CN112898075B - Metal organic frame fertilizer and solid phase synthesis method thereof - Google Patents
Metal organic frame fertilizer and solid phase synthesis method thereof Download PDFInfo
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- CN112898075B CN112898075B CN202110166554.9A CN202110166554A CN112898075B CN 112898075 B CN112898075 B CN 112898075B CN 202110166554 A CN202110166554 A CN 202110166554A CN 112898075 B CN112898075 B CN 112898075B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- 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
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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Abstract
The invention relates to a metal organic frame fertilizer and a solid phase synthesis method thereof, which react solid reactants consisting of metal node materials, organic joint materials and counter ion materials at normal temperature to synthesize a frame through mechanochemical reaction, thereby obtaining the novel slow release fertilizer of metal organic frames. The method can realize solid-phase synthesis of the metal organic frame fertilizer under low heat, and the prepared metal organic frame fertilizer has better nutrient slow release performance.
Description
Technical Field
The invention belongs to the technical field of fertilizer manufacturing, and particularly relates to a metal organic framework fertilizer and a solid-phase synthesis method thereof.
Background
As the world population grows, food safety issues become more important, and how to maintain harmony and balance between agricultural production, soil and the environment is currently a topic of concern. Continuous large-scale grain production and unreasonable fertilizer application cause many problems to the soil and environment, such as trace element scarcity[1]Acidification of soil[2]Problems of groundwater pollution and air pollution[3]Etc. in addressing these issues, scientific application of fertilizers is probably one of the most practical, convenient, and effective methods. Around the core problem of how to improve the utilization rate of the fertilizer, the novel fertilizer and the green synthesis method thereof become the research hotspots at home and abroad in recent years.
The metal organic framework is a coordination polymer which takes metal ions or ion clusters as nodes and is connected with organic ligands, different framework structures can be formed by using different ligands, and ultrahigh porosity and specific surface area are formed at the same time, so that the metal organic framework is widely researched and applied to the fields of gas adsorption and separation, heterogeneous catalysis, photocatalysis, chemical sensing, proton conduction, biological medicine and pharmacology and the like[4]。
The common synthesis methods of metal organic frameworks are as follows: slow evaporation method, solvent thermal synthesis method, microwave synthesis method, electrochemical methodChemical synthesis, ultrasonic chemical synthesis and mechanochemical synthesis, most of the synthesis methods are liquid phase synthesis; among them, mechanochemical synthesis is a faster and easier to handle solid-phase synthesis[5]. Mechanochemical synthesis, i.e. chemical synthesis reactions initiated or sustained by direct absorption of mechanical energy[6-7]Has the potential advantages of large-scale production, high quantitative yield, avoidance of a large amount of solvent and high temperature, and the like[8]. One of the most important techniques in mechanochemical synthesis is solvent-free synthesis, which usually uses hydrated metal salts as raw materials, after grinding the complex water is released[9]。
Research has preliminarily confirmed the potential of metal organic frameworks as fertilizer carriers[10-15]. The synthesis method used in the existing research is a hydrothermal synthesis method using urea as a structure directing agent, in the reaction process, urea is decomposed and then attached to the inside of a frame in the form of ammonium ions, the required reaction temperature is above 100 ℃, the autogenous pressure is high, the time is long, the yield is low (mostly between 10% and 20%), mother liquor needs to be recycled, and the separation and drying of products need to be carried out; the above points will further increase the synthesis and processing cost of the metal organic framework as fertilizer.
Reference to the literature
[1]A,K.M.,A,G.I.,A,D.S.,A,M.M.,B,K.M.,&C,W.K.,et al.(0).Controlled release micronutrient fertilizers for precision agriculture–a review.ence of The Total Environment,712.
[2]Hao,T.,Zhu,Q.,Zeng,M.,Shen,J.,&Vries,W.D..(2020).Impacts of nitrogen fertilizer type and application rate on soil acidification rate under a wheat-maize double cropping system.Journal of Environmental Management,270,110888.
[3]Chen,J.,Lu,S.,Zhang,Z.,Zhao,X.,Li,X.,&Ning,P.,et al.(2017).Environmentally friendly fertilizers:a review of materials used and their effects on the environment.ence of the Total Environment,613-614.
[4]Jiao,L.,Seow,J.Y.R.,Skinner,W.S.,Wang,Z.U.,&Jiang,H.L..(2019).Metal–organic frameworks:structures and functional applications.Materials Today,27,43-68.
[5]Dey,C.,Kundu,T.,Biswal,B.P.,Mallick,A.,&Banerjee,R..(2014).Crystalline metal-organic frameworks(mofs):synthesis,structure and function.Acta Crystallographica,70(1),3-10.
[6]Do,J.L.,&Tomislav
(2017).Mechanochemistry:a force of synthesis.Acs Cent,3(1),13-19.
[7]Tan,D.,&García,Felipe.(2019).Main group mechanochemistry:from curiosity to established protocols.Chemical Society Reviews.
[8]Tanaka,S..(2020).Mechanochemical synthesis of mofs.Metal-Organic Frameworks for Biomedical Applications,197-222.
[9]Amery,N.A.,Abid,H.R.,Al-Saadi,S.,Wang,S.,&Liu,S..(2020).Facile directions for synthesis,modification and activation of mofs.Materials Today Chemistry,17,100343.
[10]Anstoetz,M.,Clark,M.W.,&Yee,L.H..(2017).Response surface optimisation of an oxalate–phosphate–amine metal–organic framework(opa-mof)of iron and urea.Journal of Inorganic and Organometallic Polymers and Materials,27(4),996-1013.
[11]Anstoetz,M.,Rose,T.J.,Clark,M.W.,Yee,L.H.,Raymond,C.A.,&Vancov,T..(2015).Novel applications for oxalate-phosphate-amine metal-organic-frameworks(opa-mofs):can an iron-based opa-mof be used as slow-release fertilizer？.PLOS ONE,10(12),e0144169.
[12]Usman,K.A.S.,Buenviaje,S.C.,
Yasmin de Guzman,Conato,M.T.,&Payawan,L.M..(2018).Facile fabrication of a potential slow-release fertilizer based on oxalate-phosphate-amine metal-organic frameworks(opa-mofs).Materials Science Forum,936,14-19.
[13]Wu,K.,Du,C.,Ma,F.,Shen,Y.,&Zhou,J..(2019).Optimization of metal–organic(citric acid)frameworks for controlled release of nutrients.RSC Adv,9(55),32270-32277.
[14]Wu,K.；Du,C.；Ma,F.；Shen,Y.；Liang,D.；&Zhou,J..(2019).Degradation of Metal-Organic Framework Materials as Controlled-Release Fertilizers in Crop Fields.Polymers,11,947.
[15] Application of novel fertilizers of the type Wuke, Duchang Wen, Shen Asian, Ma Fei, (2019), metallorganic frameworks (mof) to rice was first explored, plant nutrition and fertilizer academy, 25(12).
Disclosure of Invention
The invention aims to provide a metal organic framework fertilizer and a solid-phase synthesis method thereof.
In order to achieve the technical purpose, the invention adopts the following technical scheme,
a solid-phase synthesis method of metal organic frame fertilizer, which synthesizes mixed solid-phase reactants into a frame through mechanical action at normal temperature;
the solid-phase reactant raw material consists of a metal node material, an organic joint material and a counter ion material;
the solid phase reactant raw material contains P, Fe and one of N and K.
Further, ferric salt is used as a metal node material, oxalic acid is used as an organic joint material, and ammonium ions or potassium ions are used as counter ions to synthesize the metal organic framework.
Further, the ammonium ion or potassium ion is present in the solid phase reactant feedstock in the form of a phosphate.
Further, the solid-phase reactant raw materials are put into a ball mill for grinding reaction, and the metal organic framework is synthesized.
Further, the reaction conditions are as follows: grinding at 600-700 rpm for 10-15 minutes; milling is preferably carried out for 12 minutes. 600-700 rpm is beneficial to the solid-phase reaction to obtain sufficient mechanical energy in the middle and later reaction stages, and can effectively improve the yield and shorten the reaction time.
Further, the grinding mode is intermittent grinding. The intermittent grinding is beneficial to the emission of heat energy generated in the high-speed grinding process, and is also beneficial to the full reaction of reactants, thereby improving the yield.
Further, each grinding cycle of the intermittent grinding, grinding time: pause time 2: 1; preferably, each cycle is ground for 2 minutes with a pause of 1 minute.
Further, after the solid phase reactant mixing reaction is finished, drying the product at the temperature of 40-135 ℃.
Further, the feeding molar ratio of reactants is iron ions: counter ions: oxalic acid is 1: 4-8: 1-2; preferably 1: 4: 1.
the invention uses mechanochemical method to synthesize new metal organic framework under the condition of low heat solid phase, and loads ammonium, phosphorus, potassium and iron as plant nutrient elements.
The invention also aims to provide a metal organic framework fertilizer, which is formed by taking iron salt as a metal node material, oxalic acid as an organic joint material and ammonium ions or potassium ions as counter ions.
Further, the metal organic framework fertilizer comprises the following components in a molar ratio: iron ions: counter ions: oxalic acid is 1: 4-8: 1-2; preferably 1: 4: 1.
under the condition of room temperature or near room temperature, the metal organic frame fertilizer is efficiently synthesized by taking iron salt as an inorganic part, oxalic acid as an organic joint and ammonium ions or potassium ions as counter ions. The framework contains the nutrient elements of N, K, P and Fe through element composition analysis. Through a test of a still water cultivation test, the metal organic frame fertilizer disclosed by the invention has higher nutrient content and good slow release performance.
Drawings
FIG. 1 is a graph of percent (%) nutrient release for the products of the examples.
FIG. 2 is an X-ray powder diffraction pattern of the product of the example.
Detailed Description
The main material types used in the examples are as follows:
planetary super-energy ball mill Pulueresette 7, FRISCH, Germany;
ICAP-OES Thermo Fisher, UK.
Example 1
Weighing 0.02 mol of ferric chloride, 0.04 mol of diammonium hydrogen phosphate and 0.02 mol of oxalic acid, placing the materials into an agate ball milling tank, grinding the materials by using a planetary super-energy ball mill at 600rpm, pausing for 1 minute every 2 minutes, and grinding for 6 times and 12 minutes in total; taking out the mixture, putting the mixture into an evaporating dish, drying the mixture at the temperature of 60 ℃, and finally washing, filtering and drying the dried mixture to obtain a product.
The nutrient slow release characteristic determination method comprises the following steps: accurately weighing 1.5g of the product, adding 50mL of deionized water into a ground reagent bottle, completely pouring out the solution every 7 days, and then adding 50mL of deionized water again; and determining the content of ammonia nitrogen by using an indophenol blue colorimetric method, and determining the content of available phosphorus, available potassium and available iron by using ICAP-OES.
The yield of example 1 is 33% to 34%, and the prepared product has the following nutrient content: 4-5.5% of N, 14-16% of P, 18-19% of Fe;
the cumulative release rate over 21 days for the product prepared in example 1 was approximately N, 40%, P, 14%, Fe, 4% by the hydrostatic incubation test.
Example 2
Weighing 0.02 mol of ferric chloride, 0.04 mol of dipotassium hydrogen phosphate and 0.02 mol of oxalic acid, placing the mixture into an agate ball milling tank, grinding the mixture by using a planetary super-energy ball mill at 700rpm, pausing for 1 minute every 2 minutes, and grinding for 6 times and 12 minutes in total; taking out the mixture, putting the mixture into an evaporating dish, drying the mixture at the temperature of 60 ℃, and finally washing, filtering and drying the dried mixture to obtain a product.
The yield of example 2 is 33% to 34%, and the prepared product has the following nutrient contents: 12-13% of K, 14-15% of P, and 15-16% of Fe;
the cumulative release rate over 21 days for the product prepared in example 1 was approximately K, 23%, P, 12%, Fe, 5% by the hydrostatic incubation test.
Example 3
The difference from example 1 is only that the feed amount is: 0.02 mol of ferric chloride, 0.02 mol of diammonium phosphate and 0.02 mol of oxalic acid. And washing, filtering and drying the dried mixture. The yield of example 3 was less than 0.1%, indicating that too low a proportion of counter ions did not give the desired product.
Example 4
The difference from example 1 is only that the feed amount is: 0.02 mol of ferric chloride, 0.06 mol of diammonium phosphate and 0.02 mol of oxalic acid.
The yield of the preparation of example 4 is 5% -8%, and the nutrient content of the prepared product is as follows: 2.5-5% of N, 11-13% of P and 18-19% of Fe.
Example 5
The only difference from example 1 is that the mixture was taken out and put into an evaporating dish, dried at 135 ℃, and finally the dried mixture was washed, filtered and dried to obtain the product.
The yield of example 5 is 42% to 43%, and the prepared product has the following nutrient content: 4-5.5% of N, 14-16% of P and 18-19% of Fe.
Example 6
The difference from example 2 is only that the feed amount is: 0.02 mol of ferric chloride, 0.06 mol of dipotassium phosphate, 0.02 mol of oxalic acid and 0.04 mol of urea. The product is then obtained.
The yield of example 6 is 33% to 34%, and the prepared product has the following nutrient content: 0.1-0.2% of N, 12-13% of K, 11-12% of P and 15-16% of Fe;
the cumulative release rate over 21 days for the product prepared in example 5 was approximately K, 16%, P, 16%, Fe, 5% by the hydrostatic incubation test.
Claims (5)
1. A solid phase synthesis method of a metal organic framework fertilizer is characterized in that a solid phase reactant raw material is put into a ball mill for grinding reaction at normal temperature, and the mixed solid phase reactant is synthesized into a metal organic framework;
the solid-phase reactant raw material consists of a metal node material, an organic joint material and a counter ion material; synthesizing the metal organic framework by taking iron salt as a metal node material, oxalic acid as an organic joint material and ammonium ions or potassium ions as counter ions;
the grinding mode is intermittent grinding;
the molar ratio of the fed reactants is iron ions: counter ions: oxalic acid = 1: 4-8: 1-2;
the reaction conditions are as follows: 600-700 rpm; the grinding time is 10-15 minutes; each grinding cycle of the intermittent grinding, grinding time: pause time = 2: 1; after the solid phase reactant mixing reaction is finished, drying the product at the temperature of 40-135 ℃.
2. The method of claim 1, wherein the milling time period is 12 minutes.
3. The method of claim 1, wherein each cycle is ground for 2 minutes with a 1 minute pause.
4. The method according to claim 1, characterized in that the reactant feed molar ratio is iron ion: counter ions: oxalic acid = 1: 4: 1.
5. a metal organic framework fertilizer prepared by the method of any one of claims 1 to 4.
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2021
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