CN114957703A - Preparation method of potassium fulvate - Google Patents
Preparation method of potassium fulvate Download PDFInfo
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- CN114957703A CN114957703A CN202210677744.1A CN202210677744A CN114957703A CN 114957703 A CN114957703 A CN 114957703A CN 202210677744 A CN202210677744 A CN 202210677744A CN 114957703 A CN114957703 A CN 114957703A
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 38
- 239000011591 potassium Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 74
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 46
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 26
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 26
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 26
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 239000003077 lignite Substances 0.000 claims abstract description 21
- 239000003245 coal Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000009210 therapy by ultrasound Methods 0.000 claims description 35
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 27
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 26
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 23
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 23
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 23
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 20
- 238000010041 electrostatic spinning Methods 0.000 claims description 18
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- -1 polydimethylsiloxane Polymers 0.000 claims description 14
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 claims description 13
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 claims description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 13
- 229940095100 fulvic acid Drugs 0.000 claims description 13
- 239000002509 fulvic acid Substances 0.000 claims description 13
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 9
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229960001484 edetic acid Drugs 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002114 nanocomposite Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 abstract description 30
- 239000004021 humic acid Substances 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 14
- 238000003916 acid precipitation Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 30
- 230000001699 photocatalysis Effects 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 230000002209 hydrophobic effect Effects 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002124 endocrine Effects 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of potassium fulvate, and particularly relates to the technical field of humic acid. The invention can crush weathered coal and lignite, and acidify and wash the crushed weathered coal and lignite; hydrogen peroxide is dripped into the filter residue, and the filter residue can be oxidized; potassium hydroxide solution is added, so that the material can be effectively alkalized, and potassium ions are provided; the oxygen decomposition method and the alkali dissolution acid precipitation method are mutually matched for use, so that the yield of humic acid can be effectively improved; the composite catalyst carries out composite catalytic treatment on the filtrate, so that the reaction process of the filtrate can be effectively accelerated; adding the hydrogen peroxide solution again, heating, preserving heat, maintaining pressure, and cooling to obtain a potassium fulvate reaction solution; ferric sulfate and copper sulfate in the composite catalyst are compounded for use, so that the catalytic treatment effect of the composite catalyst on the filtrate can be effectively enhanced; the content of the potassium fulvate is higher, and the yield of the potassium fulvate can be effectively ensured.
Description
Technical Field
The invention relates to the technical field of humic acid, in particular to a preparation method of potassium fulvate.
Background
Humic acid resources in China are rich, and are mainly distributed in lignite, particularly young lignite of the third trimester, and are distributed in peat, and besides, weathered coal also contains different amounts of secondary humic acid. Fulvic acid is a water-soluble part with the minimum molecular weight and the highest content of active groups in humic acid, and functional groups of fulvic acid interact to reflect various specific physicochemical characteristics, can exert various physiological functions after entering animal and plant organisms, act on the metabolism of the animal and plant organisms by inhibiting or activating enzymes to reflect obvious stimulation, and play a role in treatment by regulating endocrine hormones and improving the immune function of the organisms. Fulvic acid has the general characteristics of humic acid, namely: firstly, the molecular weight of the compound is small and easy to be absorbed and utilized by organisms; secondly, the humic acid has more functional groups, has higher physiological activity than that of common humic acid, and has stronger complexing ability to metal ions; thirdly, humic acid can be directly dissolved in water, the water solution of the salts is alkaline, fulvic acid can be directly dissolved in water, and the water solution is acidic. The three characteristics enable the humic acid to have more purposes and better application effects in agriculture, medicine, livestock and veterinary medicine, food and other aspects than general humic acid, but at the beginning of the application in medicine, a large amount of curative effects are not widely applied by people, but have important development values. At present, the potential technology applied in the domestic fulvic acid agriculture mainly adopts a new technology combining mineral source fulvic acid and biological fermentation products internationally, and applies a technology combining a composite flora fermentation technology and a one-step fulvic acid extraction technology in the production process, so that the application of fulvic acid in agriculture is enhanced.
At present, the domestic application mainly focuses on the aspects of production increasing element, high-efficiency plant leaf fertilizer, organic liquid fertilizer, plant growth element and the like, and the technical content of the potassium fulvate is low.
Disclosure of Invention
In order to overcome the above defects of the prior art, the embodiment of the invention provides a preparation method of potassium fulvate.
A preparation method of potassium fulvate comprises the following specific steps:
the method comprises the following steps: crushing the dried weathered coal or brown coal into 90-110 meshes to obtain crushed materials; adding the crushed materials into a hydrochloric acid aqueous solution, soaking for 25-35 minutes, filtering to obtain filter residues, and washing the filter residues to be neutral by using distilled water;
step two: dropwise adding a hydrogen peroxide solution into the filter residue, heating to 55-65 ℃ after dropwise adding, reacting for 1h, and adding into a reaction container;
step three: simultaneously, respectively adding distilled water and potassium hydroxide solid into a reaction container, stirring and dissolving, heating to 75-85 ℃, carrying out ultrasonic reaction for 1.5-2.5 h, cooling to room temperature after the reaction is finished, carrying out centrifugal separation, removing residues, and taking filtrate;
step four: transferring the filtrate into a high-pressure kettle, dropwise adding polydimethylsiloxane, adding a composite catalyst, adding disodium ethylene diamine tetraacetate, stirring and dissolving;
step five: adding a hydrogen peroxide solution under a stirring state, heating to 75-85 ℃, maintaining the system pressure at 0.7-0.9 MPa, reacting for 7-9 hours, stopping heating, cooling to room temperature, and filtering; obtaining the potassium fulvate reaction liquid.
Furthermore, the crushed weathered coal or brown coal powder, the hydrogen peroxide solution, the potassium hydroxide, the polydimethylsiloxane, the composite catalyst and the ethylene diamine tetraacetic acid are prepared from the following components in parts by weight: 140-160: 111-144.3: 20-30: 0.05-0.15: 1-2: 4-6; the adding amount of the hydrogen peroxide solution in the second step and the using amount of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 70-80: 30-50; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 12-14, and the concentration of the hydrochloric acid aqueous solution is 0.8-1.2%; in the second step and the fifth step, the concentration of the hydrogen peroxide solution is 25-35%, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 55-65 min; in the third step, the ultrasonic treatment frequency is 25-35 KHz, and the ultrasonic treatment power is 420-480W; in the fifth step, a filter screen of 400-500 meshes is adopted during filtering;
furthermore, the crushed weathered coal or brown coal powder, the hydrogen peroxide solution, the potassium hydroxide, the polydimethylsiloxane, the composite catalyst and the ethylene diamine tetraacetic acid are prepared from the following components in parts by weight: 140: 111: 20: 0.05: 1: 4; the adding amount of the hydrogen peroxide solution in the second step and the using amount of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 70: 30; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 12, and the concentration of the hydrochloric acid aqueous solution is 0.8%; the concentration of the hydrogen peroxide solution in the step two and the step five is 25 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 55 min; in the third step, the ultrasonic treatment frequency is 25KHz, and the ultrasonic treatment power is 420W; in the fifth step, a 400-mesh filter screen is adopted during filtering;
furthermore, the crushed weathered coal or brown coal powder, the hydrogen peroxide solution, the potassium hydroxide, the polydimethylsiloxane, the composite catalyst and the ethylene diamine tetraacetic acid are prepared from the following components in parts by weight: 160: 144.3: 30: 0.15: 2: 6; the adding amount of the hydrogen peroxide solution in the second step and the using amount of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 80: 50; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 14, and the concentration of the hydrochloric acid aqueous solution is 1.2%; the concentration of the hydrogen peroxide solution in the step two and the step five is 35 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 65 min; in the third step, the ultrasonic treatment frequency is 35KHz, and the ultrasonic treatment power is 480W; in the fifth step, a 500-mesh filter screen is adopted during filtering;
furthermore, the crushed weathered coal or brown coal powder, the hydrogen peroxide solution, the potassium hydroxide, the polydimethylsiloxane, the composite catalyst and the ethylene diamine tetraacetic acid are prepared from the following components in parts by weight: 150: 127.65: 25: 0.10: 1.5: 5; the adding amount of the hydrogen peroxide solution in the second step and the using amount of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 75: 40; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 13, and the concentration of the hydrochloric acid aqueous solution is 1.0 percent; in the second step and the fifth step, the concentration of the hydrogen peroxide solution is 30 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 60 min; in the third step, the ultrasonic treatment frequency is 30KHz, and the ultrasonic treatment power is 450W; in the fifth step, a filter screen of 450 meshes is adopted during filtering;
the composite catalyst in the first step comprises the following components in percentage by weight: 47.0-48.0% of ferric sulfate, 7.0-8.0% of copper sulfate, 1.5-2.5% of silver nitrate, 0.8-1.2% of hexadecyl trimethoxy silane, 1.5-2.5% of tetrabutyl titanate, 2.5-3.5% of polyacrylonitrile, 2.5-3.5% of polyvinylpyrrolidone and the balance of ethanol;
the preparation process of the composite catalyst comprises the following specific preparation steps:
s1: weighing ferric sulfate, copper sulfate, silver nitrate, hexadecyl trimethoxy silane, tetrabutyl titanate, polyacrylonitrile, polyvinylpyrrolidone and ethanol in the raw materials according to the weight parts;
s2: mixing the silver nitrate, tetrabutyl titanate, polyacrylonitrile and ethanol in the step S1, and carrying out water bath ultrasonic treatment for 50-60 min to obtain a mixed solution A;
s3: adding the hexadecyl trimethoxy silane and the polyvinylpyrrolidone in the step S1 into the mixture A in the step S2, and continuing the water bath ultrasonic treatment for 20-30 min to obtain a mixed solution B;
s4: performing electrostatic spinning treatment on the mixed solution B in the step S3 to obtain nano composite fibers;
s5: and (5) performing ball milling composite treatment on the nano composite fiber in the step S4, the ferric sulfate and the copper sulfate in the step S1 to obtain the composite catalyst.
Further, the composite catalyst comprises the following components in percentage by weight: 47.0 percent of ferric sulfate, 7.0 percent of copper sulfate, 1.5 percent of silver nitrate, 0.8 percent of hexadecyl trimethoxy silane, 1.5 percent of tetrabutyl titanate, 2.5 percent of polyacrylonitrile, 2.5 percent of polyvinylpyrrolidone and the balance of ethanol.
Further, the composite catalyst comprises the following components in percentage by weight: 47.5 percent of ferric sulfate, 7.5 percent of copper sulfate, 2.0 percent of silver nitrate, 1.0 percent of hexadecyl trimethoxy silane, 2.0 percent of tetrabutyl titanate, 3.0 percent of polyacrylonitrile, 3.0 percent of polyvinylpyrrolidone and the balance of ethanol.
Further, in step S2, the water bath temperature is 70-80 ℃, the ultrasonic frequency is 32-34 KHz, and the ultrasonic power is 800-900W; in step S3, the water bath temperature is 60-70 ℃, the ultrasonic frequency is 1.5-1.7 MHz, and the ultrasonic power is 400-500W; in step S4, in the electrostatic spinning process, the voltage is 10-12 KV, the receiving distance is 14-16 cm, and the flow rate of the mixed liquid B is 1.2-1.4 ml/h; in step S5, a planetary ball mill is adopted for processing, and the revolution speed is 510-530 r/min; the rotation speed is 1020-1060 r/min, and the power is 27-29 KW.
Further, in step S2, the water bath temperature is 75 ℃, the ultrasonic frequency is 33KHz, and the ultrasonic power is 850W; in step S3, the water bath temperature is 65 ℃, the ultrasonic frequency is 1.6MHz, and the ultrasonic power is 450W; in step S4, in the electrostatic spinning process, the voltage is 11KV, the receiving distance is 15cm, and the flow rate of the mixed liquid B is 1.3 ml/h; in step S5, a planetary ball mill is adopted for processing, and the revolution speed is 520 r/min; the rotation speed is 1040r/min and the power is 28 KW.
The invention has the technical effects and advantages that:
1. the potassium fulvate reaction solution prepared by the preparation process disclosed by the invention is higher in potassium fulvate content, and the yield of potassium fulvate can be effectively ensured; the weathered coal and the lignite can be crushed, and the crushed weathered coal and the lignite are acidified and washed; hydrogen peroxide is dripped into the filter residue, and the filter residue can be oxidized; potassium hydroxide solution is added, so that the material can be effectively alkalized, and potassium ions are provided; the oxygen hydrolysis method and the alkali dissolution and acid precipitation method can obtain higher humic acid extraction rate, the highest extraction rate of the oxygen hydrolysis method is higher than that of the alkali dissolution and acid precipitation method, but the extraction flow of the alkali dissolution and acid precipitation method is shorter; the humic acid and the water are matched with each other for use, so that the yield of the humic acid can be effectively improved; dripping a defoaming agent into the filtrate, adding a composite catalyst and disodium ethylene diamine tetraacetate for blending, wherein the disodium ethylene diamine tetraacetate can effectively prevent the product from being precipitated and oxidized; the composite catalyst carries out composite catalytic treatment on the filtrate, so that the reaction process of the filtrate can be effectively accelerated; adding the hydrogen peroxide solution again, heating, preserving heat, maintaining pressure, and cooling to obtain a potassium fulvate reaction solution; ferric sulfate and copper sulfate in the composite catalyst are compounded for use, so that the catalytic treatment effect of the composite catalyst on the filtrate can be effectively enhanced;
2. in the process of preparing the composite catalyst, silver nitrate is used as a silver source in the composite catalyst to be compounded with titanium dioxide, and the nano silver and titanium dioxide composite material can be obtained through hydrophobic modification treatment of hexadecyl trimethoxy silane (HTDMS), so that the hydrophobic property and the photocatalytic property of the composite catalyst can be effectively enhanced; in the composite catalyst, tetrabutyl titanate is used as a titanium source, and water bath ultrasonic treatment is carried out under the condition that ethanol is used as a solvent to synthesize solid amorphous titanium dioxide particles; in the composite catalyst, polyacrylonitrile is used as a carrier, polyvinylpyrrolidone is used as a pore-forming agent, and the composite catalyst is loaded by adopting an electrostatic spinning technology under the electrostatic spinning treatment to obtain a photocatalytic fiber with reusability under the visible light condition, so that a PAN/TiO2 photocatalytic fiber with a large specific surface area and a porous structure on a single fiber is prepared, and meanwhile, nano silver particles are loaded on the PAN/TiO2 photocatalytic fiber with the porous structure under the electrostatic spinning treatment, so that the yield of humic acid can be effectively improved; the ferric sulfate, the copper sulfate and the porous PAN/TiO2 photocatalytic fiber loaded with the nano silver particles are used in a matching way, so that the yield of humic acid can be further increased; in step S2, mixing silver nitrate, tetrabutyl titanate, polyacrylonitrile, and ethanol, and performing ultrasonic treatment in water bath to effectively enhance the blending reaction effect of silver nitrate, tetrabutyl titanate, polyacrylonitrile, and ethanol, and ensure rapid reaction and compounding of silver nitrate, tetrabutyl titanate, and polyacrylonitrile; in step S3, hexadecyl trimethoxy silane and polyvinylpyrrolidone are added into the mixture A for water bath ultrasonic treatment, so that the pore-forming modification hydrophobic treatment effect on the composite material can be effectively enhanced; in step S4, the mixture B is subjected to electrostatic spinning, so that the raw materials in the mixture B can be effectively subjected to rapid compounding treatment, and the bonding effect between the raw materials is ensured; in step S5, the nano composite fiber is ball-milled and combined with ferric sulfate and copper sulfate, so as to effectively ensure the contact bonding effect of the composite catalyst.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a preparation method of potassium fulvate, which comprises the following specific steps:
the method comprises the following steps: crushing dried weathered coal or lignite (the content of humic acid is 40-50%, and the content of humic acid dry-based phenolic hydroxyl groups is 0.5-1 mmol/g) to 90 meshes to obtain crushed materials; adding 140g of the crushed material into a hydrochloric acid aqueous solution, soaking for 25 minutes, filtering to obtain filter residue, and washing the filter residue to be neutral by using distilled water;
step two: dropwise adding 70ml of hydrogen peroxide solution (the density is 1.11g/ml) into the filter residue, heating to 55 ℃ after dropwise adding is finished, reacting for 1h, and adding into a three-neck flask;
step three: simultaneously, respectively adding 400ml of distilled water and 20g of potassium hydroxide solid into a three-neck flask, stirring and dissolving, heating to 75 ℃, carrying out ultrasonic reaction for 1.5h, cooling to room temperature after the reaction is finished, carrying out centrifugal separation, removing residues, and taking filtrate;
step four: transferring the filtrate into a high-pressure autoclave, dripping 1 drop of polydimethylsiloxane (0.05 ml per drop and 1g/ml density), adding 1.0g of composite catalyst, adding 4g of disodium ethylene diamine tetraacetate, stirring and dissolving;
step five: adding 30ml (density is 1.11g/ml) of hydrogen peroxide solution under stirring, heating to 75 ℃, maintaining the system pressure at 0.7MPa, reacting for 7 hours, stopping heating, cooling to room temperature, and filtering; obtaining fulvic acid potassium reaction liquid;
the composite catalyst in the first step comprises the following components in percentage by weight: 47.0 percent of ferric sulfate, 7.0 percent of copper sulfate, 1.5 percent of silver nitrate, 0.8 percent of hexadecyl trimethoxy silane, 1.5 percent of tetrabutyl titanate, 2.5 percent of polyacrylonitrile, 2.5 percent of polyvinylpyrrolidone and the balance of ethanol;
the preparation process of the composite catalyst comprises the following specific preparation steps:
s1: weighing ferric sulfate, copper sulfate, silver nitrate, hexadecyl trimethoxy silane, tetrabutyl titanate, polyacrylonitrile, polyvinylpyrrolidone and ethanol in the raw materials according to the weight parts;
s2: mixing the silver nitrate, tetrabutyl titanate, polyacrylonitrile and ethanol in the step S1, and performing water bath ultrasonic treatment for 55min to obtain a mixed solution A;
s3: adding the hexadecyl trimethoxy silane and the polyvinylpyrrolidone in the step S1 into the mixture A in the step S2, and continuing the water bath ultrasonic treatment for 25min to obtain a mixed solution B;
s4: performing electrostatic spinning treatment on the mixed solution B in the step S3 to obtain nano composite fibers;
s5: and (4) performing ball milling composite treatment on the nano composite fibers in the step S4, the ferric sulfate and the copper sulfate in the step S1 to obtain the composite catalyst.
In the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 12, and the concentration of the hydrochloric acid aqueous solution is 0.8%; the concentration of the hydrogen peroxide solution in the step two and the step five is 25 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 55 min; in the third step, the ultrasonic treatment frequency is 25KHz, and the ultrasonic treatment power is 420W; in the fifth step, a 400-mesh filter screen is adopted during filtering; in step S2, the water bath temperature is 70 ℃, the ultrasonic frequency is 32KHz, and the ultrasonic power is 800W; in step S3, the water bath temperature is 60 ℃, the ultrasonic frequency is 1.5MHz, and the ultrasonic power is 400W; in step S4, in the electrostatic spinning process, the voltage is 10KV, the receiving distance is 14cm, and the flow rate of the mixed liquid B is 1.2 ml/h; in step S5, a planetary ball mill is adopted for processing, and the revolution speed is 510 r/min; the rotation speed is 1020r/min and the power is 27 KW.
Example 2:
different from the embodiment 1, the composite catalyst comprises the following components in percentage by weight: 48.0 percent of ferric sulfate, 8.0 percent of copper sulfate, 2.5 percent of silver nitrate, 1.2 percent of hexadecyl trimethoxy silane, 2.5 percent of tetrabutyl titanate, 3.5 percent of polyacrylonitrile, 3.5 percent of polyvinylpyrrolidone and the balance of ethanol.
Example 3:
different from the examples 1-2, the composite catalyst comprises the following components in percentage by weight: 47.5 percent of ferric sulfate, 7.5 percent of copper sulfate, 2.0 percent of silver nitrate, 1.0 percent of hexadecyl trimethoxy silane, 2.0 percent of tetrabutyl titanate, 3.0 percent of polyacrylonitrile, 3.0 percent of polyvinylpyrrolidone and the balance of ethanol.
Example 4:
different from the embodiment 3, in the step one, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 14, and the concentration of the hydrochloric acid aqueous solution is 1.2 percent; the concentration of the hydrogen peroxide solution in the step two and the step five is 35 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 65 min; in the third step, the ultrasonic treatment frequency is 35KHz, and the ultrasonic treatment power is 480W; in the fifth step, a 500-mesh filter screen is adopted during filtering; in step S2, the water bath temperature is 80 ℃, the ultrasonic frequency is 34KHz, and the ultrasonic power is 900W; in step S3, the water bath temperature is 70 ℃, the ultrasonic frequency is 1.7MHz, and the ultrasonic power is 500W; in step S4, in the electrostatic spinning process, the voltage is 12KV, the receiving distance is 16cm, and the flow rate of the mixed liquid B is 1.4 ml/h; in step S5, a planetary ball mill is adopted for processing, and the revolution speed is 530 r/min; the rotation speed is 1060r/min, and the power is 29 KW.
Example 5:
different from the embodiment 3, in the step one, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 13, and the concentration of the hydrochloric acid aqueous solution is 1.0 percent; the concentration of the hydrogen peroxide solution in the step two and the step five is 30 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 60 min; in the third step, the ultrasonic treatment frequency is 30KHz, and the ultrasonic treatment power is 450W; in the fifth step, a filter screen of 450 meshes is adopted during filtering; in step S2, the water bath temperature is 75 ℃, the ultrasonic frequency is 33KHz, and the ultrasonic power is 850W; in step S3, the water bath temperature is 65 ℃, the ultrasonic frequency is 1.6MHz, and the ultrasonic power is 450W; in step S4, in the electrostatic spinning process, the voltage is 11KV, the receiving distance is 15cm, and the flow rate of the mixed liquid B is 1.3 ml/h; in step S5, a planetary ball mill is adopted for processing, and the revolution speed is 520 r/min; the rotation speed is 1040r/min and the power is 28 KW.
Example 6:
different from the embodiment 5, the preparation method of the potassium fulvate comprises the following specific steps:
the method comprises the following steps: crushing dried weathered coal or lignite (the content of humic acid is 40-50%, and the content of humic acid dry-based phenolic hydroxyl groups is 0.5-1 mmol/g) to 110 meshes to obtain crushed materials; adding 160g of the crushed material into a hydrochloric acid aqueous solution, soaking for 35 minutes, filtering to obtain filter residue, and washing the filter residue to be neutral by using distilled water;
step two: dropwise adding 80ml of hydrogen peroxide solution (the density is 1.11g/ml) into the filter residue, heating to 65 ℃ after dropwise adding, reacting for 1h, and adding into a three-neck flask;
step three: simultaneously, respectively adding 500ml of distilled water and 30g of potassium hydroxide solid into a three-neck flask, stirring and dissolving, heating to 85 ℃, carrying out ultrasonic reaction for 2.5 hours, cooling to room temperature after the reaction is finished, carrying out centrifugal separation, removing residues, and taking filtrate;
step four: transferring the filtrate into a high-pressure autoclave, dropping 3 drops of polydimethylsiloxane (0.05 ml per drop, 1g/ml density), adding 2.0g of composite catalyst, adding 6g of disodium ethylene diamine tetraacetate, stirring and dissolving;
step five: adding 50ml of hydrogen peroxide solution (density is 1.11g/ml) under stirring, heating to 85 ℃, maintaining the system pressure at 0.9MPa, reacting for 9 hours, stopping heating, cooling to room temperature, and filtering; obtaining the fulvic acid potassium reaction solution.
Example 7:
different from the embodiment 5, the preparation method of the potassium fulvate comprises the following specific steps:
the method comprises the following steps: crushing dried weathered coal or lignite (the content of humic acid is 40-50%, and the content of humic acid dry-based phenolic hydroxyl groups is 0.5-1 mmol/g) to 100 meshes to obtain crushed materials; adding 150g of the crushed material into a hydrochloric acid aqueous solution, soaking for 30 minutes, filtering to obtain filter residue, and washing the filter residue to be neutral by using distilled water;
step two: dropwise adding 75ml of hydrogen peroxide solution into the filter residue, heating to 60 ℃ after dropwise adding, reacting for 1h, and adding into a three-neck flask;
step three: simultaneously adding 450ml of distilled water and 25g of potassium hydroxide solid into a three-neck flask respectively, stirring and dissolving, heating to 80 ℃, carrying out ultrasonic reaction for 2.0h, cooling to room temperature after the reaction is finished, carrying out centrifugal separation, removing residues, and taking filtrate;
step four: transferring the filtrate into a high-pressure autoclave, dripping 2 drops of polydimethylsiloxane, adding 1.5g of composite catalyst, adding 5g of disodium ethylene diamine tetraacetate, stirring and dissolving;
step five: adding 40ml of hydrogen peroxide solution under the stirring state, heating to 80 ℃, maintaining the system pressure at 0.8MPa, reacting for 8 hours, stopping heating, cooling to room temperature, and filtering; obtaining the fulvic acid potassium reaction solution.
Example 8:
different from the embodiment 7, the composite catalyst is prepared by compounding ferric sulfate and copper sulfate according to the weight ratio of 7: 1.
Comparative example 1:
the difference from example 3 is: the composite catalyst comprises the following components in percentage by weight: 47.5 percent of ferric sulfate, 7.5 percent of copper sulfate, 1.0 percent of hexadecyl trimethoxy silane, 2.0 percent of tetrabutyl titanate, 3.0 percent of polyacrylonitrile, 3.0 percent of polyvinylpyrrolidone and the balance of ethanol.
Comparative example 2:
the difference from example 3 is: the composite catalyst comprises the following components in percentage by weight: 47.5 percent of ferric sulfate, 7.5 percent of copper sulfate, 2.0 percent of silver nitrate, 1.0 percent of hexadecyl trimethoxy silane, 3.0 percent of polyacrylonitrile, 3.0 percent of polyvinylpyrrolidone and the balance of ethanol.
Comparative example 3:
the difference from example 3 is: the composite catalyst comprises the following components in percentage by weight: 47.5 percent of ferric sulfate, 7.5 percent of copper sulfate, 2.0 percent of silver nitrate, 2.0 percent of tetrabutyl titanate, 3.0 percent of polyacrylonitrile, 3.0 percent of polyvinylpyrrolidone and the balance of ethanol.
Comparative example 4:
the difference from example 7 is: in step S2, silver nitrate, hexadecyl trimethoxy silane, polyvinylpyrrolidone, tetrabutyl titanate, polyacrylonitrile, and ethanol are mixed, and then subjected to water bath ultrasonic treatment.
Comparative example 5:
the difference from example 7 is: there is no operation in step S4.
The potassium humate content, the fulvic acid content and the humic acid dry-based phenolic hydroxyl group content of the potassium fulvate reaction liquid in the examples and the comparative examples of the invention are measured according to HGT5334-2018 standard, and the obtained results are shown in the table I:
table one:
from the above table, it can be seen that: the reaction solution of the potassium fulvate has higher potassium fulvate content, and can effectively ensure the yield of the potassium fulvate.
In the invention, in the first step, the weathered coal and the lignite are crushed, and the crushed weathered coal and the lignite are acidified and washed; in the second step, hydrogen peroxide is dripped into the filter residue, and the filter residue can be oxidized; in the third step, potassium hydroxide solution is added, so that the material can be effectively alkalized, and potassium ions are provided; the oxygen hydrolysis method and the alkali dissolution and acid precipitation method can obtain higher humic acid extraction rate, the highest extraction rate of the oxygen hydrolysis method is higher than that of the alkali dissolution and acid precipitation method, but the extraction flow of the alkali dissolution and acid precipitation method is shorter; the humic acid and the water are matched with each other for use, so that the yield of the humic acid can be effectively improved; in the fourth step, the filtrate is dripped with the defoaming agent, the composite catalyst and the disodium ethylene diamine tetraacetate for blending, and the disodium ethylene diamine tetraacetate can effectively prevent the product from being precipitated and oxidized; the composite catalyst carries out composite catalytic treatment on the filtrate, so that the reaction process of the filtrate can be effectively accelerated; in the fifth step, adding the hydrogen peroxide solution again, heating, preserving heat, maintaining pressure, and cooling to obtain a potassium fulvate reaction solution; ferric sulfate and copper sulfate in the composite catalyst are compounded for use, so that the catalytic treatment effect of the composite catalyst on the filtrate can be effectively enhanced; in the composite catalyst, silver nitrate is used as a silver source to be compounded with titanium dioxide, and the nano silver and titanium dioxide composite material can be obtained through hydrophobic modification treatment of hexadecyl trimethoxy silane (HTDMS), so that the hydrophobic property and the photocatalytic property of the composite catalyst can be effectively enhanced; in the composite catalyst, tetrabutyl titanate is used as a titanium source, and water bath ultrasonic treatment is carried out under the condition that ethanol is used as a solvent to synthesize solid amorphous titanium dioxide particles; in the composite catalyst, polyacrylonitrile is used as a carrier, polyvinylpyrrolidone is used as a pore-foaming agent, and the composite catalyst is loaded by an electrostatic spinning technology under the electrostatic spinning treatment to obtain a photocatalytic fiber with reusability under the visible light condition, so that PAN/TiO2 photocatalytic fiber with a large specific surface area and a porous structure on a single fiber is prepared, and meanwhile, nano silver particles are loaded on the PAN/TiO2 photocatalytic fiber with the porous structure under the electrostatic spinning treatment, so that the yield of humic acid can be effectively improved; the ferric sulfate, the copper sulfate and the porous PAN/TiO2 photocatalytic fiber loaded with the nano silver particles are used in a matching way, so that the yield of humic acid can be further increased; the nano silver particles and hexadecyl trimethoxy silane are matched to realize hydrophobic self-cleaning anti-contamination treatment on the titanium dioxide composite fiber; ensuring the subsequent impurity removal and reusability of the titanium dioxide composite fiber as a catalyst; the hydrophobic purpose is to ensure the hydrophobic property of the titanium dioxide composite fiber, so that the composite fiber in the composite catalyst can be conveniently separated from the reaction liquid in the follow-up process; the humic acid dissolved in water is prevented from remaining in the composite fiber of the composite catalyst to influence the accuracy of detection data; in step S2, mixing silver nitrate, tetrabutyl titanate, polyacrylonitrile and ethanol, and performing ultrasonic treatment in water bath, so as to effectively enhance the blending reaction effect of silver nitrate, tetrabutyl titanate, polyacrylonitrile and ethanol, and ensure rapid reaction and compounding of silver nitrate, tetrabutyl titanate and polyacrylonitrile; in step S3, hexadecyl trimethoxy silane and polyvinylpyrrolidone are added into the mixture A for water bath ultrasonic treatment, so that the pore-forming modification hydrophobic treatment effect on the composite material can be effectively enhanced; in step S4, the mixture B is subjected to electrostatic spinning, so that the raw materials in the mixture B can be effectively subjected to rapid compounding treatment, and the bonding effect between the raw materials is ensured; in step S5, the nano composite fiber is ball-milled and combined with ferric sulfate and copper sulfate, so as to effectively ensure the contact bonding effect of the composite catalyst.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of potassium fulvate is characterized by comprising the following steps: the preparation method comprises the following specific steps:
the method comprises the following steps: crushing the dried weathered coal or brown coal into 90-110 meshes to obtain crushed materials; adding the crushed materials into a hydrochloric acid aqueous solution, soaking for 25-35 minutes, filtering to obtain filter residues, and washing the filter residues to be neutral by using distilled water;
step two: dropwise adding a hydrogen peroxide solution into the filter residue, heating to 55-65 ℃ after dropwise adding, reacting for 1h, and adding into a reaction container;
step three: simultaneously, respectively adding distilled water and potassium hydroxide solid into a reaction container, stirring and dissolving, heating to 75-85 ℃, carrying out ultrasonic reaction for 1.5-2.5 h, cooling to room temperature after the reaction is finished, carrying out centrifugal separation, removing residues, and taking filtrate;
step four: transferring the filtrate into a high-pressure kettle, dropwise adding polydimethylsiloxane, adding a composite catalyst, adding disodium ethylene diamine tetraacetate, stirring and dissolving;
step five: adding a hydrogen peroxide solution under a stirring state, heating to 75-85 ℃, maintaining the system pressure at 0.7-0.9 MPa, reacting for 7-9 hours, stopping heating, cooling to room temperature, and filtering; obtaining the fulvic acid potassium reaction solution.
2. The method for preparing potassium fulvate according to claim 1, wherein: the weathered coal or brown coal powder crushed aggregates, hydrogen peroxide solution, potassium hydroxide, polydimethylsiloxane, composite catalyst and ethylene diamine tetraacetic acid are mixed according to the weight portion ratio: 140-160: 111-144.3: 20-30: 0.05-0.15: 1-2: 4-6; the addition amount of the hydrogen peroxide solution in the second step and the dosage of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 70-80: 30-50; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 12-14, and the concentration of the hydrochloric acid aqueous solution is 0.8-1.2%; in the second step and the fifth step, the concentration of the hydrogen peroxide solution is 25-35%, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 55-65 min; in the third step, the ultrasonic treatment frequency is 25-35 KHz, and the ultrasonic treatment power is 420-480W; in the fifth step, a 400-500 mesh filter screen is adopted during filtering.
3. The method for preparing potassium fulvate according to claim 1, wherein: the weathered coal or brown coal powder crushed aggregates, hydrogen peroxide solution, potassium hydroxide, polydimethylsiloxane, composite catalyst and ethylene diamine tetraacetic acid are mixed according to the weight portion ratio: 140: 111: 20: 0.05: 1: 4; the adding amount of the hydrogen peroxide solution in the second step and the using amount of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 70: 30; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 12, and the concentration of the hydrochloric acid aqueous solution is 0.8%; the concentration of the hydrogen peroxide solution in the step two and the step five is 25 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 55 min; in the third step, the ultrasonic treatment frequency is 25KHz, and the ultrasonic treatment power is 420W; in the fifth step, a 400-mesh filter screen is adopted during filtering.
4. The method for preparing potassium fulvate according to claim 1, wherein: the weathered coal or brown coal powder crushed aggregates, hydrogen peroxide solution, potassium hydroxide, polydimethylsiloxane, composite catalyst and ethylene diamine tetraacetic acid are mixed according to the weight portion ratio: 160: 144.3: 30: 0.15: 2: 6; the adding amount of the hydrogen peroxide solution in the second step and the using amount of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 80: 50; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 14, and the concentration of the hydrochloric acid aqueous solution is 1.2%; the concentration of the hydrogen peroxide solution in the step two and the step five is 35 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 65 min; in the third step, the ultrasonic treatment frequency is 35KHz, and the ultrasonic treatment power is 480W; in the fifth step, a 500-mesh filter screen is adopted during filtering.
5. The method for preparing potassium fulvate according to claim 1, wherein: the weathered coal or brown coal powder crushed aggregates, hydrogen peroxide solution, potassium hydroxide, polydimethylsiloxane, composite catalyst and ethylene diamine tetraacetic acid are mixed according to the weight portion ratio: 150: 127.65: 25: 0.10: 1.5: 5; the addition amount of the hydrogen peroxide solution in the second step and the dosage of the hydrogen peroxide solution in the fifth step are as follows according to the weight ratio: 75: 40; in the first step, the volume ratio of the crushed material to the hydrochloric acid aqueous solution is 1: 13, and the concentration of the hydrochloric acid aqueous solution is 1.0%; the concentration of the hydrogen peroxide solution in the step two and the step five is 30 percent, and the dropping process of the hydrogen peroxide solution is controlled to be finished within 60 min; in the third step, the ultrasonic treatment frequency is 30KHz, and the ultrasonic treatment power is 450W; in the fifth step, a 450-mesh filter screen is adopted during filtering.
6. The method for preparing potassium fulvate according to claim 1, wherein: the composite catalyst in the first step comprises the following components in percentage by weight: 47.0-48.0% of ferric sulfate, 7.0-8.0% of copper sulfate, 1.5-2.5% of silver nitrate, 0.8-1.2% of hexadecyl trimethoxy silane, 1.5-2.5% of tetrabutyl titanate, 2.5-3.5% of polyacrylonitrile, 2.5-3.5% of polyvinylpyrrolidone and the balance of ethanol;
the preparation process of the composite catalyst comprises the following specific preparation steps:
s1: weighing ferric sulfate, copper sulfate, silver nitrate, hexadecyl trimethoxy silane, tetrabutyl titanate, polyacrylonitrile, polyvinylpyrrolidone and ethanol in the raw materials according to the weight parts;
s2: mixing the silver nitrate, tetrabutyl titanate, polyacrylonitrile and ethanol in the step S1, and carrying out water bath ultrasonic treatment for 50-60 min to obtain a mixed solution A;
s3: adding the hexadecyl trimethoxy silane and the polyvinylpyrrolidone in the step S1 into the mixture A in the step S2, and continuing the water bath ultrasonic treatment for 20-30 min to obtain a mixed solution B;
s4: performing electrostatic spinning treatment on the mixed solution B in the step S3 to obtain nano composite fibers;
s5: and (4) performing ball milling composite treatment on the nano composite fibers in the step S4, the ferric sulfate and the copper sulfate in the step S1 to obtain the composite catalyst.
7. The method for preparing potassium fulvate according to claim 6, wherein: the composite catalyst comprises the following components in percentage by weight: 47.0 percent of ferric sulfate, 7.0 percent of copper sulfate, 1.5 percent of silver nitrate, 0.8 percent of hexadecyl trimethoxy silane, 1.5 percent of tetrabutyl titanate, 2.5 percent of polyacrylonitrile, 2.5 percent of polyvinylpyrrolidone and the balance of ethanol.
8. The method for preparing potassium fulvate according to claim 6, wherein: the composite catalyst comprises the following components in percentage by weight: 47.5 percent of ferric sulfate, 7.5 percent of copper sulfate, 2.0 percent of silver nitrate, 1.0 percent of hexadecyl trimethoxy silane, 2.0 percent of tetrabutyl titanate, 3.0 percent of polyacrylonitrile, 3.0 percent of polyvinylpyrrolidone and the balance of ethanol.
9. The method for preparing potassium fulvate according to claim 6, wherein: in step S2, the water bath temperature is 70-80 ℃, the ultrasonic frequency is 32-34 KHz, and the ultrasonic power is 800-900W; in step S3, the water bath temperature is 60-70 ℃, the ultrasonic frequency is 1.5-1.7 MHz, and the ultrasonic power is 400-500W; in step S4, in the electrostatic spinning process, the voltage is 10-12 KV, the receiving distance is 14-16 cm, and the flow rate of the mixed liquid B is 1.2-1.4 ml/h; in step S5, a planetary ball mill is adopted for processing, and the revolution speed is 510-530 r/min; the rotation speed is 1020-1060 r/min, and the power is 27-29 KW.
10. The method for preparing potassium fulvate according to claim 9, wherein: in step S2, the water bath temperature is 75 ℃, the ultrasonic frequency is 33KHz, and the ultrasonic power is 850W; in step S3, the water bath temperature is 65 ℃, the ultrasonic frequency is 1.6MHz, and the ultrasonic power is 450W; in step S4, in the electrostatic spinning process, the voltage is 11KV, the receiving distance is 15cm, and the flow rate of the mixed liquid B is 1.3 ml/h; in step S5, a planetary ball mill is adopted for processing, and the revolution speed is 520 r/min; the rotation speed is 1040r/min and the power is 28 KW.
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