CN117586067A - Amino acid chelated organic fertilizer and production process thereof - Google Patents
Amino acid chelated organic fertilizer and production process thereof Download PDFInfo
- Publication number
- CN117586067A CN117586067A CN202311674043.3A CN202311674043A CN117586067A CN 117586067 A CN117586067 A CN 117586067A CN 202311674043 A CN202311674043 A CN 202311674043A CN 117586067 A CN117586067 A CN 117586067A
- Authority
- CN
- China
- Prior art keywords
- amino acid
- organic fertilizer
- stir
- acid chelated
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001413 amino acids Chemical class 0.000 title claims abstract description 171
- 239000003895 organic fertilizer Substances 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 238000000855 fermentation Methods 0.000 claims abstract description 35
- 230000004151 fermentation Effects 0.000 claims abstract description 35
- 239000010902 straw Substances 0.000 claims abstract description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011575 calcium Substances 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- -1 compound amino acid Chemical class 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 235000019764 Soybean Meal Nutrition 0.000 claims abstract description 11
- 239000004455 soybean meal Substances 0.000 claims abstract description 11
- 108010059892 Cellulase Proteins 0.000 claims abstract description 9
- 241000209140 Triticum Species 0.000 claims abstract description 9
- 235000021307 Triticum Nutrition 0.000 claims abstract description 9
- 240000008042 Zea mays Species 0.000 claims abstract description 9
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims abstract description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 9
- 229940106157 cellulase Drugs 0.000 claims abstract description 9
- 235000005822 corn Nutrition 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 33
- 239000003337 fertilizer Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000002244 precipitate Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 21
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 claims description 17
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 17
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 claims description 17
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- XDTYUYVIGLIFCW-UHFFFAOYSA-N 4-phenylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=CC=C1 XDTYUYVIGLIFCW-UHFFFAOYSA-N 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003957 anion exchange resin Substances 0.000 claims description 8
- 239000004021 humic acid Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000013522 chelant Substances 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 6
- 230000009920 chelation Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 229920002101 Chitin Polymers 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007853 buffer solution Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 244000168141 Geotrichum candidum Species 0.000 claims description 2
- 235000017388 Geotrichum candidum Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000002689 soil Substances 0.000 abstract description 8
- 241000894006 Bacteria Species 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 241000196324 Embryophyta Species 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 235000013619 trace mineral Nutrition 0.000 description 9
- 239000011573 trace mineral Substances 0.000 description 9
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 description 7
- 229960003067 cystine Drugs 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000703 high-speed centrifugation Methods 0.000 description 4
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 3
- 235000002566 Capsicum Nutrition 0.000 description 3
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002509 fulvic acid Substances 0.000 description 3
- 229940095100 fulvic acid Drugs 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000203593 Piper nigrum Species 0.000 description 2
- 241000758706 Piperaceae Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000035558 fertility Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000016761 Piper aduncum Nutrition 0.000 description 1
- 235000017804 Piper guineense Nutrition 0.000 description 1
- 235000008184 Piper nigrum Nutrition 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012272 crop production Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940088598 enzyme Drugs 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
- C05F17/20—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation using specific microorganisms or substances, e.g. enzymes, for activating or stimulating the treatment
-
- 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
- C05G3/80—Soil conditioners
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/10—Solid or semi-solid fertilisers, e.g. powders
- C05G5/12—Granules or flakes
-
- 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
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Tropical Medicine & Parasitology (AREA)
- Soil Sciences (AREA)
- Fertilizers (AREA)
Abstract
本发明公开了一种氨基酸螯合有机肥及其生产工艺,属于氨基酸加工技术领域,氨基酸螯合有机肥包括以下重量份原料:复合氨基酸螯合钙42‑50份、成膜液16‑22份、玉米秸秆12‑20份、小麦秸秆12‑15份、豆粕8‑12份、发酵菌种0.3‑0.5份、纤维素酶0.2‑0.4份。本发明公开了一种氨基酸螯合有机肥,原料包括复合氨基酸螯合钙、成膜液、玉米秸秆、小麦秸秆、豆粕、发酵菌种和纤维素酶,本发明制备的氨基酸有机肥可改良土壤,农作物能够直接吸收并利用氨基酸,本发明所制备的氨基酸螯合有机肥不仅对作物生长具有良好的促生效果,而且,氨基酸的生产可充分利用生物资源。The invention discloses an amino acid chelated organic fertilizer and its production process, which belongs to the technical field of amino acid processing. The amino acid chelated organic fertilizer includes the following parts by weight of raw materials: 42-50 parts of compound amino acid chelated calcium and 16-22 parts of film-forming liquid. , 12-20 parts of corn straw, 12-15 parts of wheat straw, 8-12 parts of soybean meal, 0.3-0.5 parts of fermentation bacteria, and 0.2-0.4 parts of cellulase. The invention discloses an amino acid chelated organic fertilizer. The raw materials include complex amino acid chelated calcium, film-forming liquid, corn straw, wheat straw, soybean meal, fermentation bacteria and cellulase. The amino acid organic fertilizer prepared by the invention can improve soil. Crops can directly absorb and utilize amino acids. The amino acid chelated organic fertilizer prepared by the invention not only has a good growth-promoting effect on crop growth, but also can make full use of biological resources in the production of amino acids.
Description
技术领域Technical field
本发明属于氨基酸加工技术领域,具体涉及一种氨基酸螯合有机肥及其生产工艺。The invention belongs to the technical field of amino acid processing, and specifically relates to an amino acid chelated organic fertilizer and its production process.
背景技术Background technique
肥料可以分为无机肥(化学肥料)和有机肥,无机肥可及时、快速地为作物生长提供所需养分,但过量施用会导致土壤板结及质量下降,进一步引起环境问题。相对而言,有机肥对于土壤环境的影响更小,有机肥所含养分及矿质元素对土壤酶活性、微生物数量以及土壤养分等的增加具有重要作用,但有机肥养分含量有限且肥效起效慢。因此近年来,许多厂家致力于开发改良有机肥,其中,氨基酸有机肥是研究热点之一。Fertilizers can be divided into inorganic fertilizers (chemical fertilizers) and organic fertilizers. Inorganic fertilizers can provide the nutrients needed for crop growth in a timely and rapid manner, but excessive application can lead to soil hardening and quality degradation, further causing environmental problems. Relatively speaking, organic fertilizers have less impact on the soil environment. The nutrients and mineral elements contained in organic fertilizers play an important role in increasing soil enzyme activity, the number of microorganisms, and soil nutrients. However, organic fertilizers have limited nutrient content and slow onset of fertilizer effect. . Therefore, in recent years, many manufacturers have devoted themselves to the development of improved organic fertilizers, among which amino acid organic fertilizers are one of the research hotspots.
氨基酸种类繁多且不同氨基酸生理功能不同,大部分氨基酸具有生长调节剂的功能,可以促进植物的光合作用和呼吸作用。同时,由于氨基酸中含有的羧基和氨基等官能团,使其具有一定的螯合能力,氨基酸的羧基与微量元素通过一个或多个配位键共价结合,形成稳定性的络合物。There are many types of amino acids and different physiological functions of different amino acids are different. Most amino acids have the function of growth regulators and can promote photosynthesis and respiration of plants. At the same time, due to the functional groups such as carboxyl and amino groups contained in amino acids, they have a certain chelating ability. The carboxyl groups of amino acids and trace elements are covalently combined through one or more coordination bonds to form a stable complex.
在现在农业生产过程中,作物生产上施用微量元素多采用叶面喷施的方式,某些微量元素因其相对分子质量较大,难以通过叶表扩散至植物体内,因此,利用氨基酸与微量元素的螯合能力,开发一种氨基酸螯合有机肥,其中,氨基酸微量元素络合物以氨基酸为载体,参与植物机体内蛋白质的合成,可被植物直接吸收利用,与无机肥相比,有助于提高微量元素的有效吸收,同时,有助于提高植物对微量元素的吸收和转运速率。因此,开发一种氨基酸螯合有机肥十分必要。In the current agricultural production process, the application of trace elements in crop production mostly adopts the method of foliar spraying. Some trace elements are difficult to diffuse into the plant through the leaf surface due to their relatively large molecular weight. Therefore, the use of amino acids and trace elements Based on the chelating ability, an amino acid chelated organic fertilizer was developed, in which the amino acid trace element complex uses amino acids as carriers to participate in the synthesis of protein in plants and can be directly absorbed and utilized by plants. Compared with inorganic fertilizers, it helps It improves the effective absorption of trace elements and at the same time helps increase the absorption and transport rate of trace elements by plants. Therefore, it is very necessary to develop an amino acid chelated organic fertilizer.
发明内容Contents of the invention
本发明旨在利用生物资源(动物羽毛和毛发等)等开发氨基酸螯合有机肥,旨在提高植株对微量元素的吸收效率,进而提高肥料的利用率,本发明的一个目的是提供一种氨基酸螯合有机肥,本发明的另一个目的是提供上述氨基酸螯合有机肥的其生产工艺。The present invention aims to utilize biological resources (animal feathers and hair, etc.) to develop amino acid chelated organic fertilizers, and aims to improve the absorption efficiency of trace elements by plants, thereby improving the utilization rate of fertilizers. One purpose of the present invention is to provide an amino acid Chelated organic fertilizer, another object of the present invention is to provide the production process of the above-mentioned amino acid chelated organic fertilizer.
本发明的目的可以通过以下技术方案实现:The object of the present invention can be achieved through the following technical solutions:
一种氨基酸螯合有机肥,包括以下重量份原料:An amino acid chelated organic fertilizer includes the following raw materials in parts by weight:
进一步地,所述复合氨基酸螯合钙由以下步骤制备:Further, the complex amino acid chelated calcium is prepared by the following steps:
向2mol/L的稀盐酸溶液中搅拌加入贝壳粉,搅拌至固体组分完全溶解,得到氯化钙溶液,再向氯化钙溶液中加入复合氨基酸,搅拌混合3-4h,再向体系中加入pH为10.4的NH3-NHCl3缓冲溶液调节pH至8.9-9.2,pH调毕后,得到混合溶液,将混合溶液升温至65-70℃,搅拌螯合1.2-1.5h,螯合反应完毕后,得到螯合液,将螯合液进行高速离心10-12min,离心完毕后,取上清液进行减压浓缩,再用无水乙醇透析纯化2-3d,离心分离,取沉淀,得到复合氨基酸螯合钙。Stir and add shell powder to 2mol/L dilute hydrochloric acid solution, stir until the solid components are completely dissolved to obtain a calcium chloride solution, then add complex amino acids to the calcium chloride solution, stir and mix for 3-4 hours, and then add to the system Adjust the pH to 8.9-9.2 with an NH 3 -NHCl 3 buffer solution with a pH of 10.4. After the pH adjustment is completed, a mixed solution is obtained. The mixed solution is heated to 65-70°C, stirred and chelated for 1.2-1.5 hours. After the chelation reaction is completed , to obtain the chelate solution, centrifuge the chelate solution at high speed for 10-12 minutes. After the centrifugation is completed, take the supernatant and concentrate it under reduced pressure, then dialyze and purify with absolute ethanol for 2-3 days, centrifuge, and take the precipitate to obtain the complex amino acid. Chelated calcium.
进一步地,所述2mol/L的稀盐酸溶液、贝壳粉、复合氨基酸的用量比为190-200mL:85-90g:35.4-36.0g。Further, the dosage ratio of the 2 mol/L dilute hydrochloric acid solution, shell powder, and complex amino acid is 190-200 mL: 85-90 g: 35.4-36.0 g.
进一步地,所述高速离心的离心速率为3500-4000r/min。Further, the centrifugation speed of the high-speed centrifugation is 3500-4000r/min.
进一步地,所述贝壳粉由以下步骤制备:Further, the shell powder is prepared by the following steps:
用清水冲洗贝壳表面,将处理后的贝壳用2mol/L稀盐酸浸泡30-40min,使贝壳表面的壳聚物和壳质素等溶解,取出贝壳,用蒸馏水进行冲洗8-10min,然后置于80-100℃烘箱内干燥至恒重,粉碎后过100目筛,得到贝壳粉。Rinse the shell surface with clean water, soak the treated shells in 2mol/L dilute hydrochloric acid for 30-40 minutes to dissolve the chitosan and chitin on the shell surface, take out the shells, rinse them with distilled water for 8-10 minutes, and then place them in Dry in an oven at 80-100°C until constant weight, crush and pass through a 100-mesh sieve to obtain shell powder.
进一步地,所述复合氨基酸由以下步骤制备:Further, the composite amino acid is prepared by the following steps:
步骤S1、向6-8mol/L的盐酸溶液中搅拌加入洗净干燥后的动物毛发,置于90-95℃条件下水解4-5h,水解完毕后,继续向中加入6-8mol/L的盐酸溶液,直至体系pH为1.4-1.6,得到毛发水解液;Step S1: Stir and add washed and dried animal hair to 6-8 mol/L hydrochloric acid solution, and place it at 90-95°C for hydrolysis for 4-5 hours. After the hydrolysis is completed, continue to add 6-8 mol/L of hydrochloric acid solution. hydrochloric acid solution until the pH of the system is 1.4-1.6 to obtain a hair hydrolyzate;
步骤S2、向毛发水解液中搅拌加入总量1/3的联苯-4-磺酸,混合搅拌3-4h,得到第一混液,将第一混液冷却至8-10℃,静置24h后过滤,得到酪氨酸沉淀物和第一母液,再利用201×7型阴离子交换树脂进行酪氨酸沉淀物的分离提纯,得到氨基酸A;再向第一母液中搅拌加入剩余的联苯-4-磺酸,混合搅拌2-3h,得到第二混液,将第二混液冷却至0-4℃,静置36h后过滤,得到亮氨酸沉淀物和第二母液,再利用201×7型阴离子交换树脂进行亮氨酸沉淀物的分离提纯,得到氨基酸B;最后向第二母液中搅拌加入6mol/L的氨水调节pH至4.9-5.1,静置24h后过滤,得到固体组分,固体组分置于40-45℃条件下干燥至恒重,得到氨基酸C,将氨基酸A、氨基酸B和氨基酸C按照质量比3.5-4.0:1.2-1.5:1.2-1.5混合均匀,得到复合氨基酸。Step S2: Stir and add 1/3 of the total amount of biphenyl-4-sulfonic acid to the hair hydrolyzate, mix and stir for 3-4 hours to obtain a first mixed liquid, cool the first mixed liquid to 8-10°C, and let it stand for 24 hours. Filter to obtain the tyrosine precipitate and the first mother liquor, and then use 201×7 anion exchange resin to separate and purify the tyrosine precipitate to obtain amino acid A; then stir and add the remaining biphenyl-4 to the first mother liquor. -Sulfonic acid, mix and stir for 2-3h to obtain a second mixed liquid. Cool the second mixed liquid to 0-4°C, let it stand for 36 hours and then filter it to obtain the leucine precipitate and the second mother liquid, and then use the 201×7 type anion The exchange resin is used to separate and purify the leucine precipitate to obtain amino acid B; finally, stir and add 6 mol/L ammonia water to the second mother liquor to adjust the pH to 4.9-5.1, let it stand for 24 hours and then filter, to obtain the solid component. The solid component Dry to constant weight at 40-45°C to obtain amino acid C. Mix amino acid A, amino acid B and amino acid C according to a mass ratio of 3.5-4.0:1.2-1.5:1.2-1.5 to obtain a compound amino acid.
进一步地,步骤S1中所述6-8mol/L的盐酸溶液、洗净干燥后的动物毛发的用量比为2L:1.5-1.8kg。Further, the dosage ratio of the 6-8 mol/L hydrochloric acid solution and the washed and dried animal hair described in step S1 is 2L:1.5-1.8kg.
进一步地,步骤S2中所述毛发水解液、联苯-4-磺酸的用量比为1L:180-210g。Further, the dosage ratio of the hair hydrolyzate and biphenyl-4-sulfonic acid described in step S2 is 1L:180-210g.
进一步地,所述成膜液由以下步骤制备:Further, the film-forming liquid is prepared by the following steps:
向去离子水中搅拌加入聚乙烯醇、腐殖酸、聚乙烯接枝马来酸酐和吐温-60,搅拌混合30-50min,得到成膜液。Stir and add polyvinyl alcohol, humic acid, polyethylene grafted maleic anhydride and Tween-60 to the deionized water, stir and mix for 30-50 minutes, and obtain a film-forming liquid.
进一步地,所述去离子水、聚乙烯醇、腐殖酸、聚乙烯接枝马来酸酐和吐温-60的用量比为80-90mL:35-42g:5-7g:0.5-1.0g:0.1-0.2mL。Further, the usage ratio of the deionized water, polyvinyl alcohol, humic acid, polyethylene grafted maleic anhydride and Tween-60 is 80-90mL:35-42g:5-7g:0.5-1.0g: 0.1-0.2mL.
进一步地,所述氨基酸螯合有机肥的生产工艺,包括以下步骤:Further, the production process of the amino acid chelated organic fertilizer includes the following steps:
按照重量份称取各原料,将玉米秸秆和小麦秸秆洗净烘干,用揉丝机粉碎混合,然后在110-120℃的条件下蒸汽软化2-3h,得到软化秸秆料,将软化秸秆料和豆粕转移至发酵罐中,加入发酵菌种和纤维素酶,升温至45-48℃,pH调节至6.2-6.5,恒温发酵36-48h,发酵完毕后过滤,所得固体组分置于100-120℃下灭菌15-20min,得到发酵组分,将发酵组分和复合氨基酸螯合钙搅拌混合30min,得到氨基酸螯合有机肥肥芯,再将氨基酸螯合有机肥肥芯置于喷雾转鼓造粒机中,将成膜液包覆于氨基酸螯合有机肥肥芯的表面,烘干后,得到氨基酸螯合有机肥。Weigh each raw material according to the weight portion, wash and dry the corn straw and wheat straw, crush and mix them with a kneading machine, and then steam soften them at 110-120°C for 2-3 hours to obtain softened straw material. The softened straw material Transfer the soybean meal and soybean meal to the fermentation tank, add fermentation strains and cellulase, raise the temperature to 45-48°C, adjust the pH to 6.2-6.5, ferment at a constant temperature for 36-48 hours, filter after the fermentation is completed, and place the solid component at 100- Sterilize at 120°C for 15-20 minutes to obtain the fermentation component, stir and mix the fermentation component and complex amino acid chelated calcium for 30 minutes to obtain the amino acid chelated organic fertilizer core, and then place the amino acid chelated organic fertilizer core in the spray transfer In the drum granulator, the film-forming liquid is coated on the surface of the amino acid chelated organic fertilizer fertilizer core, and after drying, the amino acid chelated organic fertilizer is obtained.
进一步地,所述发酵菌种为白地霉酵母。Further, the fermentation strain is Geotrichum candidum yeast.
本发明的有益效果:Beneficial effects of the present invention:
本发明公开了一种氨基酸螯合有机肥,原料包括复合氨基酸螯合钙、成膜液、玉米秸秆、小麦秸秆、豆粕、发酵菌种和纤维素酶,本发明制备的氨基酸有机肥可改良土壤,农作物能够直接吸收并利用氨基酸,所制备的氨基酸螯合有机肥不仅对作物生长具有良好的促生效果,而且,氨基酸的生产可充分利用生物资源。The invention discloses an amino acid chelated organic fertilizer. The raw materials include complex amino acid chelated calcium, film-forming liquid, corn straw, wheat straw, soybean meal, fermentation bacteria and cellulase. The amino acid organic fertilizer prepared by the invention can improve soil. , crops can directly absorb and utilize amino acids. The prepared amino acid chelated organic fertilizer not only has a good growth-promoting effect on crop growth, but also the production of amino acids can make full use of biological resources.
同时,本发明制备的氨基酸螯合有机肥的外层包覆有包膜,一方面,延长肥料的作用时间,另一方面,包膜中含有腐殖酸,能够促进土壤对氨基酸、微量元素和有机质的吸收作用,提高氨基酸螯合有机肥的肥力。At the same time, the outer layer of the amino acid chelated organic fertilizer prepared by the present invention is covered with a coating. On the one hand, it prolongs the action time of the fertilizer. On the other hand, the coating contains humic acid, which can promote the soil's response to amino acids, trace elements and The absorption of organic matter improves the fertility of amino acid chelated organic fertilizer.
具体实施方式Detailed ways
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
实施例1Example 1
制备复合氨基酸:Prepare complex amino acids:
毛发水解:向2L的6mol/L的盐酸溶液中搅拌加入1.5kg的洗净干燥后的动物毛发,置于90℃条件下水解4h,水解完毕后,继续向中加入6mol/L的盐酸溶液,直至体系pH为1.4,得到毛发水解液。Hair hydrolysis: Stir and add 1.5kg of washed and dried animal hair into 2L of 6mol/L hydrochloric acid solution, and place it at 90°C for hydrolysis for 4 hours. After the hydrolysis is completed, continue to add 6mol/L hydrochloric acid solution. Until the pH of the system reaches 1.4, a hair hydrolyzate is obtained.
氨基酸提取:向1L的毛发水解液中搅拌加入60g的联苯-4-磺酸(98%,购自上海麦克林生化科技有限公司),混合搅拌3h,得到第一混液,将第一混液冷却至8℃,静置24h后过滤,得到酪氨酸沉淀物和第一母液,再利用201×7型阴离子交换树脂(购自天津瀛海化集团有限公司)进行酪氨酸沉淀物的分离提纯,得到氨基酸A(酪氨酸);再向第一母液中搅拌加入120g的联苯-4-磺酸,混合搅拌2h,得到第二混液,将第二混液冷却至0℃,静置36h后过滤,得到亮氨酸沉淀物和第二母液,再利用201×7型阴离子交换树脂(购自天津瀛海化集团有限公司)进行亮氨酸沉淀物的分离提纯,得到氨基酸B(亮氨酸);最后向第二母液中搅拌加入6mol/L的氨水调节pH至4.9,静置24h后过滤,得到固体组分,固体组分置于40℃条件下干燥至恒重,得到氨基酸C(胱氨酸),将氨基酸A、氨基酸B和氨基酸C按照质量比3.5:1.2:1.2混合均匀,得到复合氨基酸,其中,氨基酸A(酪氨酸)、氨基酸B(亮氨酸)和氨基酸C(胱氨酸)的收率(相对于洗净干燥后的动物毛发重量)分别为2.5%、4.0%和5.6%,纯度分别为96%、97%、97%。Amino acid extraction: Stir and add 60g of biphenyl-4-sulfonic acid (98%, purchased from Shanghai McLean Biochemical Technology Co., Ltd.) to 1L of hair hydrolyzate, mix and stir for 3 hours to obtain the first mixed liquid, and cool the first mixed liquid. to 8°C, let it stand for 24 hours and then filter to obtain the tyrosine precipitate and the first mother liquor. Then use 201×7 anion exchange resin (purchased from Tianjin Yinghai Chemical Group Co., Ltd.) to separate and purify the tyrosine precipitate. Obtain amino acid A (tyrosine); then stir and add 120g of biphenyl-4-sulfonic acid to the first mother liquid, mix and stir for 2 hours to obtain a second mixed liquid, cool the second mixed liquid to 0°C, and let it stand for 36 hours before filtering. , obtain the leucine precipitate and the second mother liquor, and then use 201×7 type anion exchange resin (purchased from Tianjin Yinghai Chemical Group Co., Ltd.) to separate and purify the leucine precipitate to obtain amino acid B (leucine); Finally, stir and add 6 mol/L ammonia to the second mother liquor to adjust the pH to 4.9, let it stand for 24 hours and then filter to obtain a solid component. The solid component is dried at 40°C to constant weight to obtain amino acid C (cystine). ), mix amino acid A, amino acid B and amino acid C according to the mass ratio of 3.5:1.2:1.2 to obtain a compound amino acid, in which amino acid A (tyrosine), amino acid B (leucine) and amino acid C (cystine ) yields (relative to the weight of washed and dried animal hair) were 2.5%, 4.0% and 5.6% respectively, and the purity were 96%, 97% and 97% respectively.
实施例2Example 2
制备复合氨基酸:Prepare complex amino acids:
毛发水解:向2L的7mol/L的盐酸溶液中搅拌加入1.6kg的洗净干燥后的动物毛发,置于92℃条件下水解5h,水解完毕后,继续向中加入7mol/L的盐酸溶液,直至体系pH为1.5,得到毛发水解液。Hair hydrolysis: Stir and add 1.6kg of washed and dried animal hair into 2L of 7mol/L hydrochloric acid solution, and place it at 92°C for hydrolysis for 5 hours. After the hydrolysis is completed, continue to add 7mol/L hydrochloric acid solution. Until the pH of the system reaches 1.5, a hair hydrolyzate is obtained.
氨基酸提取:向1L的毛发水解液中搅拌加入64g的联苯-4-磺酸(98%,购自上海麦克林生化科技有限公司),混合搅拌4h,得到第一混液,将第一混液冷却至9℃,静置24h后过滤,得到酪氨酸沉淀物和第一母液,再利用201×7型阴离子交换树脂(购自天津瀛海化集团有限公司)进行酪氨酸沉淀物的分离提纯,得到氨基酸A(酪氨酸);再向第一母液中搅拌加入125g的联苯-4-磺酸,混合搅拌3h,得到第二混液,将第二混液冷却至2℃,静置36h后过滤,得到亮氨酸沉淀物和第二母液,再利用201×7型阴离子交换树脂(购自天津瀛海化集团有限公司)进行亮氨酸沉淀物的分离提纯,得到氨基酸B(亮氨酸);最后向第二母液中搅拌加入6mol/L的氨水调节pH至5.0,静置24h后过滤,得到固体组分,固体组分置于42℃条件下干燥至恒重,得到氨基酸C(胱氨酸),将氨基酸A、氨基酸B和氨基酸C按照质量比3.8:1.4:1.3混合均匀,得到复合氨基酸,其中,氨基酸A(酪氨酸)、氨基酸B(亮氨酸)和氨基酸C(胱氨酸)的收率(相对于洗净干燥后的动物毛发重量)分别为2.5%、4.0%和5.8%,纯度分别为97%、97%、98%。Amino acid extraction: Stir and add 64g of biphenyl-4-sulfonic acid (98%, purchased from Shanghai McLean Biochemical Technology Co., Ltd.) to 1L of hair hydrolyzate, mix and stir for 4 hours to obtain the first mixed liquid, and cool the first mixed liquid. to 9°C, let it stand for 24 hours and then filter to obtain the tyrosine precipitate and the first mother liquor. Then use 201×7 anion exchange resin (purchased from Tianjin Yinghai Chemical Group Co., Ltd.) to separate and purify the tyrosine precipitate. Obtain amino acid A (tyrosine); then stir and add 125g of biphenyl-4-sulfonic acid to the first mother liquid, mix and stir for 3 hours to obtain a second mixed liquid, cool the second mixed liquid to 2°C, let it stand for 36 hours, and then filter , obtain the leucine precipitate and the second mother liquor, and then use 201×7 type anion exchange resin (purchased from Tianjin Yinghai Chemical Group Co., Ltd.) to separate and purify the leucine precipitate to obtain amino acid B (leucine); Finally, stir and add 6 mol/L ammonia to the second mother liquor to adjust the pH to 5.0, let it stand for 24 hours and then filter to obtain a solid component. The solid component is dried at 42°C to constant weight to obtain amino acid C (cystine). ), mix amino acid A, amino acid B and amino acid C according to the mass ratio of 3.8:1.4:1.3 to obtain a composite amino acid, in which amino acid A (tyrosine), amino acid B (leucine) and amino acid C (cystine ) yields (relative to the weight of washed and dried animal hair) were 2.5%, 4.0% and 5.8% respectively, and the purity were 97%, 97% and 98% respectively.
实施例3Example 3
制备复合氨基酸:Prepare complex amino acids:
毛发水解:向2L的8mol/L的盐酸溶液中搅拌加入1.8kg的洗净干燥后的动物毛发,置于95℃条件下水解5h,水解完毕后,继续向中加入8mol/L的盐酸溶液,直至体系pH为1.6,得到毛发水解液。Hair hydrolysis: Stir and add 1.8kg of washed and dried animal hair into 2L of 8mol/L hydrochloric acid solution, and place it at 95°C for hydrolysis for 5 hours. After the hydrolysis is completed, continue to add 8mol/L hydrochloric acid solution. Until the pH of the system reaches 1.6, a hair hydrolyzate is obtained.
氨基酸提取:向1L的毛发水解液中搅拌加入70g的联苯-4-磺酸(98%,购自上海麦克林生化科技有限公司),混合搅拌4h,得到第一混液,将第一混液冷却至10℃,静置24h后过滤,得到酪氨酸沉淀物和第一母液,再利用201×7型阴离子交换树脂(购自天津瀛海化集团有限公司)进行酪氨酸沉淀物的分离提纯,得到氨基酸A(酪氨酸);再向第一母液中搅拌加入140g的联苯-4-磺酸,混合搅拌3h,得到第二混液,将第二混液冷却至4℃,静置36h后过滤,得到亮氨酸沉淀物和第二母液,再利用201×7型阴离子交换树脂(购自天津瀛海化集团有限公司)进行亮氨酸沉淀物的分离提纯,得到氨基酸B(亮氨酸);最后向第二母液中搅拌加入6mol/L的氨水调节pH至5.1,静置24h后过滤,得到固体组分,固体组分置于45℃条件下干燥至恒重,得到氨基酸C(胱氨酸),将氨基酸A、氨基酸B和氨基酸C按照质量比4.0:1.5:1.5混合均匀,得到复合氨基酸,其中,氨基酸A(酪氨酸)、氨基酸B(亮氨酸)和氨基酸C(胱氨酸)的收率(相对于洗净干燥后的动物毛发重量)分别为2.5%、3.9%和5.7%,纯度分别为96%、96%、97%。Amino acid extraction: Stir and add 70g of biphenyl-4-sulfonic acid (98%, purchased from Shanghai McLean Biochemical Technology Co., Ltd.) to 1L of hair hydrolyzate, mix and stir for 4 hours to obtain the first mixed liquid, and cool the first mixed liquid. to 10°C, let it stand for 24 hours and then filter to obtain the tyrosine precipitate and the first mother liquor. Then use 201×7 anion exchange resin (purchased from Tianjin Yinghai Chemical Group Co., Ltd.) to separate and purify the tyrosine precipitate. Obtain amino acid A (tyrosine); then stir and add 140g of biphenyl-4-sulfonic acid to the first mother liquid, mix and stir for 3 hours to obtain a second mixed liquid, cool the second mixed liquid to 4°C, let it stand for 36 hours, and then filter , obtain the leucine precipitate and the second mother liquor, and then use 201×7 type anion exchange resin (purchased from Tianjin Yinghai Chemical Group Co., Ltd.) to separate and purify the leucine precipitate to obtain amino acid B (leucine); Finally, stir and add 6 mol/L ammonia to the second mother liquor to adjust the pH to 5.1, let it stand for 24 hours and then filter to obtain a solid component. The solid component is dried at 45°C to constant weight to obtain amino acid C (cystine). ), mix amino acid A, amino acid B and amino acid C according to the mass ratio of 4.0:1.5:1.5 to obtain a composite amino acid, in which amino acid A (tyrosine), amino acid B (leucine) and amino acid C (cystine ) yields (relative to the weight of washed and dried animal hair) were 2.5%, 3.9% and 5.7% respectively, and the purity were 96%, 96% and 97% respectively.
实施例4Example 4
制备复合氨基酸螯合钙:Preparation of complex amino acid chelated calcium:
首先,用清水冲洗贝壳(市售)表面,除去贝壳表面杂物,将处理后的贝壳用2mol/L稀盐酸浸泡30min,使贝壳表面的壳聚物和壳质素等溶解,取出贝壳,用蒸馏水进行冲洗8min,然后置于80℃烘箱内干燥至恒重,粉碎后过100目筛,得到贝壳粉。First, rinse the surface of the shells (commercially available) with clean water to remove debris on the surface of the shells. Soak the treated shells in 2mol/L dilute hydrochloric acid for 30 minutes to dissolve the chitosan and chitin on the surface of the shells. Take out the shells and use Rinse with distilled water for 8 minutes, then dry in an oven at 80°C to constant weight, crush and pass through a 100-mesh sieve to obtain shell powder.
向190mL的2mol/L的稀盐酸溶液中搅拌加入85g的贝壳粉,搅拌至固体组分完全溶解,得到氯化钙溶液,再向氯化钙溶液中加入35.4g的实施例1制备的复合氨基酸,搅拌混合3h,再向体系中加入pH为10.4的NH3-NHCl3缓冲溶液调节pH至8.9,pH调毕后,得到混合溶液,将混合溶液升温至65℃,搅拌螯合1.2h,螯合反应完毕后,得到螯合液,将螯合液进行高速离心10min,高速离心的离心速率设定为3500r/min,离心完毕后,取上清液进行减压浓缩,再用无水乙醇透析纯化2d,离心分离,取沉淀,得到复合氨基酸螯合钙。Stir and add 85g of shell powder to 190 mL of 2 mol/L dilute hydrochloric acid solution. Stir until the solid components are completely dissolved to obtain a calcium chloride solution. Then add 35.4g of the complex amino acid prepared in Example 1 to the calcium chloride solution. , stir and mix for 3 hours, then add NH 3 -NHCl 3 buffer solution with a pH of 10.4 to the system to adjust the pH to 8.9. After the pH adjustment is completed, a mixed solution is obtained. The mixed solution is heated to 65°C, stirred for 1.2 hours, and chelated. After the chelation reaction is completed, the chelating solution is obtained. The chelating solution is centrifuged at high speed for 10 minutes. The centrifugation rate of the high-speed centrifugation is set to 3500r/min. After the centrifugation is completed, the supernatant is taken and concentrated under reduced pressure, and then dialyzed with absolute ethanol. Purify for 2 days, centrifuge, and collect the precipitate to obtain complex amino acid chelated calcium.
实施例5Example 5
制备复合氨基酸螯合钙:Preparation of complex amino acid chelated calcium:
首先,用清水冲洗贝壳(市售)表面,除去贝壳表面杂物,将处理后的贝壳用2mol/L稀盐酸浸泡35min,使贝壳表面的壳聚物和壳质素等溶解,取出贝壳,用蒸馏水进行冲洗9min,然后置于90℃烘箱内干燥至恒重,粉碎后过100目筛,得到贝壳粉。First, rinse the surface of the shells (commercially available) with clean water to remove debris on the surface of the shells. Soak the treated shells in 2mol/L dilute hydrochloric acid for 35 minutes to dissolve the chitosan and chitin on the surface of the shells. Take out the shells and use Rinse with distilled water for 9 minutes, then dry in a 90°C oven to constant weight, crush and pass through a 100-mesh sieve to obtain shell powder.
向195mL的2mol/L的稀盐酸溶液中搅拌加入88g的贝壳粉,搅拌至固体组分完全溶解,得到氯化钙溶液,再向氯化钙溶液中加入35.8g的实施例2制备的复合氨基酸,搅拌混合4h,再向体系中加入pH为10.4的NH3-NHCl3缓冲溶液调节pH至9.0,pH调毕后,得到混合溶液,将混合溶液升温至68℃,搅拌螯合1.5h,螯合反应完毕后,得到螯合液,将螯合液进行高速离心1min,高速离心的离心速率设定为3800r/min,离心完毕后,取上清液进行减压浓缩,再用无水乙醇透析纯化3d,离心分离,取沉淀,得到复合氨基酸螯合钙。Stir and add 88g of shell powder to 195 mL of 2 mol/L dilute hydrochloric acid solution. Stir until the solid components are completely dissolved to obtain a calcium chloride solution. Then add 35.8g of the complex amino acid prepared in Example 2 to the calcium chloride solution. , stir and mix for 4 hours, then add NH 3 -NHCl 3 buffer solution with a pH of 10.4 to the system to adjust the pH to 9.0. After the pH adjustment is completed, a mixed solution is obtained. The mixed solution is heated to 68°C, stirred for 1.5 hours, and chelated. After the chelation reaction is completed, the chelating solution is obtained. The chelating solution is centrifuged at high speed for 1 min. The centrifugation rate of the high-speed centrifugation is set to 3800r/min. After the centrifugation is completed, the supernatant is taken and concentrated under reduced pressure, and then dialyzed with absolute ethanol. Purify for 3 days, centrifuge, and collect the precipitate to obtain complex amino acid chelated calcium.
实施例6Example 6
制备复合氨基酸螯合钙:Preparation of complex amino acid chelated calcium:
首先,用清水冲洗贝壳(市售)表面,除去贝壳表面杂物,将处理后的贝壳用2mol/L稀盐酸浸泡40min,使贝壳表面的壳聚物和壳质素等溶解,取出贝壳,用蒸馏水进行冲洗10min,然后置于100℃烘箱内干燥至恒重,粉碎后过100目筛,得到贝壳粉。First, rinse the surface of the shells (commercially available) with clean water to remove debris on the surface of the shells. Soak the treated shells in 2mol/L dilute hydrochloric acid for 40 minutes to dissolve the chitosan and chitin on the surface of the shells. Take out the shells and use Rinse with distilled water for 10 minutes, then dry in a 100°C oven to constant weight, crush and pass through a 100-mesh sieve to obtain shell powder.
向200mL的2mol/L的稀盐酸溶液中搅拌加入90g的贝壳粉,搅拌至固体组分完全溶解,得到氯化钙溶液,再向氯化钙溶液中加入36.0g的实施例3制备的复合氨基酸,搅拌混合4h,再向体系中加入pH为10.4的NH3-NHCl3缓冲溶液调节pH至9.2,pH调毕后,得到混合溶液,将混合溶液升温至70℃,搅拌螯合1.5h,螯合反应完毕后,得到螯合液,将螯合液进行高速离心12min,高速离心的离心速率设定为4000r/min,离心完毕后,取上清液进行减压浓缩,再用无水乙醇透析纯化3d,离心分离,取沉淀,得到复合氨基酸螯合钙。Stir and add 90 g of shell powder to 200 mL of 2 mol/L dilute hydrochloric acid solution. Stir until the solid components are completely dissolved to obtain a calcium chloride solution. Then add 36.0 g of the complex amino acid prepared in Example 3 to the calcium chloride solution. , stir and mix for 4 hours, then add NH 3 -NHCl 3 buffer solution with a pH of 10.4 to the system to adjust the pH to 9.2. After the pH adjustment is completed, a mixed solution is obtained. The mixed solution is heated to 70°C, stirred for 1.5 hours, and chelated. After the chelation reaction is completed, the chelating solution is obtained. The chelating solution is centrifuged at high speed for 12 minutes. The centrifugation rate of the high-speed centrifugation is set to 4000r/min. After the centrifugation is completed, the supernatant is taken and concentrated under reduced pressure, and then dialyzed with absolute ethanol. Purify for 3 days, centrifuge, and collect the precipitate to obtain complex amino acid chelated calcium.
实施例7Example 7
制备氨基酸螯合有机肥:Preparation of amino acid chelated organic fertilizer:
首先,氨基酸螯合有机肥,包括以下重量份原料:First, amino acid chelated organic fertilizer includes the following raw materials by weight:
其中,成膜液由以下步骤制备:Among them, the film-forming liquid is prepared by the following steps:
向80mL去离子水中搅拌加入35g聚乙烯醇(Mw89000-98000;90%水解;黏度25.0-31.0mPa·s;购自上海阿拉丁生化科技股份有限公司)、5g腐殖酸(黄腐酸FA≥90%;购自上海阿拉丁生化科技股份有限公司)、0.5g聚乙烯接枝马来酸酐(接枝率8%;平均分子量3000-8000;购自上海阿拉丁生化科技股份有限公司)和0.mL吐温-60(购自上海阿拉丁生化科技股份有限公司),搅拌混合30min,得到成膜液。Stir and add 35g polyvinyl alcohol (Mw89000-98000; 90% hydrolysis; viscosity 25.0-31.0mPa·s; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) and 5g humic acid (fulvic acid FA≥ 90%; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), 0.5g polyethylene grafted maleic anhydride (grafting rate 8%; average molecular weight 3000-8000; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) and 0 .mL Tween-60 (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), stir and mix for 30 min to obtain a film-forming liquid.
然后,氨基酸螯合有机肥的生产工艺,包括以下步骤:Then, the production process of amino acid chelated organic fertilizer includes the following steps:
按照重量份称取各原料,将玉米秸秆和小麦秸秆洗净烘干,用揉丝机粉碎混合,然后在110℃的条件下蒸汽软化2h,得到软化秸秆料,将软化秸秆料和豆粕转移至发酵罐中,加入发酵菌种(白地霉酵母)和纤维素酶(700u/g;购自西格玛奥德里奇(上海)贸易有限公司),升温至45℃,pH调节至6.2,恒温发酵36h,发酵完毕后过滤,所得固体组分置于100℃下灭菌15min,得到发酵组分,将发酵组分和实施例4制备的复合氨基酸螯合钙搅拌混合30min,得到氨基酸螯合有机肥肥芯,再将氨基酸螯合有机肥肥芯置于喷雾转鼓造粒机中,将成膜液包覆于氨基酸螯合有机肥肥芯的表面,烘干后,得到氨基酸螯合有机肥,经检测,氨基酸螯合有机肥的粒径大小为3.2mm。Weigh each raw material according to the weight portion, wash and dry the corn straw and wheat straw, crush and mix with a kneader, and then steam soften at 110°C for 2 hours to obtain softened straw material. Transfer the softened straw material and soybean meal to In the fermentation tank, add the fermentation strain (Grotrichia candidum yeast) and cellulase (700u/g; purchased from Sigma Aldrich (Shanghai) Trading Co., Ltd.), raise the temperature to 45°C, adjust the pH to 6.2, and ferment at a constant temperature for 36 hours. After the fermentation is completed, filter, and the solid component obtained is sterilized at 100°C for 15 minutes to obtain the fermentation component. The fermentation component and the complex amino acid chelated calcium prepared in Example 4 are stirred and mixed for 30 minutes to obtain the amino acid chelated organic fertilizer core. , then place the amino acid chelated organic fertilizer fertilizer core in a spray drum granulator, coat the surface of the amino acid chelated organic fertilizer fertilizer core with the film-forming liquid, and after drying, obtain the amino acid chelated organic fertilizer. , the particle size of amino acid chelated organic fertilizer is 3.2mm.
实施例8Example 8
制备氨基酸螯合有机肥:Preparation of amino acid chelated organic fertilizer:
首先,氨基酸螯合有机肥,包括以下重量份原料:First, amino acid chelated organic fertilizer includes the following raw materials by weight:
其中,成膜液由以下步骤制备:Among them, the film-forming liquid is prepared by the following steps:
向85mL去离子水中搅拌加入40g聚乙烯醇(Mw89000-98000;90%水解;黏度25.0-31.0mPa·s;购自上海阿拉丁生化科技股份有限公司)、6g腐殖酸(黄腐酸FA≥90%;购自上海阿拉丁生化科技股份有限公司)、0.8g聚乙烯接枝马来酸酐(接枝率8%;平均分子量3000-8000;购自上海阿拉丁生化科技股份有限公司)和0.15mL吐温-60(购自上海阿拉丁生化科技股份有限公司),搅拌混合40min,得到成膜液。Stir and add 40g polyvinyl alcohol (Mw89000-98000; 90% hydrolysis; viscosity 25.0-31.0mPa·s; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) and 6g humic acid (fulvic acid FA≥ 90%; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), 0.8g polyethylene grafted maleic anhydride (grafting rate 8%; average molecular weight 3000-8000; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) and 0.15 mL Tween-60 (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), stir and mix for 40 min to obtain a film-forming liquid.
然后,氨基酸螯合有机肥的生产工艺,包括以下步骤:Then, the production process of amino acid chelated organic fertilizer includes the following steps:
按照重量份称取各原料,将玉米秸秆和小麦秸秆洗净烘干,用揉丝机粉碎混合,然后在115℃的条件下蒸汽软化3h,得到软化秸秆料,将软化秸秆料和豆粕转移至发酵罐中,加入发酵菌种(白地霉酵母)和纤维素酶(700u/g;购自西格玛奥德里奇(上海)贸易有限公司),升温至46℃,pH调节至6.4,恒温发酵40h,发酵完毕后过滤,所得固体组分置于110℃下灭菌18min,得到发酵组分,将发酵组分和实施例5制备的复合氨基酸螯合钙搅拌混合30min,得到氨基酸螯合有机肥肥芯,再将氨基酸螯合有机肥肥芯置于喷雾转鼓造粒机中,将成膜液包覆于氨基酸螯合有机肥肥芯的表面,烘干后,得到氨基酸螯合有机肥,经检测,氨基酸螯合有机肥的粒径大小为4.0mm。Weigh each raw material according to the weight portion, wash and dry the corn straw and wheat straw, crush and mix them with a kneader, and then steam soften them at 115°C for 3 hours to obtain softened straw material. Transfer the softened straw material and soybean meal to In the fermentation tank, add fermentation bacteria (Glococcus candidum yeast) and cellulase (700u/g; purchased from Sigma Aldrich (Shanghai) Trading Co., Ltd.), raise the temperature to 46°C, adjust the pH to 6.4, and ferment at a constant temperature for 40 hours. After the fermentation is completed, filter, and the solid component obtained is sterilized at 110°C for 18 minutes to obtain the fermentation component. The fermentation component and the complex amino acid chelated calcium prepared in Example 5 are stirred and mixed for 30 minutes to obtain the amino acid chelated organic fertilizer core. , then place the amino acid chelated organic fertilizer fertilizer core in a spray drum granulator, coat the surface of the amino acid chelated organic fertilizer fertilizer core with the film-forming liquid, and after drying, obtain the amino acid chelated organic fertilizer. , the particle size of amino acid chelated organic fertilizer is 4.0mm.
实施例9Example 9
制备氨基酸螯合有机肥:Preparation of amino acid chelated organic fertilizer:
首先,氨基酸螯合有机肥,包括以下重量份原料:First, amino acid chelated organic fertilizer includes the following raw materials by weight:
其中,成膜液由以下步骤制备:Among them, the film-forming liquid is prepared by the following steps:
向90mL去离子水中搅拌加入42g聚乙烯醇(Mw89000-98000;90%水解;黏度25.0-31.0mPa·s;购自上海阿拉丁生化科技股份有限公司)、7g腐殖酸(黄腐酸FA≥90%;购自上海阿拉丁生化科技股份有限公司)、1.0g聚乙烯接枝马来酸酐(接枝率8%;平均分子量3000-8000;购自上海阿拉丁生化科技股份有限公司)和0.2mL吐温-60(购自上海阿拉丁生化科技股份有限公司),搅拌混合50min,得到成膜液。Stir and add 42g polyvinyl alcohol (Mw89000-98000; 90% hydrolysis; viscosity 25.0-31.0mPa·s; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) and 7g humic acid (fulvic acid FA≥ 90%; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), 1.0g polyethylene grafted maleic anhydride (grafting rate 8%; average molecular weight 3000-8000; purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.) and 0.2 mL Tween-60 (purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.), stir and mix for 50 min to obtain a film-forming liquid.
然后,氨基酸螯合有机肥的生产工艺,包括以下步骤:Then, the production process of amino acid chelated organic fertilizer includes the following steps:
按照重量份称取各原料,将玉米秸秆和小麦秸秆洗净烘干,用揉丝机粉碎混合,然后在120℃的条件下蒸汽软化3h,得到软化秸秆料,将软化秸秆料和豆粕转移至发酵罐中,加入发酵菌种(白地霉酵母)和纤维素酶(700u/g;购自西格玛奥德里奇(上海)贸易有限公司),升温至48℃,pH调节至6.5,恒温发酵48h,发酵完毕后过滤,所得固体组分置于120℃下灭菌20min,得到发酵组分,将发酵组分和实施例6制备的复合氨基酸螯合钙搅拌混合30min,得到氨基酸螯合有机肥肥芯,再将氨基酸螯合有机肥肥芯置于喷雾转鼓造粒机中,将成膜液包覆于氨基酸螯合有机肥肥芯的表面,烘干后,得到氨基酸螯合有机肥,经检测,氨基酸螯合有机肥的粒径大小为5.0mm。Weigh each raw material according to the weight portion, wash and dry the corn straw and wheat straw, crush and mix with a kneader, and then steam soften at 120°C for 3 hours to obtain softened straw material. Transfer the softened straw material and soybean meal to In the fermentation tank, add fermentation bacteria (Glococcus candidum yeast) and cellulase (700u/g; purchased from Sigma Aldrich (Shanghai) Trading Co., Ltd.), raise the temperature to 48°C, adjust the pH to 6.5, and ferment at a constant temperature for 48 hours. After the fermentation is completed, filter, and the solid component obtained is sterilized at 120°C for 20 minutes to obtain the fermentation component. The fermentation component and the complex amino acid chelated calcium prepared in Example 6 are stirred and mixed for 30 minutes to obtain the amino acid chelated organic fertilizer core. , then place the amino acid chelated organic fertilizer fertilizer core in a spray drum granulator, coat the surface of the amino acid chelated organic fertilizer fertilizer core with the film-forming liquid, and after drying, obtain the amino acid chelated organic fertilizer. , the particle size of amino acid chelated organic fertilizer is 5.0mm.
对比例1Comparative example 1
对比例1为实施例8的对照组,将实施例8中的实施例5制备复合氨基酸螯合钙过程中实施例2制备的复合氨基酸替换为氨基酸A(酪氨酸),其余制备过程和生产工艺中与实施例5和实施例8的保持一致,最终得到氨基酸螯合有机肥,氨基酸螯合有机肥的粒径大小为4.0mm。Comparative Example 1 is the control group of Example 8. In the process of preparing complex amino acid chelate calcium in Example 5 in Example 8, the complex amino acid prepared in Example 2 was replaced with amino acid A (tyrosine). The remaining preparation processes and production The process is consistent with Example 5 and Example 8, and finally an amino acid chelated organic fertilizer is obtained. The particle size of the amino acid chelated organic fertilizer is 4.0 mm.
对比例2Comparative example 2
对比例1为实施例8的对照组,将实施例8中的实施例5制备复合氨基酸螯合钙过程中实施例2制备的复合氨基酸替换为氨基酸B(亮氨酸),其余制备过程和生产工艺中与实施例5和实施例8的保持一致,最终得到氨基酸螯合有机肥,氨基酸螯合有机肥的粒径大小为4.0mm。Comparative Example 1 is the control group of Example 8. In the process of preparing complex amino acid chelate calcium in Example 5 in Example 8, the complex amino acid prepared in Example 2 was replaced with amino acid B (leucine). The remaining preparation processes and production The process is consistent with Example 5 and Example 8, and finally an amino acid chelated organic fertilizer is obtained. The particle size of the amino acid chelated organic fertilizer is 4.0 mm.
对比例3Comparative example 3
对比例1为实施例8的对照组,将实施例8中的实施例5制备复合氨基酸螯合钙过程中实施例2制备的复合氨基酸替换为氨基酸C(胱氨酸),其余制备过程和生产工艺中与实施例5和实施例8的保持一致,最终得到氨基酸螯合有机肥,氨基酸螯合有机肥的粒径大小为4.0mm。Comparative Example 1 is the control group of Example 8. In the process of preparing complex amino acid chelate calcium in Example 5 in Example 8, the complex amino acid prepared in Example 2 was replaced with amino acid C (cystine). The remaining preparation processes and production The process is consistent with Example 5 and Example 8, and finally an amino acid chelated organic fertilizer is obtained. The particle size of the amino acid chelated organic fertilizer is 4.0 mm.
对比例4Comparative example 4
对比例1为实施例8的对照组,将实施例8中的成膜液替换为去离子水,然后,氨基酸螯合有机肥的生产工艺,包括以下步骤:Comparative Example 1 is the control group of Example 8. The film-forming liquid in Example 8 is replaced with deionized water. Then, the production process of amino acid chelated organic fertilizer includes the following steps:
按照重量份称取各原料,将玉米秸秆和小麦秸秆洗净烘干,用揉丝机粉碎混合,然后在115℃的条件下蒸汽软化3h,得到软化秸秆料,将软化秸秆料和豆粕转移至发酵罐中,加入发酵菌种(白地霉酵母)和纤维素酶(700u/g;购自西格玛奥德里奇(上海)贸易有限公司),升温至46℃,pH调节至6.4,恒温发酵40h,发酵完毕后过滤,所得固体组分置于110℃下灭菌18min,得到发酵组分,将发酵组分和实施例5制备的复合氨基酸螯合钙搅拌混合30min,得到氨基酸螯合有机肥肥芯,再将氨基酸螯合有机肥肥芯置于喷雾转鼓造粒机中,利用去离子将氨基酸螯合有机肥肥芯进行造粒,烘干后,得到氨基酸螯合有机肥,经检测,氨基酸螯合有机肥的粒径大小为3.8mm。Weigh each raw material according to the weight portion, wash and dry the corn straw and wheat straw, crush and mix them with a kneader, and then steam soften them at 115°C for 3 hours to obtain softened straw material. Transfer the softened straw material and soybean meal to In the fermentation tank, add fermentation bacteria (Glococcus candidum yeast) and cellulase (700u/g; purchased from Sigma Aldrich (Shanghai) Trading Co., Ltd.), raise the temperature to 46°C, adjust the pH to 6.4, and ferment at a constant temperature for 40 hours. After the fermentation is completed, filter, and the solid component obtained is sterilized at 110°C for 18 minutes to obtain the fermentation component. The fermentation component and the complex amino acid chelated calcium prepared in Example 5 are stirred and mixed for 30 minutes to obtain the amino acid chelated organic fertilizer core. , then place the amino acid chelated organic fertilizer fertilizer core in a spray drum granulator, use deionization to granulate the amino acid chelated organic fertilizer fertilizer core, and after drying, the amino acid chelated organic fertilizer fertilizer is obtained. After testing, the amino acid chelated organic fertilizer fertilizer core is The particle size of chelated organic fertilizer is 3.8mm.
对实施例4-实施例6和对比例1-对比例4制备的氨基酸螯合有机肥进行田野试验,试验过程如下,试验结果如表1所示:Field tests were conducted on the amino acid chelated organic fertilizers prepared in Examples 4 to 6 and Comparative Examples 1 to 4. The test process was as follows, and the test results are shown in Table 1:
试验地选在乐山峨眉山市九里镇辣椒种植示范田,试验地长75m,宽9m,面积675m2,山地黄壤,pH=4.65,有机质3.2-5.4g/kg、有效氮55.0-71.8mg/kg、速效磷1.27-2.30mg/kg。将试验地划分为若干区域,每个区域的面积为32.5m2,在每个区域种植辣椒,其中,辣椒额度行距为65cm,株距为33cm,每个区域种植约152株。其中,氨基酸复合微肥的施肥量为40kg/亩,每隔1月,取样(区域对角三点取样调查)调查辣椒株高和叶片数。The test site was selected as a pepper planting demonstration field in Jiuli Town, Emeishan City, Leshan. The test site is 75m long, 9m wide, and covers an area of 675m 2 . It has mountainous yellow soil, pH=4.65, organic matter 3.2-5.4g/kg, available nitrogen 55.0-71.8mg/kg, Available phosphorus 1.27-2.30mg/kg. The experimental plot was divided into several areas, each with an area of 32.5m 2 , and peppers were planted in each area. The row spacing of peppers was 65cm, the plant spacing was 33cm, and about 152 plants were planted in each area. Among them, the fertilizer amount of amino acid compound micro-fertilizer is 40kg/acre. Every January, sampling (regional diagonal three-point sampling survey) is conducted to investigate the pepper plant height and leaf number.
表1Table 1
由表1可以看出,本发明制备的氨基酸螯合有机肥能够显著提高肥料的肥力和作用时间。It can be seen from Table 1 that the amino acid chelated organic fertilizer prepared by the present invention can significantly improve the fertility and action time of the fertilizer.
需要说明的是,在本文中,诸如术语“包括、包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、物品或者设备所固有的要素。It should be noted that, as used herein, terms such as "comprising," or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or device that includes a list of elements not only includes those elements, but also It also includes other elements not expressly listed or that are inherent to the process, method, article or equipment.
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art will appreciate that various changes, modifications, substitutions and changes can be made to these embodiments without departing from the principles and spirit of the invention. Alternatively, the scope of the invention is defined by the appended claims and their equivalents.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311674043.3A CN117586067A (en) | 2023-12-07 | 2023-12-07 | Amino acid chelated organic fertilizer and production process thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311674043.3A CN117586067A (en) | 2023-12-07 | 2023-12-07 | Amino acid chelated organic fertilizer and production process thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117586067A true CN117586067A (en) | 2024-02-23 |
Family
ID=89916629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311674043.3A Pending CN117586067A (en) | 2023-12-07 | 2023-12-07 | Amino acid chelated organic fertilizer and production process thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117586067A (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102442871A (en) * | 2010-10-12 | 2012-05-09 | 青岛大学 | Preparation method of compound amino acid chelated calcium using shell and scallop skirt as raw material |
CN103044144A (en) * | 2013-01-05 | 2013-04-17 | 杨彪 | Preparation method of organic chelate fertilizer |
CN103570450A (en) * | 2012-08-11 | 2014-02-12 | 江苏友峰化肥有限公司 | Organic fertilizer containing amino acid and humic acid trace element chelates |
CN103570427A (en) * | 2012-07-30 | 2014-02-12 | 江苏友峰化肥有限公司 | Organic and inorganic composite fertilizer containing amino acid trace element chelates |
CN104326848A (en) * | 2014-10-14 | 2015-02-04 | 马鞍山科邦生态肥有限公司 | Water and fertilizer retention organic fertilizer and preparation method thereof |
CN110028353A (en) * | 2019-05-23 | 2019-07-19 | 山东中创亿丰肥料集团有限公司 | A kind of control release type chelating microbial manure and preparation method thereof |
AU2020103884A4 (en) * | 2020-12-04 | 2021-02-11 | Institute Of Agricultural Resources And Environment, Shandong Academy Of Agricultural Sciences | A soil conditioner prepared from waste materials by biological fermentation bed and its preparation method |
CN115925568A (en) * | 2022-12-27 | 2023-04-07 | 峨眉山市龙腾生物科技有限公司 | Method for preparing various amino acids based on hair hydrolysis process |
CN116589313A (en) * | 2023-04-18 | 2023-08-15 | 江西正合生态农业有限公司 | A kind of preparation method of organic compost |
-
2023
- 2023-12-07 CN CN202311674043.3A patent/CN117586067A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102442871A (en) * | 2010-10-12 | 2012-05-09 | 青岛大学 | Preparation method of compound amino acid chelated calcium using shell and scallop skirt as raw material |
CN103570427A (en) * | 2012-07-30 | 2014-02-12 | 江苏友峰化肥有限公司 | Organic and inorganic composite fertilizer containing amino acid trace element chelates |
CN103570450A (en) * | 2012-08-11 | 2014-02-12 | 江苏友峰化肥有限公司 | Organic fertilizer containing amino acid and humic acid trace element chelates |
CN103044144A (en) * | 2013-01-05 | 2013-04-17 | 杨彪 | Preparation method of organic chelate fertilizer |
WO2014106423A1 (en) * | 2013-01-05 | 2014-07-10 | 迟英娟 | Method for preparing organic chelate fertilizer |
CN104326848A (en) * | 2014-10-14 | 2015-02-04 | 马鞍山科邦生态肥有限公司 | Water and fertilizer retention organic fertilizer and preparation method thereof |
CN110028353A (en) * | 2019-05-23 | 2019-07-19 | 山东中创亿丰肥料集团有限公司 | A kind of control release type chelating microbial manure and preparation method thereof |
AU2020103884A4 (en) * | 2020-12-04 | 2021-02-11 | Institute Of Agricultural Resources And Environment, Shandong Academy Of Agricultural Sciences | A soil conditioner prepared from waste materials by biological fermentation bed and its preparation method |
CN115925568A (en) * | 2022-12-27 | 2023-04-07 | 峨眉山市龙腾生物科技有限公司 | Method for preparing various amino acids based on hair hydrolysis process |
CN116589313A (en) * | 2023-04-18 | 2023-08-15 | 江西正合生态农业有限公司 | A kind of preparation method of organic compost |
Non-Patent Citations (2)
Title |
---|
刘音, 呼世斌, 张升堂, 王家洪, 宋凤敏: "利用动物有机废弃物制备氨基酸螯合微肥的工艺研究", 西北农林科技大学学报(自然科学版), no. 02, 25 February 2004 (2004-02-25) * |
许丽娟;梁明龙;何觉勤;陈劲礼;: "复合氨基酸微量元素螯合肥的制备及应用研究", 广东化工, no. 02, 30 January 2014 (2014-01-30) * |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112759488A (en) | Fish peptide organic water-soluble fertilizer and preparation method thereof | |
CN107602262B (en) | Controlled-release fertilizer for southern potato drip irrigation and preparation method thereof | |
CN106800435B (en) | Synergistic urea and preparation method thereof | |
CN104030790A (en) | Long-acting modified sustained-release fertilizer coated by urea-formaldehyde resin | |
CN107337504A (en) | Excellent magnet organic fertilizer material containing sodium alginate of a kind of retain water and nutrients and preparation method thereof | |
CN107512953A (en) | A kind of stalk fermentation compost with soil remediation ability | |
CN108484300A (en) | Ureaformaldehyde Synergistic composite fertilizer production technology | |
CN107235767A (en) | A kind of biodegradable composite coated material of slow release fertilizer and preparation method thereof | |
CN114163272A (en) | Selenium-rich microbial agent and preparation method thereof | |
CN108314555A (en) | One cultivates peanut full price organic composite fertilizer and preparation method thereof | |
CN113683463A (en) | Production process of compound fertilizer based on biological agent | |
CN104030789A (en) | Modified-acrylic-acid coated synergic sustained-release composite fertilizer | |
CN107032925A (en) | Method for producing tea tree special fertilizer by taking jasmine flower residue and tea dust as raw materials | |
CN109220647B (en) | Planting method of rice with high trace elements and high enzyme activity | |
CN117586067A (en) | Amino acid chelated organic fertilizer and production process thereof | |
CN102503650A (en) | Amino acid chelated fertilizer and preparation method thereof | |
CN118619785A (en) | Polyamino acid type composite microbial organic fertilizer for crop planting and preparation method thereof | |
CN118307373A (en) | A biomass-based soil conditioner and preparation method thereof | |
CN117586074A (en) | Method for preparing crop nutrition agent by using by-product of procambarus clarkii and application thereof | |
CN109180326A (en) | A kind of preparation method of legume crop gel biological bacterial manure | |
CN102428914B (en) | Method for preparing vector substrate of plant growth promoting bacterium agent from green straws | |
CN116120122A (en) | A kind of polytetrazyme selenium-enriched bio-organic fertilizer and preparation method thereof | |
CN116535261A (en) | Special fermentation and decomposition biological organic fertilizer for peanuts and preparation method thereof | |
CN108503462A (en) | A kind of polymeric amino acid fertilizer and preparation method thereof improving plant recovery of nutrient | |
CN107197708A (en) | A kind of preparation method of the composite modified sulfate organic nutrient soil of fermentation of seaweed |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20240223 |
|
RJ01 | Rejection of invention patent application after publication |