 15.5%.
Example 5:
a controlled release fertilizer and a preparation method thereof comprise the following steps:
(1) adding 1Kg of rape straw powder and 1Kg of wheat straw powder into 20Kg of water, and stirring at normal temperature to obtain a straw powder aqueous solution; adding 0.4Kg of ammonium sulfite, 0.1Kg of urea, 3g of anthraquinone, 6g of copper nitrate and 4g of copper sulfate into the straw powder aqueous solution in sequence while stirring; and sealing the high-pressure reaction device, heating to 140 ℃, stirring for reaction for 6 hours, and spray-drying to obtain 2.5Kg of solid powder.
(2) Dispersing the solid powder obtained in the step (1) in 30Kg of ethanol aqueous solution (85%) by stirring, adding 3Kg of sodium hydroxide, heating to 35 ℃, and reacting for 60min by stirring; after the reaction is finished, adding 2.5Kg of chloroacetic acid into the prepared reactant solution, heating to 80 ℃, stirring for reaction for 3h, cooling to room temperature, neutralizing with nitric acid until the pH value is 7-8, centrifuging, washing with 65% ethanol water solution for 2-3 times, centrifuging and drying to obtain the controlled release fertilizer, wherein the content of sodium carboxymethylcellulose is 43.6%, and the content of lignin is 12.1%.
Test example: the impact of the controlled release fertilizer and the lignin fertilizer on the growth of the tomato
Through the pot experiment, the experimental fertilizers are as follows:
test 1: lignin solution fertilizer, test 2: lignin solution + sodium carboxymethyl cellulose; test 3: the controlled release fertilizer of example 1 of the present invention. Wherein,
the lignin solution fertilizer of test 1 is a lignin solution prepared by stirring and reacting at 160 ℃ for 3 hours in the step (1) of example 1, and is concentrated until the lignin content is 10%; spray drying was not performed.
Test 2 was prepared by blending the lignin solution of test 1 (lignin content 10% after concentration) with sodium carboxymethylcellulose in the same ratio as in test 3.
Tomato variety for experiment Aiji 112 (Pink tomato)
The experiment was carried out in a pot culture in a greenhouse at 2016.8.20-2016.10.10, with 5kg of soil per pot, 3 treatments, each 4 replicates, the specific design being shown in Table 1. Selecting tomato seedlings with consistent growth vigor, transplanting the tomato seedlings into a plastic basin, treating the tomato seedlings after 15 days of seedling recovering, flushing fertilizer 1 time after the seedling recovering of the test 1 and the test 2, flushing water 1 time for a control group, flushing 400mL of water every 7 days later, and flushing water 3 times in total.
TABLE 1 test design
TABLE 2 influence of different fertilizers on physiological growth indexes of tomato
As can be seen from table 2, compared with a control, it can be seen from test 1 that lignin has a certain promotion effect on plants, and the data of test 2 shows that the addition of sodium carboxymethyl cellulose has no significant promotion effect on the growth of plants, while the promotion effect of the controlled release fertilizer prepared by test 3 on plants is obviously better than that of test 2, which indicates that the prepared controlled release fertilizer can improve the utilization rate of lignin and better promote the growth of crops.
Claims (8)
1. A controlled-release fertilizer is prepared from straw powder through sulfonating in the presence of sulfite, buffering agent, anthraquinone and copper salt, alkalizing with sodium hydroxide, and treating with chloroacetic acid.
2. A preparation method of a controlled release fertilizer comprises the following steps: in an aqueous system, performing sulfonation treatment on straw powder in the presence of sulfite, a buffering agent, anthraquinone and copper salt; a spray drying step after sulfonation treatment; dispersing the spray-dried solid powder in an ethanol aqueous solution for alkalization; adding chloroacetic acid to perform carboxylation; wherein,
adding 10-40 parts of sulfite, 2-10 parts of a buffering agent, 0.1-0.5 part of anthraquinone and 0.5-2 parts of copper salt by 100 parts of straw powder.
3. The method of preparing a controlled release fertilizer of claim 2 comprising one or more of the following conditions:
the straw powder is one or a combination of corn straw powder, wheat straw powder, rice straw powder, rape straw powder and cotton straw powder;
a1. the sulfite is one or a combination of potassium sulfite, potassium bisulfite, ammonium sulfite and ammonium bisulfite;
a2. the buffer is one or a combination of urea and ammonia water;
a3. the copper salt is one or a combination of copper sulfate, copper chloride and copper nitrate;
a4. the mass ratio of the chloroacetic acid to the solid powder is 0.5-1.2: 1.
4. The method for preparing a controlled release fertilizer of claim 2 comprising the steps of:
(1) adding straw powder and water into a high-pressure reaction device, stirring, adding sulfite, a buffering agent, anthraquinone and copper salt, uniformly stirring, sealing the high-pressure reaction device, heating to 100-200 ℃, stirring for reaction for 1-10 hours, and spray drying to obtain solid powder;
(2) taking the solid powder obtained in the step (1), stirring and dispersing the solid powder in an ethanol water solution, adding sodium hydroxide, heating to 20-60 ℃, and stirring for reacting for 20-90 min;
(3) and (3) after the reaction is finished, adding chloroacetic acid into the reactant in the step (2), heating to 50-90 ℃, stirring for reaction for 1-7 h, cooling to room temperature, neutralizing with acid until the pH value is 7-8, centrifuging, and centrifugally drying to obtain the controlled release fertilizer.
5. The method for preparing a controlled release fertilizer of claim 4, wherein step (1) further comprises one or more of the following conditions:
b1, the mass ratio of the straw powder to the water is 0.05-0.5: 1; preferably, the mass ratio of the straw powder to water is 0.1-0.3: 1;
b2, the mass ratio of the sulfite to the straw powder is 0.1-0.4: 1;
b3, the mass ratio of the buffering agent to the straw powder is 0.02-0.1: 1;
b4, wherein the mass ratio of the anthraquinone to the straw powder is 0.001-0.005: 1;
b5, the mass ratio of the copper salt to the straw powder is 0.005-0.02: 1;
b6, wherein the reaction temperature is 100-220 ℃.
6. The method for preparing a controlled release fertilizer of claim 4, wherein step (2) further comprises one or more of the following conditions:
c1, the mass ratio of the solid powder to the ethanol water solution is 0.05-0.5: 1; preferably 0.06-0.15: 1;
c2, wherein the mass fraction of ethanol in the ethanol aqueous solution is 50-90%;
c3, wherein the mass ratio of the sodium hydroxide to the solid powder is 0.4-1.2: 1; preferably, the mass ratio of the sodium hydroxide to the solid powder is 0.5-1: 1;
c4, wherein the reaction temperature is 30-50 ℃, and the reaction time is 30-60 min.
7. The method for preparing a controlled release fertilizer of claim 4, wherein step (3) further comprises one or more of the following conditions:
d1, the mass ratio of the chloroacetic acid to the solid powder in the step (2) is 0.5-1.2: 1;
d2, the acid for neutralization is hydrochloric acid, sulfuric acid or nitric acid;
d3, washing for 2-3 times by using an ethanol water solution; the mass fraction of ethanol in the ethanol water solution is 40-95%;
d4, wherein the reaction temperature is 60-80 ℃.
8. The use of the controlled release fertilizer of claim 1, wherein the controlled release fertilizer is applied by water, or directly applied to soil as a base fertilizer or top dressing.
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