CN105778585A - Method for producing waterborne coating with phosphated residue - Google Patents
Method for producing waterborne coating with phosphated residue Download PDFInfo
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- CN105778585A CN105778585A CN201610281390.3A CN201610281390A CN105778585A CN 105778585 A CN105778585 A CN 105778585A CN 201610281390 A CN201610281390 A CN 201610281390A CN 105778585 A CN105778585 A CN 105778585A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Health & Medical Sciences (AREA)
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Abstract
The invention provides a method for producing waterborne coating with phosphated residue. The method includes: heating the phosphated residue and ammonia water in water bath with stirring, filtering prior to adding sodium hydroxide to obtain ferric hydroxide precipitate, and subjecting the ferric hydroxide precipitate to washing, filtering and drying prior to calcination at the temperature of 700-800 DEG C for 2-3 hours and crushing to obtain iron oxide red; stirring and mixing the iron oxide red, nanofiller, chelating agent, triethanolamine, methacrylic acid, acrylic acid, modified polyurethane, isothiazolinone and propylene glycol methyl ether acetate to obtain the waterborne coating. The phosphated residue is fully utilized to convert additives for preparing waterborne coating, the phosphated residue is turned into treasure, and the waterborne coating prepared is non-toxic, pollution free, green, environmentally friendly, zero in degree of adhesion, strong in corrosion resistance, few in metal spots and excellent in comprehensive performance; the method is simple in production process, continuous production of the phosphating technology is facilitated, zero emission of the phosphated residue is achieved, production cost can be lowered, and industrial production is promoted.
Description
Technical field
The invention belongs to paint field, be specifically related to a kind of method utilizing phosphatization slag to produce water paint.
Background technology
Water paint be a kind of with water be diluent, coating without organic solvent, there is abnormal smells from the patient nontoxic, non-stimulated, the harmless feature such as free from environmental pollution, receive the common concern of people in recent years, can be used in metal, plastics, glass and various material.
There is the defects such as antiseptic property difference, poor adhesive force more in water paint domestic at present, causing that metal surface there will be substantial amounts of metal mottling and Emulsified spot, what produce disadvantages described above is primarily due to it using water as solvent or disperse medium, owing to characteristic and the organic solvent of water have a great difference, as surface tension is big, vapourizing temperature is high, difficult moistening, less soluble etc., and therefore it exists poor adhesive force, during spray painting not volatile, affected by humidity greatly, be difficult to control, the problem such as corrosion-resistant.In the face of the harsh conditions of commercial Application, water paint in use suffers from restriction.Therefore the standard for water paint combination property is also more and more higher, and especially for different fields, it has different functional water paints becomes the exploitation focus of people especially.
Phosphatization slag is the inevitable outcome in phosphating process, wherein contain the mixture of substantial amounts of zinc phosphate and iron phosphate, phosphatization slag to be cleared up in time, otherwise phosphating process can be impacted, as using substantial amounts of phosphatization slag as garbage emission, then the material such as phosphate therein, nitrite can make soil acidification, causes soil pollution.If can substantial amounts of phosphatization slag be made full use of in water paint, then it be possible not only to promote the development of phosphating process and new thinking of development is provided for water paint field.
Summary of the invention
For overcoming deficiency of the prior art, the invention provides a kind of method utilizing phosphatization slag to produce water paint.Phosphatization slag is turned waste into wealth by the method, and is prepared for the washing coating of excellent combination property, has the advantages such as low, the environmental protection of cost.
In order to achieve the above object, the present invention is achieved in that a kind of method utilizing phosphatization slag to produce water paint, comprise the following steps: phosphatization slag and ammonia are heated according to solid-to-liquid ratio 4:1～3:1 in 55～65 DEG C of water-baths and is stirred continuously 5～6 hours, filter, filtering residue is washed to pH=7～8, according to waste residue: water: alkali=(1～2): (7～8): the mass ratio of (0.8～2) adds sodium hydroxide, it is stirred continuously 3～4 hours and obtains ferric hydroxide precipitate, by ferric hydroxide precipitate then through washing, filter, calcine at 700～800 DEG C 2～3 hours after drying and pulverize, obtain iron oxide red；Iron oxide red and Nano filling are added to the water dispersed, add chelating agen and stir 2～3 hours, be slowly added dropwise triethanolamine and regulate pH；Methacrylic acid, acrylic acid and modified polyurethane being added in solution, react 1～2 hour, addition isothiazolone and propylene glycol methyl ether acetate stand 1～2 hour after stirring 20～30 minutes, obtain water paint.
Further, the main raw materials in proportion of above-mentioned water paint is iron oxide red 15～20 parts, Nano filling 10～30 parts, chelating agen 5～10 parts, triethanolamine 2～6 parts, methacrylic acid 45～55 parts, 25～40 parts of acrylic acid, modified poly-ammonia 10～30 parts, isothiazolone 3～15 parts, propylene glycol methyl ether acetate 15～20 parts, 100～150 parts of water.
Described Nano filling is nano-calcium carbonate or nano silicon.
Described chelating agen is 1-hydroxy ethylidene-1,1-diphosphonic acid or ethylenediaminetetraacetic acid.
Described modified polyurethane by 4-4 '-methyl diphenylene diisocyanate and Polyethylene Glycol according to mol ratio (1～2): 1 polymerisation in bulk obtains.
This modified poly ester can adopt any one bulk polymerization known in the art to obtain, present invention preferably employs following methods: Polyethylene Glycol and Polyethylene Glycol monododecyl ether are according to (2～3): the mixed in molar ratio stirring of 1, it is warming up to 100 DEG C of evacuation, continuous dehydration 4 hours, it is cooled to 75 DEG C and adds 4-4 '-methyl diphenylene diisocyanate, high-speed stirred 15min, add stannous octoate, stir while adding and be brought rapidly up to 120 DEG C, obtain modified polyurethane.
Further, stannous octoate is (0.01～0.02) with the mol ratio of Polyethylene Glycol: (2.5～3).
Phosphatization slag is dissolved by the present invention, iron oxide red is obtained by adding applicable compound conversion, auxiliary agent of dosing as water paint cooperatively forms, with modified polyurethane, chelating agen, filler, antibacterial and film former etc., the water paint that combination property is good, without harmful material in this water paint composition, environmentally safe, and by the garbage phosphatization slag twice laid of phosphating process, not only increase the seriality of phosphating process, provide new approaches more to the selection of aqueous paint additive.Modified polyurethane can improve the thixotropy of water paint as thickening agent, and its main chain is more hydrophilic, and thickening agent is attached together with each component hydrophobic structure in coating, forms space network, makes coating have certain thixotropy, be conducive to processing in water.With propylene glycol methyl ether acetate as film former, this film former is not only nontoxic but also can form stable network structure with modified polyurethane.For the problem such as prevent coating to be chronically under moisture easy mouldization of coating, rotten, add isothiazolone,
Compared with prior art, present invention have the advantage that the present invention makes full use of phosphatization slag converting additive and prepares water paint, phosphatization slag is turned waste into wealth, gained water paint nontoxic pollution-free, environmental protection；Adhesive force 0 grade, difficult drop-off, corrosion resistance is strong, and metal mottling is few, excellent combination property；Production technology of the present invention is simple, not only contributes to phosphating process continuous prodution, reaches phosphatization slag zero-emission, and can reduce production cost, promotes industrialized production.
Detailed description of the invention
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.Experimental technique described in following embodiment, if no special instructions, is conventional method；Described reagent and material, if no special instructions, all commercially obtain.
Embodiment 1
(1) modified polyurethane is prepared:
By PEG20000 2.5mol and 2mol Polyethylene Glycol monododecyl ether mix and blend, it is warming up to 100 DEG C of evacuation, continuous dehydration 4 hours, it is cooled to 75 DEG C and adds 2.5mol4-4 '-methyl diphenylene diisocyanate, high-speed stirred 15min, add 0.01mol stannous octoate, stir while adding and be brought rapidly up to 120 DEG C, obtain modified polyurethane.
(2) phosphatization slag converts:
1000kg phosphatization slag and ammonia are heated according to solid-to-liquid ratio 4:1 in 65 DEG C of water-baths and is stirred continuously 5～6 hours, filter, filtering residue is washed to pH=7.5, according to waste residue: water: the mass ratio of alkali=1.5:7:1 adds sodium hydroxide, it is stirred continuously 3～4 hours and obtains ferric hydroxide precipitate 107.1g, ferric hydroxide precipitate is pulverized then through calcining at 800 DEG C 2～3 hours after washing, filtration, drying, obtains iron oxide red 32.9g.
(3) water paint is prepared:
Iron oxide red is added to the water dispersed with nano-calcium carbonate 15g, adds 1-hydroxy ethylidene-1,1-diphosphonic acid 11.7g and stir 2～3 hours, be slowly added dropwise triethanolamine 4g and regulate pH；100g methacrylic acid, 72g acrylic acid and 23g modified polyurethane being added in solution, react 1～2 hour, addition 6g isothiazolone and 30g propylene glycol methyl ether acetate stand 1～2 hour after stirring 20～30 minutes, obtain water paint.
Embodiment 2
(1) modified polyurethane is prepared:
By PEG20000 3mol and 2mol Polyethylene Glycol monododecyl ether mix and blend, it is warming up to 100 DEG C of evacuation, continuous dehydration 4 hours, it is cooled to 75 DEG C and adds 1.5mol4-4 '-methyl diphenylene diisocyanate, high-speed stirred 20min, add 0.01mol stannous octoate, stir while adding and be brought rapidly up to 120 DEG C, obtain modified polyurethane.
(2) phosphatization slag converts:
1000kg phosphatization slag and ammonia are heated according to solid-to-liquid ratio 4:1 in 65 DEG C of water-baths and is stirred continuously 5～6 hours, filter, filtering residue is washed to pH=7.5, according to waste residue: water: the mass ratio of alkali=1:8:2 adds sodium hydroxide, it is stirred continuously 3～4 hours and obtains ferric hydroxide precipitate 93.6g, ferric hydroxide precipitate is pulverized then through calcining at 800 DEG C 2～3 hours after washing, filtration, drying, obtains iron oxide red 33.8g.
(3) water paint is prepared:
Iron oxide red is added to the water dispersed with nano-calcium carbonate 25g, adds ethylenediaminetetraacetic acid 19.7g and stir 2～3 hours, be slowly added dropwise triethanolamine 2.9g and regulate pH；55g methacrylic acid, 36g acrylic acid and 22g modified polyurethane being added in solution, react 1～2 hour, addition 6g isothiazolone and 15g propylene glycol methyl ether acetate stand 1～2 hour after stirring 20～30 minutes, obtain water paint.
Embodiment 3
(1) modified polyurethane is prepared:
By PEG20000 3mol and 2mol Polyethylene Glycol monododecyl ether mix and blend, it is warming up to 100 DEG C of evacuation, continuous dehydration 4 hours, it is cooled to 75 DEG C and adds 1.5mol4-4 '-methyl diphenylene diisocyanate, high-speed stirred 15min, add 0.02mol stannous octoate, stir while adding and be brought rapidly up to 120 DEG C, obtain modified polyurethane.
(2) phosphatization slag converts:
1000kg phosphatization slag and ammonia are heated according to solid-to-liquid ratio 3:1 in 65 DEG C of water-baths and is stirred continuously 5～6 hours, filter, filtering residue is washed to pH=7.5, according to waste residue: water: the mass ratio of alkali=1:7.5:2 adds sodium hydroxide, it is stirred continuously 3～4 hours and obtains ferric hydroxide precipitate 106.3g, ferric hydroxide precipitate is pulverized then through calcining at 800 DEG C 2～3 hours after washing, filtration, drying, obtains iron oxide red 38.2g.
(3) water paint is prepared:
Iron oxide red is added to the water dispersed with nano-calcium carbonate 25g, adds ethylenediaminetetraacetic acid 16.3g and stir 2～3 hours, be slowly added dropwise triethanolamine 2.9g and regulate pH；45g methacrylic acid, 36g acrylic acid and 22g modified polyurethane being added in solution, react 1～2 hour, addition 10g isothiazolone and 16g propylene glycol methyl ether acetate stand 1～2 hour after stirring 20～30 minutes, obtain water paint.
Embodiment 4
(1) modified polyurethane is prepared:
By PEG20000 2.5mol and 2mol Polyethylene Glycol monododecyl ether mix and blend, it is warming up to 100 DEG C of evacuation, continuous dehydration 4 hours, it is cooled to 75 DEG C and adds 2.5mol4-4 '-methyl diphenylene diisocyanate, high-speed stirred 15min, add 0.02mol stannous octoate, stir while adding and be brought rapidly up to 120 DEG C, obtain modified polyurethane.
(2) phosphatization slag converts:
1000kg phosphatization slag and ammonia are heated according to solid-to-liquid ratio 4:1 in 65 DEG C of water-baths and is stirred continuously 5～6 hours, filter, filtering residue is washed to pH=7.5, according to waste residue: water: the mass ratio of alkali=1:7.5:2 adds sodium hydroxide, it is stirred continuously 3～4 hours and obtains ferric hydroxide precipitate 106.3g, ferric hydroxide precipitate is pulverized then through calcining at 800 DEG C 2～3 hours after washing, filtration, drying, obtains iron oxide red 38.2g.
(3) water paint is prepared:
Iron oxide red is added to the water dispersed with nano-calcium carbonate 25g, adds ethylenediaminetetraacetic acid 16.3g and stir 2～3 hours, be slowly added dropwise triethanolamine 2.9g and regulate pH；55g methacrylic acid, 36g acrylic acid and 28g modified polyurethane being added in solution, react 1～2 hour, addition 10g isothiazolone and 18g propylene glycol methyl ether acetate stand 1～2 hour after stirring 20～30 minutes, obtain water paint.
By on embodiment 1～4 gained water paint pre-coated metal test block surface, at room temperature dry in the sun can become dry film in 2-4 hour, film is carried out main performance test, wherein adhesive force detects according to the required standard of GB/T9286-1998, and resistance to impact detects according to the required standard of GB/T1732-1993.Above-mentioned dry film being carried out acid and alkali resistance test, is respectively placed in sulphuric acid and the sodium hydroxide of 0.1mol/L, at 15～25 DEG C, keep the time of regulation, take out sample and clean, dry up, whether visual examination phosphatization surface there is corrosion.Specific experiment data please refer to table 1.
Table 1 embodiment 1～4 water paint the performance test results
By test result indicate that above, water paint prepared by the present invention has good adhesive force and shock resistance, it is possible to meet the industrial circle requirement for coating acid resistance and alkali resistance, and paint ingredient green environmentally safe.
The above; it is only the present invention preferably detailed description of the invention; but protection scope of the present invention is not limited thereto; any those familiar with the art is in the technical scope of present disclosure; it is equal to replacement according to technical scheme and inventive concept thereof or is changed, all should be encompassed within protection scope of the present invention.
Claims (7)
1. one kind utilizes the method that phosphatization slag produces water paint, it is characterized in that, comprise the following steps: phosphatization slag and ammonia are heated according to solid-to-liquid ratio 4:1～3:1 in 55～65 DEG C of water-baths and is stirred continuously 5～6 hours, filter, filtering residue is washed to pH=7～8, according to waste residue: water: alkali=(1～2): (7～8): the mass ratio of (0.8～2) adds sodium hydroxide, it is stirred continuously 3～4 hours and obtains ferric hydroxide precipitate, by ferric hydroxide precipitate then through washing, filter, calcine at 700～800 DEG C 2～3 hours after drying and pulverize, obtain iron oxide red；Iron oxide red and Nano filling are added to the water dispersed, add chelating agen and stir 2～3 hours, be slowly added dropwise triethanolamine and regulate pH；Methacrylic acid, acrylic acid and modified polyurethane being added in solution, react 1～2 hour, addition isothiazolone and propylene glycol methyl ether acetate stand 1～2 hour after stirring 20～30 minutes, obtain water paint.
2. the method utilizing phosphatization slag to produce water paint according to claim 1, it is characterized in that, this water paint main raw materials in proportion is iron oxide red 15～20 parts, Nano filling 10～30 parts, chelating agen 5～10 parts, triethanolamine 2～6 parts, methacrylic acid 45～55 parts, 25～40 parts of acrylic acid, modified poly-ammonia 10～30 parts, isothiazolone 3～15 parts, propylene glycol methyl ether acetate 15～20 parts, 100～150 parts of water.
3. the method utilizing phosphatization slag to produce water paint according to claim 1, it is characterised in that described Nano filling is nano-calcium carbonate or nano silicon.
4. the method utilizing phosphatization slag to produce water paint according to claim 1, it is characterised in that described chelating agen is 1-hydroxy ethylidene-1,1-diphosphonic acid or ethylenediaminetetraacetic acid.
5. the method utilizing phosphatization slag to produce water paint according to claim 1, it is characterised in that described modified polyurethane by 4-4 '-methyl diphenylene diisocyanate and Polyethylene Glycol according to mol ratio (1～2): 1 polymerisation in bulk obtains.
6. the method utilizing phosphatization slag to produce water paint according to claim 5, it is characterized in that, the preparation method of described modified polyurethane is: Polyethylene Glycol and Polyethylene Glycol monododecyl ether are according to (2～3): the mixed in molar ratio stirring of 1, it is warming up to 100 DEG C of evacuation, continuous dehydration 4 hours, it is cooled to 75 DEG C and adds 4-4 '-methyl diphenylene diisocyanate, high-speed stirred 15min, add stannous octoate, stir while adding and be brought rapidly up to 120 DEG C, obtain modified polyurethane.
7. the method utilizing phosphatization slag to produce water paint according to claim 6, it is characterised in that the mol ratio of stannous octoate and Polyethylene Glycol is (0.01～0.02): (2.5～3).
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610281390.3A CN105778585A (en) | 2016-04-29 | 2016-04-29 | Method for producing waterborne coating with phosphated residue |
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| CN201610281390.3A CN105778585A (en) | 2016-04-29 | 2016-04-29 | Method for producing waterborne coating with phosphated residue |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111017897A (en) * | 2019-12-23 | 2020-04-17 | 泰安市永达环保科技有限公司 | Phosphating waste residue recycling treatment equipment and treatment method |
| CN111705528A (en) * | 2020-06-23 | 2020-09-25 | 广州明诺新材料科技有限公司 | Multifunctional auxiliary agent and preparation method thereof |
| CN113307693A (en) * | 2021-07-09 | 2021-08-27 | 石家庄学院 | Preparation method of slow-release water-soluble fertilizer |
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| CN103395761A (en) * | 2013-07-29 | 2013-11-20 | 丁忠华 | Method for preparing phosphate and iron oxide red by utilizing phosphated residue |
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| CN1840587A (en) * | 2005-03-28 | 2006-10-04 | 深圳市海川实业股份有限公司 | Method for preparing aqueous polyurethane thickener |
| US20100144925A1 (en) * | 2006-10-02 | 2010-06-10 | Ivan Cabrera | Plasters and Renders and Paints, Copolymer Dispersions and Their Use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111017897A (en) * | 2019-12-23 | 2020-04-17 | 泰安市永达环保科技有限公司 | Phosphating waste residue recycling treatment equipment and treatment method |
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| CN113307693A (en) * | 2021-07-09 | 2021-08-27 | 石家庄学院 | Preparation method of slow-release water-soluble fertilizer |
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