METAL-ORGANIC FRAMEWORK MATERIAL FERTILIZER AND PREPARATION METHOD THEREFOR

Abstract

A metal-organic framework material fertilizer and a preparation method therefor is provided. The novel fertilizer consists of nutrient molecules and external frameworks thereof, and is characterized in that the external frameworks are formed by coordination of inorganic metal ion clusters to organic joints under hydrothermal conditions. The metal-organic framework materials include two types, i.e., zinc-free and zinc-containing. The hydrothermal synthesis conditions of the novel metal-organic framework material fertilizer are that: the reaction temperature is 100° C., the reaction time is 24 h, the heating rate of the reactor is 2° C./min, and the speed of the stir bar is 120 revolutions per minute. The nutrient contents of the novel fertilizer are as follows: compound I: N: 4-5%, and P: 16-20%; and compound II: N: 5-7%, P: 15-18%, and Zn: 2-3%.

Claims

1. A metal-organic framework material fertilizer, comprising: nutrient molecules; and external frameworks thereof, wherein the external frameworks are formed by coordination of inorganic metal ion clusters to organic joints under hydrothermal conditions.

2. The new type of metal-organic framework material fertilizer according to claim 1, wherein the molar ratio composition of the raw materials of the synthesized metal-organic framework material includes: TABLE-US-00005 ferric chloride 0.25-2,   phosphoric acid 5-8, oxalic acid 0.5-15,  urea 3-5, deionized water 100.

3. The metal-organic framework material fertilizer according to claim 2, wherein in the molar ratio composition of the components of the metal-organic framework material, zinc sulfate 0.1-0.5 mol is added.

4. The metal-organic framework material fertilizer according to claim 2, wherein the molar ratio of a formula of the synthesized organic framework material fertilizer is as follows: ferric chloride 1, phosphoric acid 6, oxalic acid 1, urea 3, and deionized water 100.

5. The metal-organic framework material fertilizer according to claim 3, wherein the molar ratio of a formula of the synthesized organic framework material fertilizer is as follows: ferric chloride 1, zinc sulfate 0.25, phosphoric acid 6, oxalic acid 1, urea 3, and deionized water 100.

6. The metal-organic framework material fertilizer according to claim 1, wherein the hydrothermal synthesis parameters include: reaction temperature 100° C., reaction time 24 h, reactor heating rate 2° C./min, and stir bar speed 120 rpm.

7. Preparation of the metal-organic framework material fertilizer according to claim 2, wherein there are the following steps, a. completely dissolve ferric chloride, phosphoric acid, oxalic acid and urea in deionized water and mix them well to form a mixed solution; b. pour the mixed solution into a stainless steel reactor and then completely seal the reactor, and set the reaction temperature at 100° C., the reaction time at 24 h and the reactor heating rate at 2° C./min; and c. open the reactor when the temperature drops to room temperature after the reaction is over, filter the solution with filter paper and then wash with deionized water 3 times to obtain a product.

8. Preparation of the metal-organic framework material fertilizer according to claim 3, wherein there are the following steps, a. completely dissolve ferric chloride, zinc sulfate, phosphoric acid, oxalic acid and urea in deionized water and mix them well to form a mixed solution; b. pour the mixed solution into a stainless steel reactor and then completely seal the reactor, and set the reaction temperature at 100° C., the reaction time at 24 h and the reactor heating rate at 2° C./min; and c. open the reactor when the temperature drops to room temperature after the reaction is over, filter the solution with filter paper and then wash with deionized water 3 times to obtain a product.

Description

BRIEF DESCRIPTION

[0044] Some of the embodiments will be described in detail, with references to the following Figures, wherein like designations denote like members, wherein:

[0045] FIG. 1 depicts a curve of the release percentage (%) of available nitrogen (ammonium nitrogen and nitrate nitrogen);

[0046] FIG. 2 depicts a curve of the release percentage (%) of available phosphorus; and

[0047] FIG. 3 depicts a curve of the release percentage (%) of available zinc.

DETAILED DESCRIPTION

[0048] Embodiment 1, a metal-organic framework material fertilizer and a preparation method therefor, preparation of compound I: Weigh 1 mol of ferric chloride, 6 mol of phosphoric acid, 1 mol of oxalic acid, 3 mol of urea (CO(NH.sub.2).sub.2) and 100 mol of deionized water (H.sub.2O), put them in a beaker, stir them with a glass rod, pour them into a reactor after the oligomers are completely dissolved and mixed well, completely seal the reactor, set the reaction temperature at 100° C., the reaction time at 24 h, the reactor heating rate at 2° C./min and the speed of the stir bar at 120 rpm, open the reactor when the temperature drops to room temperature after the reaction is over, filter the solution with filter paper and then wash with deionized water 3 times to obtain a product.

[0049] Nutrient release determination method: Accurately weigh 0.13 g of urea, mix it with 300 g of the test soil, and then add them to a culture plate with a diameter of 15 cm. Weigh the samples with the same nitrogen content according to the nitrogen contents of compound I and compound II, mix each of them with 300 g of the test soil, and add the mixtures to plates and then adjust the water content of each culture plate to 38%. Cover the culture plates with plastic wraps to prevent the water from evaporating too quickly, repeat each treatment 3 times and place all the plates in a cool place in the laboratory. Take soil samples once every two weeks. Use a discrete automatic analyzer (SmartChem200, Alliance, France) to determine the content of available nitrogen (ammonium nitrogen and nitrate nitrogen) and use ICAP-OES (ICAP 7000, Thermo Fisher, UK) to determine the contents of available phosphorus and available zinc.

[0050] Embodiment 2, a metal-organic framework material fertilizer and a preparation method therefor, preparation of compound II: Weigh 1 mol of ferric chloride, 0.25 mol of zinc sulfate, 6 mol of phosphoric acid, 1 mol of oxalic acid, 3 mol of urea (CO(NH.sub.2).sub.2) and 100 mol of deionized water (H.sub.2O), put them in a beaker, stir them with a glass rod, pour them into a reactor after the oligomers are completely dissolved and mixed well, completely seal the reactor, set the reaction temperature at 100° C., the reaction time at 24 h, the reactor heating rate at 2° C./min and the speed of the stir bar at 120 rpm, open the reactor when the temperature drops to room temperature after the reaction is over, filter the solution with filter paper and then wash with deionized water 3 times to obtain a product.

[0051] Embodiment 3, basically the same as Embodiment 1, except the following changes: The molar ratio of the raw materials of the metal-organic framework material is as follows: Ferric chloride (FeCl.sub.3.6H.sub.2O) 0.25, phosphoric acid (H.sub.3PO.sub.4) 5, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 0.5, urea (CO(NH.sub.2).sub.2) 3, and deionized water (H.sub.2O) 100.

[0052] Embodiment 4, basically the same as Embodiment 1, except the following changes: The molar ratio of the raw materials of the metal-organic framework material is as follows: Ferric chloride (FeCl.sub.3.6H.sub.2O) 2, phosphoric acid (H.sub.3PO.sub.4) 8, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 1.5, urea (CO(NH.sub.2).sub.2) 5, and deionized water (H.sub.2O) 100.

[0053] Embodiment 5, basically the same as Embodiment 1, except the following changes: The molar ratio of the raw materials of the metal-organic framework material is as follows: Ferric chloride (FeCl.sub.3.6H.sub.2O) 0.25, phosphoric acid (H.sub.3PO.sub.4) 8, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 0.5, urea (CO(NH.sub.2).sub.2) 5, and deionized water (H.sub.2O) 100.

[0054] Embodiment 6, basically the same as Embodiment 1, except the following changes: The molar ratio of the raw materials of the metal-organic framework material is as follows: Ferric chloride (FeCl.sub.3.6H.sub.2O) 2, phosphoric acid (H.sub.3PO.sub.4) 5, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 1.5, urea (CO(NH.sub.2).sub.2) 3, and deionized water (H.sub.2O) 100.

[0055] Embodiment 7, basically the same as Embodiment 1, except the following changes: The molar ratio of the raw materials of the metal-organic framework material is as follows: Ferric chloride (FeCl.sub.3 6H.sub.2O) 0.25, zinc sulfate (ZnSO.sub.4.7H.sub.2O) 0.1, phosphoric acid (H.sub.3PO.sub.4) 5, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 0.5, urea (CO(NH.sub.2).sub.2) 1, and deionized water (H.sub.2O) 100.

[0056] Embodiment 8, basically the same as Embodiment 2, except the following changes: The molar ratio of the raw materials of the zinc-containing metal-organic framework material (compound II) is as follows: Ferric chloride (FeCl.sub.3.6H.sub.2O) 2, zinc sulfate (ZnSO.sub.4.7H.sub.2O) 0.5, phosphoric acid (H.sub.3PO.sub.4) 8, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 1.5, urea (CO(NH.sub.2).sub.2) 5, and deionized water (H.sub.2O) 100.

[0057] Embodiment 9, basically the same as Embodiment 2, except the following changes: The molar ratio of the raw materials of the zinc-containing metal-organic framework material is as follows: Ferric chloride (FeCl.sub.3.6H.sub.2O) 0.25, zinc sulfate (ZnSO.sub.4.7H.sub.2O) 0.5, phosphoric acid (H.sub.3PO.sub.4) 5, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 1.5, urea (CO(NH.sub.2).sub.2) 1, and deionized water (H.sub.2O) 100.

[0058] Embodiment 10, basically the same as Embodiment 2, except the following changes: The molar ratio of the raw materials of the zinc-containing metal-organic framework material is as follows: Ferric chloride (FeCl.sub.3.6H.sub.2O) 2, zinc sulfate (ZnSO.sub.4.7H.sub.2O) 0.1, phosphoric acid (H.sub.3PO.sub.4) 8, oxalic acid (H.sub.2C.sub.2O.sub.4.2H.sub.2O) 0.5, urea (CO(NH.sub.2).sub.2) 5, and deionized water (H.sub.2O) 100.

[0059] Although the present invention has been disclosed in the form of preferred embodiments and variations thereon, it will be understood that numerous additional modifications and variations could be made thereto without departing from the scope of the invention.

[0060] For the sake of clarity, it is to be understood that the use of “a” or “an” throughout this application does not exclude a plurality, and “comprising” does not exclude other steps or elements. The mention of a “unit” or a “module” does not preclude the use of more than one unit or module.