# US 12,180,125 B2 · Method for preparing weathered coal-derived humic acid/urea-formaldehyde slow-release fertilizer granules by reactive extrusion process with depolymerization-activation-polycondensation trinity and fertilization method

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- Number: US 12,180,125 B2
- Document ID: US12180125B2
- Status: Granted
- Kind: B2
- Application number: 18/431,971
- Filed: 2024-02-03
- Published: 2024-05-30
- Granted: 2024-12-31
- Earliest claimed: 2023-08-22
- Assignees: North University of China; Shanxi Zhongbei New Material Technology Co., Ltd.
- Applicants: North University of China; Shanxi Zhongbei New Material Technology Co., Ltd.
- Inventors: Yaqing Liu; Yingfang Tong; Peng Gao; Guizhe Zhao
- Web page: https://patentgrep.com/patent/US12180125B2

## CPC

- C05C 9/02: containing urea-formaldehyde condensates
- A01C 21/00: Methods of fertilising {, sowing or planting}
- B01J 2/20: by expressing the material, e.g. through sieves and fragmenting the extruded length
- C05F 11/02: from peat, brown coal, and similar vegetable deposits
- C05G 3/40: for affecting fertiliser dosage or release rate; for affecting solubility
- C05G 3/80: Soil conditioners
- C05G 5/12: Granules or flakes
- C08H 6/00: {Macromolecular compounds derived from lignin, e.g. tannins, humic acids}
- C05C: NITROGENOUS FERTILISERS
- A01C: PLANTING; SOWING; FERTILISING (parts, details or accessories of agricultural machines or implements, in general A01B51/00 - A01B75/00)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C05F: ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- 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 (organic fertilisers containing added bacterial cultures, mycelia, or the like C05F11/08; organic fertilisers containing plant vitamins or hormones C05F11/10); FERTILISERS CHARACTERISED BY THEIR FORM
- C08H: DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS (polysaccharides C08B; natural rubber C08C; natural resins or their derivatives C09F; bituminous materials C10)

## Abstract

A method for preparing a weathered coal-derived humic acid/urea-formaldehyde slow-release fertilizer granule by reactive extrusion process with depolymerization-activation-polycondensation trinity is provided. In an alkaline environment, paraformaldehyde is depolymerized into formaldehyde small molecules, which react with urea to form monohydroxymethylurea and dihydroxymethylurea. Under the strong shearing action of screws of the twin-screw reactive extruder, the macromolecular weathered coal-derived humic acid is depolymerized into relatively small molecule weathered coal-derived humic acid, and abundant active carboxyl groups are exposed, some of which immediately undergo dehydration condensation with —NH2 on the urea-formaldehyde molecule produced by the polycondensation of hydroxymethylurea during the reactive extrusion process to generate weathered coal-derived humic acid/urea-formaldehyde and its granules.

## Claims

### Claim 1

A method for preparing a weathered coal-derived humic acid/urea-formaldehyde slow-release fertilizer granule by reactive extrusion process with depolymerization-activation-polycondensation trinity, comprising:
(1) adding urea, paraformaldehyde, and water to a reactor followed by adjustment to pH 8-12 and reaction at 30-80° C. for 1-3 h to obtain a hydroxymethylurea solution;
wherein a mass ratio of urea to paraformaldehyde is 2-4:1, and the water is 10-50% of a total mass of urea and paraformaldehyde;
(2) adding a weathered coal-derived humic acid and an alkaline activator to the hydroxymethylurea solution obtained in the step (1) followed by reaction at 30-80° C. for 5-30 min to obtain a reaction mixture;
wherein the weathered coal-derived humic acid is 10-50% of the total mass of urea and paraformaldehyde; and the alkaline activator is 0-10% of a mass of the weathered coal-derived humic acid;
(3) sealing a die orifice between a reaction unit and an extrusion unit of a reaction-extrusion integrated machine; and adjusting the reaction mixture obtained in the step (2) to pH 3-5 followed by feeding to a twin-screw reactive extruder of the reaction unit of the reaction-extrusion integrated machine;
(4) starting screws of the twin-screw reactive extruder, and simultaneously starting a vacuumization-devolatilization device of the twin-screw reactive extruder to remove moisture from the reaction mixture, and reacting the reaction mixture at a temperature of 50-90° C. and a screw rotation speed of 50-150 rpm for 10-30 min; during this process, depolymerization and activation reactions of the weathered coal-derived humic acid, a condensation reaction of the hydroxymethylurea to generate urea-formaldehyde, and a polycondensation reaction between the generated activated weathered coal-derived humic acid and the generated urea-formaldehyde are carried out simultaneously;
(5) opening the die orifice between the reaction unit and the extrusion unit, and starting a twin-screw extruder of the extrusion unit such that a reaction product obtained in the step (4) is delivered by the twin-screw reactive extruder of the reaction unit to the twin-screw extruder of the extrusion unit; and extruding the reaction product at an extrusion temperature of 50-90° C. and a screw rotation speed of 50-150 rpm through the twin-screw extruder to obtain a strip product; and
(6) drying the strip product obtained in the step (5) at a preset temperature followed by granulation to obtain the weathered coal-derived humic acid/urea formaldehyde slow-release fertilizer in a cylindrical particle form, wherein weathered coal-derived humic acid molecules are inserted into a main chain of urea formaldehyde.

### Claim 2

A fertilization method, comprising:
(1) adding urea, paraformaldehyde, and water to a reactor followed by adjustment to pH 8-12 and reaction at 30-80° C. for 1-3 h to obtain a hydroxymethylurea solution;
wherein a mass ratio of urea to paraformaldehyde is 2-4:1, and the water is 10-50% of a total mass of urea and paraformaldehyde;
(2) adding a weathered coal-derived humic acid and an alkaline activator to the hydroxymethylurea solution obtained in the step (1) followed by reaction at 30-80° C. for 5-30 min to obtain a reaction mixture;
wherein the weathered coal-derived humic acid is 10-50% of the total mass of urea and paraformaldehyde; and the alkaline activator is 0-10% of a mass of the weathered coal-derived humic acid;
(3) sealing a die orifice between a reaction unit and an extrusion unit of a reaction-extrusion integrated machine; and adjusting the reaction mixture obtained in the step (2) to pH 3-5 followed by feeding to a twin-screw reactive extruder of the reaction unit of the reaction-extrusion integrated machine;
(4) starting screws of the twin-screw reactive extruder, and simultaneously starting a vacuumization-devolatilization device of the twin-screw reactive extruder to remove moisture from the reaction mixture, and reacting the reaction mixture at a temperature of 50-90° C. and a screw rotation speed of 50-150 rpm for 10-30 min; during this process, depolymerization and activation reactions of the weathered coal-derived humic acid, a condensation reaction of the hydroxymethylurea to generate urea-formaldehyde, and a polycondensation reaction between the generated activated weathered coal-derived humic acid and the generated urea-formaldehyde are carried out simultaneously;
(5) opening the die orifice between the reaction unit and the extrusion unit, and starting a twin-screw extruder of the extrusion unit such that a reaction product obtained in the step (4) is delivered by the twin-screw reactive extruder of the reaction unit to the twin-screw extruder of the extrusion unit; and extruding the reaction product at an extrusion temperature of 50-90° C. and a screw rotation speed of 50-150 rpm through the twin-screw extruder to obtain a strip product;
(6) drying the strip product obtained in the step (5) at a preset temperature followed by granulation to obtain a weathered coal-derived humic acid/urea formaldehyde slow-release fertilizer granule in a cylindrical particle form, wherein weathered coal-derived humic acid molecules are inserted into a main chain of urea formaldehyde; and
(7) applying, by a sowing-fertilization machine, the weathered coal-derived humic acid/urea formaldehyde slow-release fertilizer granule while performing sowing.

### Claim 3 (depends on 2)

The fertilization method of claim 2, wherein an application amount of the weathered coal-derived humic acid/urea formaldehyde slow-release fertilizer granule is 8-15 kg of nitrogen per mu.