CN111574284B

CN111574284B - Metal organic framework material fertilizer and preparation method thereof

Info

Publication number: CN111574284B
Application number: CN202010424615.2A
Authority: CN
Inventors: 杜昌文; 吴珂
Original assignee: Institute of Soil Science of CAS
Current assignee: Institute of Soil Science of CAS
Priority date: 2019-07-29
Filing date: 2020-05-19
Publication date: 2021-12-07
Anticipated expiration: 2040-05-19
Also published as: CN111574284A

Abstract

The novel fertilizer is composed of nutrient molecules and an external framework thereof, and is characterized in that the external framework is formed by self-assembling inorganic metal ion clusters and organic ligands under hydrothermal conditions. The hydro-thermal synthesis conditions of the novel fertilizer of the metal organic framework material are as follows: the reaction temperature is 115 ℃, the reaction time is 18h, the heating rate of the reaction kettle is 1.2 ℃/min, and the rotating speed of the stirrer is 80 r/min. The novel fertilizer has the following nutrient contents: nitrogen-10.78%, phosphorus-14.10%, iron-16.68%. Through soil cultivation tests, the results show that the novel fertilizer of the metal organic framework material has the advantage of good nutrient controlled release, the nutrient release period exceeds 100 days, the cumulative release rate of nitrogen and phosphorus nutrient elements in 100 days is 68.6%, the P is 46.8%, the controlled release effect is good, and the environment is friendly. The utilization rate of nutrients is improved.

Description

Metal organic framework material fertilizer and preparation method thereof

Technical Field

The invention belongs to the technical field of fertilizer manufacturing, and particularly designs a novel fertilizer made of a metal organic framework material and a preparation method of the novel fertilizer made of the metal organic framework material.

Background

The world population has now reached about 70 billion, approaching 95 billion by 2050, which requires more crop yield and food supply. Therefore, the agricultural sector must use larger amounts of chemical fertilizers to increase grain yield. In addition to the increase in fertilizer demand, the low utilization of fertilizers worldwide is also a serious problem. In agricultural production, 45-55% of nitrogen fertilizer is lost due to volatilization, leaching and runoff^[1,2]In the case of phosphate fertilizer, the utilization rate is usually only 10-25%^[3]. This not only causes a large amount of waste of resources, but also may cause unavoidable environmental problems such as water pollution and increased emission of harmful gases (e.g., NH)₃And N₂O）^[4,5]。

Currently, many scientists have actively sought ways to improve nutrient utilization. Some traditional methods, such as proper fertilizer application amount, deep nitrogen fertilizer application and divided fertilizer application, fertilizer and water regulation and control technology, balanced fertilizer application, soil testing formula fertilizer application and the like, and some newer methods, such as real-time nitrogen fertilizer management (such as SPAD field in-situ measurement of nitrogen content of plant leaves), accurate management technology of farmland nutrients and the like. The methods have the advantages and the disadvantages, firstly, the application amount of the fertilizer is reduced, the utilization rate of the fertilizer can be theoretically improved, and the environmental risk is reduced, but the method is difficult to implement in developing countries with rapidly increased population and high grain demand pressure; secondly, the application of the fertilizer can be guided more accurately theoretically by measures such as a fertilizer water regulation and control technology, a soil testing and formula fertilization technology, a balanced fertilization and the like, but the measures not only increase the labor cost for applying the fertilizer, but also have large technical popularization difficulty and more limitations, and are particularly suitable for China with scattered land operation modes; thirdly, similar to the farmland nutrient accurate management technology, the method has wide prospect, but currently, the method stays in the research stage.

The application of the controlled release fertilizer provides a new solution to the problem of low nutrient utilization rate^[6,7]. Most of the currently used controlled release fertilizers belong to coated fertilizers, and most of the coating layers are organic polymers, such as polyolefin, dicyclopentadiene, polystyrene, polysulfone and glyceride^[8-10]. However, the high cost and complex manufacturing process of these materials limits their large scale application to controlled release fertilizers^[11]. In addition, the high polymer materials may have potential harm to the ecological environment of soil, and related researches show that the accumulation of the materials in the soil not only reduces the soil fertility, but also releases toxic gas in the degradation process of the materials^[12]. Therefore, there is a need to develop a low-cost and environmentally friendly controlled release fertilizer.

A Metal Organic Framework (MOF) is a material with adjustable pore size that is formed by the self-assembly of metal ions or clusters of metal ions with organic ligands. MOFs have been used in many fields, such as gas storage^13-15Catalyzing the reaction of¹⁶And a drug carrier^17-19And the like. However, it is a fertilizer and has been reported only rarely. Therefore, the temperature of the molten metal is controlled,the invention synthesizes two original metal organic framework compounds under the hydrothermal condition by using nontoxic ferric chloride, phosphoric acid as an inorganic part, citric acid as an organic ligand and urea as a structure directing agent through optimizing process conditions, particularly reaction temperature rise rate, wherein the two compounds are rich in nitrogen, phosphorus and iron nutrient elements. Is expected to realize the controlled release of nutrients, particularly nitrogen nutrient elements, so as to improve the nutrient utilization rate and reduce the environmental risk.

201810724689.0, discloses a metal organic frame material fertilizer, which is composed of nutrient molecules and an external frame, and is characterized in that the external frame is composed of inorganic metal ion clusters and organic joints through coordination under hydrothermal conditions. The synthesized metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride, phosphoric acid, oxalic acid, urea and deionized water. The invention synthesizes the metal organic framework material from a microscopic level, and has the advantages of stable fertilizer nutrient release, longer period, good controlled release effect and environmental friendliness.

201810724689.0, the metal organic frame material fertilizer disclosed in the patent application has many advantages but still has many disadvantages. Firstly, the nutrient content is low, particularly the nitrogen content is only 5.16%; secondly, the synthesis yield is lower and is 26.5 percent; finally, the release rate of nutrients is too slow, and the cumulative release rate in 100 days is lower than 40%. Aiming at the problems, the invention aims to select a new organic ligand, and synthesize a novel organic framework material with higher nutrient content, higher yield and higher nutrient release rate by optimizing a synthesis process under a hydrothermal condition.

Reference to the literature

[1] Yang, Y. C.; Zhang, M.; Li, Y. C.; Fan, X. H.; Geng, Y. Q. Controlled release urea improved nitrogen use efficiency, activities of leaf enzymes, and Rice Yield. Soil Sci. Soc. Am. J.2012, 76, 2307−2317.

[2] Shavit, U.; Shaviv, A.; Shalit, G.; Zaslavsky, D. Release characteristics of a new controlled release fertilizer. J. Controlled Release1997, 43, 131−138.

[3] Shen, J.; Li, R.; Zhang, F.; Tang, C.; Rengel, Z. Crop yields, soil fertility and phosphorus fractions in response to long-term fertilization under the rice monoculture system on a calcareous soil. Field Crop. Res. 2004, 86(2-3), 225–238.

[4] Yan, X.; Jin, J. Y.; He, P.; Liang, M. Z. Recent advances on the technologies to increase fertilizer use efficiency. Agric. Sci. China 2008, 7, 469−479.

[5] Choudhury, A. T. M. A; Kennedy, I. R. Nitrogen fertilizer losses from rice soils and control of environmental pollution problems. Commun. Soil Sci. Plant Anal.2005, 36, 1625−1639.

[6] Zhang, M.; Yang, Y. C.; Shi, Y. X. Coated controlled release fertilizer research and industrialization development. Chem. Fert. Ind. 2001, 32, 25−27.

[7] Jin, S. P.; Yue, G. R.; Feng, L.; Han, Y. Q.; Yu, X. H.; Zhang, Z. H. Preparation and properties of a coated slow-release and water retention biuret phosphoramide fertilizer with superabsorbent. J. Agric. Food Chem. 2011, 59, 322−327.

[8] Jain, S. K. Agrawal, G,P; Kumar, M; Anande, Nalini. Controlled release fertilizers: Trends and Technologies. Pharm. Rev.2007, 5(1),1 -7.

[9] Shaviv, A. Improvement of fertilizer efficiency–Product processing, positioning and application methods. Proc. Int. Fert. Soc. 2001, 469, 1– 23.

[10] Tomaszewska, M.; Jarosiewicz, A. Use of polysulfone in controlled release NPK fertilizer formulations. J. Agric. Food Chem. 2002, 50, 4634– 4639.

[11] Ye, Y. S.; Liang, X. Q.; Chen, Y. X.; Liu, J.; Gu, J. T.; Guo, R.; Li, L. Alternate wetting and drying irrigation and controlled-release nitrogen fertilizer in late-season rice. Effects on dry matter accumulation, yield, water and nitrogen use. Field Crop Res. 2013, 144, 212−224.

[12] Briassoulis, D.; Dejean, C. Critical review of norms and standards for biodegradable agricultural plastics part I. Biodegradation in soil. J. Polym. Environ.2010, 18, 384−400.

[13] Eddaoudi, M.; Hailian, L.; Yaghi, O.M. Highly porous and stable metal-organic frameworks: structure design and sorption properties. J. Am. Chem. Soc. 2000, 122(7), 1391-1397.

[14] Kitagawa, S.; Kitaura, R.; Noro, S. Functional porous coordination polymers. Angew. Chem. Int. Ed. Engl. 2004, 43(18), 2334-2375.

[15] Murray, L.J.; Dinca, M.; Long, J.R. Hydrogen storage in metal-organic frameworks. Chem. Soc. Rev. 2009, 38(5), 1294-1314.

[16] Farrusseng, D.; Aguado, S.; Pinel, C. Metal-organic frameworks: opportunities for catalysis. Angew. Chem. Int. Ed. Engl. 2009, 48(41), 7502-7513.

[17] Janiak, C. Engineering coordination polymers towards applications, Dalton Transactions 2003, 14, 2781-2804.

[18] Mueller, U.; Schubert, M.; Teich, F.; Puetter, H.; Schierle-Arndt, K.; Pastre, J. Metal-organic frameworks-prospective industrial applications. J. Mater. Chem. 2006, 16(7), 626-636.

[19] McKinlay, A.C.; Morris, R.E.; Horcajada, P.; Férey, G.; Gref, R.; Couvreur, P.; Serre, C. Bio-MOFs: metal-organic frameworks for biological and medical applications, Angewandte. Chemie. Int. Edition. 2010, 49 (36), 6260-6266。

Disclosure of Invention

The invention aims to provide a novel fertilizer of metal organic framework materials. The invention also relates to a preparation method of the novel fertilizer of the metal organic framework material. According to the invention, a mild hydrothermal synthesis method is adopted, urea is used as a structure directing agent, ferric ions and phosphoric acid are used as inorganic parts, citric acid is used as an organic ligand, a metal organic framework material is synthesized by optimizing a synthesis process, particularly the heating rate, and then the nutrient content (nitrogen, phosphorus and iron) of the metal organic framework material is measured, and the result shows that the material contains higher nutrients. Finally, the release of the material is measured through soil cultivation, and experimental results show that the nutrient release period of the metal organic framework material can reach more than 100 days.

The technical scheme for completing the task of the first invention is as follows: the novel fertilizer of metal organic framework material is composed of nitrogen nutrient molecules and an external framework thereof, and is characterized in that the external framework is formed by self-assembling inorganic metal ion clusters and organic joints.

The nutrient molecules can be selected from various amine fertilizer molecules.

The metal organic framework material comprises the following components in a molar ratio:

ferric chloride (FeCl)₃·6H₂O） 0.25-3，

Phosphoric acid (H)₃PO₄） 3-7，

Citric acid (H)₈C₆O₇·H₂O） 0.5-2.5，

Urea (CO (NH)₂）₂） 2-5，

Deionized water (H)₂O） 65。

Through hydrothermal reaction synthesis, the recommended optimal formula and optimal synthesis parameters of the metal organic framework material fertilizer are as follows:

ferric chloride (FeCl)₃·6H₂O） 0.5-2，

Phosphoric acid (H)₃PO₄） 2-7，

Citric acid (H)₈C₆O₇·H₂O） 2-3，

Urea (CO (NH)₂）₂） 3-5，

Deionized water (H)₂O） 65。

The reaction temperature is 115 ℃, the reaction time is 18h, and the heating rate of the reaction kettle is 1.2 ℃/min.

Compared with the invention patent No. 201810724689.0, the invention has the following differences. (1) The invention adopts a new organic ligand citric acid, a tricarboxylic acid polydentate ligand, and has the following advantages compared with oxalic acid: firstly, citric acid is a flexible acid, and the distance between teeth, the included angle between teeth and the connection mode of radicals can be adjusted according to different coordination environments when the citric acid is coordinated with metal or metal clusters; secondly, citric acid is a hydroxyl tricarboxylic acid and contains rich oxygen atoms, so that the citric acid has stronger coordination capacity and more various coordination modes; finally, under different pH conditions, the deprotonation capacity of the hydroxyl group is different, so that the requirements of different metal coordination modes, coordination angles and coordination capacities can be met. Therefore, the citric acid is selected as the organic ligand, so that the coordination types and modes are greatly enriched, and flexible and changeable support is provided for discussing the assembly mode, the structure type and the performance research of the MOF material. (2) The speed of temperature rise plays an important role in the formation of initial crystal nuclei of the MOF material, and further influences the size of MOF crystal grains, so that the temperature rise rate of the hydrothermal reaction is emphasized in the invention.

The technical scheme for completing the second invention task is as follows: the preparation method of the novel fertilizer of the metal organic framework material is characterized by comprising the following steps:

completely dissolving ferric chloride, phosphoric acid, citric acid and urea in deionized water, and uniformly mixing to obtain a mixed solution;

pouring the mixed solution into a stainless steel reaction kettle, and then completely sealing. The reaction temperature is set to be 115 ℃, the reaction time is 18h, and the temperature rise rate of the reaction kettle is 1.2 ℃/min;

after the reaction is finished, opening the reaction kettle when the temperature is reduced to room temperature, filtering the solution by using filter paper, and then washing for 3 times by using deionized water to obtain a product.

Under the mild hydrothermal reaction condition, metal iron ions and phosphoric acid are used as inorganic parts, citric acid is used as an organic ligand, urea is used as a structure directing agent, and a metal organic framework material is synthesized from a molecular level and is used as a fertilizer, wherein the fertilizer contains nutrient elements, namely nitrogen, phosphorus and iron, which are necessary for crops. The nutrient content is as follows: nitrogen-10.78%, phosphorus-14.10%, iron-16.68%. Through soil cultivation tests, the metal organic framework material fertilizer produced by the invention has stable nutrient release and long period, the cumulative release rate of nitrogen and phosphorus nutrient elements in 100 days is 68.6%, the P is 46.8%, the controlled release effect is good, and the environment is friendly.

Drawings

FIG. 1 is a graph of cumulative release (%) of mineral nitrogen (ammonium nitrogen and nitrate nitrogen);

FIG. 2 is a graph showing the cumulative release (%) of effective phosphorus;

FIG. 3 is a graph showing the cumulative release (%) of effective iron.

Detailed Description

Example 1, a metal organic framework material fertilizer and a preparation method thereof: weighing ferric chloride (FeCl)₃·6H₂O) 1 mol, phosphoric acid (H)₃PO₄) 4.5 moles of citric acid (H)₈C₆O₇·H₂O) 1.5 mol, Urea (CO (NH)₂）₂) 4.5 moles, deionized water (H)₂O) 65 mol of the raw materials are put into a beaker, stirred by a glass rod, poured into a reaction kettle after a reaction substrate is completely dissolved and uniformly mixed, completely sealed, the reaction temperature is set to be 115 ℃, the reaction time is 18 hours, the heating rate of the reaction kettle is 1.2 ℃/min, the rotating speed of a stirrer is set to be 80r/min, after the reaction is finished, the reaction kettle is opened when the temperature is reduced to the room temperature, the solution is filtered by filter paper, and then the solution is washed by deionized water for 3 times to obtain a product.

Nutrient release determination method: 100g of soil samples were placed in a petri dish having a diameter of 8cm, and the water content of each tank was adjusted to 38% (w/w). Two processing methods were prepared. 1) Control treatment (no fertilizer). 2) Treating with metal organic frame, nitrogen application rate is 75 kg N ha^-1. Three replicates of each treatment were performed. All dishes were kept in the shade. In addition, a preservative film was coated on the petri dish to reduce soil moisture evaporation. Collected at 20, 40, 60, 80 and 100 daysA soil sample. Mineral Nitrogen (NH) was measured using a SmartChem 200 automatic analyser (AMS Alliance, Fripillon, France)₄ ⁺-N and NO₃ ^--N) content. The available phosphorus and available iron content of the soil samples were measured using an iCAP 7000 ICP-OES spectrometer (Thermo Fisher Scientific, USA).

Example 2, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 0.25, phosphoric acid (H)₃PO₄) 3, citric acid (H)₈C₆O₇·H₂O) 0.5, Urea (CO (NH)₂）₂) 2, deionized water (H)₂O）65。

Example 3, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 3, phosphoric acid (H)₃PO₄) 7, citric acid (H)₈C₆O₇·H₂O) 2.5, urea (CO (NH)₂）₂) 5, deionized water (H)₂O）65。

Example 4, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 0.25, phosphoric acid (H)₃PO₄) 7, citric acid (H)₈C₆O₇·H₂O) 0.5, Urea (CO (NH)₂）₂) 5, deionized water (H)₂O）65。

Example 5, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 3, phosphoric acid (H)₃PO₄) 3, citric acid (H)₈C₆O₇·H₂O) 2.5, urea (CO (NH)₂）₂) 2, deionized water (H)₂O）65。

Example 6, essentially the same as example 1, with the following modifications: metal organicThe frame material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 0.5, phosphoric acid (H)₃PO₄) 2, citric acid (H)₈C₆O₇·H₂O) 2, urea (CO (NH)₂）₂) 3, deionized water (H)₂O）65。

Example 7, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 2, phosphoric acid (H)₃PO₄) 7, citric acid (H)₈C₆O₇·H₂O) 3, urea (CO (NH)₂）₂) 5, deionized water (H)₂O）65。

Example 8, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 0.5, phosphoric acid (H)₃PO₄) 7, citric acid (H)₈C₆O₇·H₂O) 2, urea (CO (NH)₂）₂) 5, deionized water (H)₂O）65。

Example 9, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 2, phosphoric acid (H)₃PO₄) 2, citric acid (H)₈C₆O₇·H₂O) 3, urea (CO (NH)₂）₂) 3, deionized water (H)₂O）65。

Example 10, essentially the same as example 1, with the following modifications: the metal organic framework material comprises the following raw materials in a molar ratio: ferric chloride (FeCl)₃·6H₂O) 0.25, phosphoric acid (H)₃PO₄) 7, citric acid (H)₈C₆O₇·H₂O) 0.5, Urea (CO (NH)₂）₂) 5, deionized water (H)₂O）65。

Example 11, essentially the same as example 1, with the following modifications: metal is provided withThe molar ratio of the raw materials of the machine frame material is as follows: ferric chloride (FeCl)₃·6H₂O) 3, phosphoric acid (H)₃PO₄) 3, citric acid (H)₈C₆O₇·H₂O) 2.5, urea (CO (NH)₂）₂) 2, deionized water (H)₂O）65。

Claims

1. A metal organic framework material fertilizer is composed of nutrient molecules and an external framework thereof, and is characterized in that the external framework is formed by self-assembling inorganic metal ion clusters and organic ligands under hydrothermal conditions;

the molar ratio of the formula of the metal organic framework material fertilizer is as follows: 1 part of ferric chloride, 4.5 parts of phosphoric acid, 1.5 parts of citric acid, 4.5 parts of urea and 65 parts of deionized water;

the metal organic framework material fertilizer is prepared by the following method:

pouring the mixed solution into a stainless steel reaction kettle, and then completely sealing; the reaction temperature is set to be 115 ℃, the reaction time is 18h, the heating rate of the reaction kettle is 1.2 ℃/min, and the rotating speed of the stirrer is 80 r/min;

2. The method for preparing a metal organic framework type fertilizer according to claim 1, wherein: the steps are as follows,

weighing 1 mol of ferric chloride, 4.5 mol of phosphoric acid, 1.5 mol of citric acid, 4.5 mol of urea and 65 mol of deionized water, completely dissolving the ferric chloride, the phosphoric acid, the citric acid and the urea in the deionized water, and uniformly mixing to obtain a mixed solution;

pouring the mixed solution into a stainless steel reaction kettle, and then completely sealing; the reaction temperature is set to be 115 ℃, the reaction time is 18h, and the temperature rise rate of the reaction kettle is 1.2 ℃/min;