CN108129524B - Method for preparing fulvic acid salt by activating low-rank coal through composite photocatalyst - Google Patents
Method for preparing fulvic acid salt by activating low-rank coal through composite photocatalyst Download PDFInfo
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- CN108129524B CN108129524B CN201711270432.4A CN201711270432A CN108129524B CN 108129524 B CN108129524 B CN 108129524B CN 201711270432 A CN201711270432 A CN 201711270432A CN 108129524 B CN108129524 B CN 108129524B
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- 239000003245 coal Substances 0.000 title claims abstract description 69
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical class 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 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000003213 activating effect Effects 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 18
- 230000004913 activation Effects 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 73
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000003077 lignite Substances 0.000 claims description 10
- 239000003415 peat Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 3
- 239000004021 humic acid Substances 0.000 abstract description 35
- 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 34
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 33
- 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 description 29
- 239000002509 fulvic acid Substances 0.000 description 29
- 229940095100 fulvic acid Drugs 0.000 description 29
- 239000000243 solution Substances 0.000 description 25
- 239000011787 zinc oxide Substances 0.000 description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 14
- 229910052700 potassium Inorganic materials 0.000 description 14
- 239000011591 potassium Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 10
- 230000001678 irradiating effect Effects 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- -1 nitro humic acid Chemical compound 0.000 description 1
- 239000003895 organic fertilizer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G99/00—Subject matter not provided for in other groups of this subclass
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
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- 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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a method for preparing fulvic acid salt by activating low-rank coal through a composite photocatalyst, which comprises the following steps: uniformly mixing low-rank coal powder and water, adding alkali to adjust the pH value to 8-11, stirring for 1-2h, adding an oxidant, reacting for 1-3h at the temperature of 25-55 ℃, and performing solid-liquid separation to obtain a humate solution; adding a composite photocatalyst, stirring and reacting for 2-6h under the condition of ultraviolet irradiation, carrying out solid-liquid separation, taking the solution, and evaporating to dryness to obtain a solid fulvic acid salt product. The method has the advantages of simple production process, environmental protection, low production cost and high humic acid activation rate in the low-rank coal, and can obviously improve the yield of the fulvic acid salt prepared from the low-rank coal.
Description
Technical Field
The invention relates to a method for preparing fulvic acid salt by activating low-rank coal through a composite photocatalyst, and belongs to the technical field of coal chemical industry.
Background
The low-rank coal is coal which has long flame, smoke and low coalification degree during combustion, and comprises lignite, peat and weathered coal. The humic acid content in the low-rank coal can reach 30% -80%, and the humic acid can be used as a fertilizer synergist, a soil conditioner, a pesticide slow-release synergist and the like, and is a green and environment-friendly organic fertilizer. The humic acid comprises three types of fulvic acid, ulmic acid and fulvic acid, the molecular weight is sequentially increased, the smaller the molecular weight of the humic acid is, and the more obvious the effects of improving soil and promoting plant growth are. However, the content of the small-molecular fulvic acid in the low-rank coal is not high, and the yield of the small-molecular fulvic acid needs to be increased by activating the low-rank coal, so that how to effectively prepare the high-yield fulvic acid by using the low-rank coal becomes a key point for whether the low-rank coal can be applied in the field of fertilizers.
The method for preparing fulvic acid by activating low-rank coal at the present stage comprises a mechanical method, a nitric acid oxidation method and a biological oxidation degradation method, but the methods generally have the problems of high production cost, low activation rate of humic acid in the low-rank coal, easy pollution to the environment and the like, and are difficult to be used for large-scale production, so that the popularization and the use of the low-rank coal in the agricultural field are greatly limited. For example, EP00117223a1 discloses a process for extracting fulvic acid from humus such as peat, which comprises the steps of alkali extraction, precipitation by acid precipitation, separation and fractionation, and the fulvic acid thus obtained can be used in agricultural production. However, in the invention, a large amount of humic acid is precipitated by acid precipitation, a large amount of acid is needed, and the environment is easily polluted; meanwhile, macromolecular humic acid is difficult to be effectively converted into micromolecular fulvic acid. For another example, chinese patent document CN1456539A discloses a method for preparing agricultural fulvic acid, wherein the raw materials of the invention are raw materials containing humic acid, water and potassium permanganate as an oxidant, and the raw materials containing humic acid are brown coal powder, nitro humic acid or peat. The oxidizing agent potassium permanganate used in the invention is easy to decompose fulvic acid in the process of oxidizing humic acid, and the yield of fulvic acid is influenced finally. For another example, chinese patent document CN101033231A discloses a method for preparing high-purity medical Fulvic Acid (FA), which is a method for purifying low-grade coal by acid extraction and resin adsorption-desorption. The method comprises the following specific steps: (1) extracting low-grade coal containing FA with low-concentration hydrochloric acid or sulfuric acid to obtain FA solution; (2) adsorbing FA by using specific resin, and desorbing FA by using a desorption agent; (3) desalting and purifying with cation exchange resin; (4) concentrating FA water solution, and drying. Although the separation process of the method is simple and convenient, macromolecular humic acid is difficult to effectively convert into micromolecular fulvic acid, the preparation steps are more, the operation is complex, the resin cost is high, the resin is difficult to recycle, large-scale industrial production is difficult, and the method is not favorable for popularization and use in agriculture.
The fulvic acid salt is a substance obtained by salifying fulvic acid, and has the same application effect and prospect as fulvic acid. Therefore, the method for preparing the fulvic acid salt by activating the low-rank coal, which has the advantages of simple production process, low production cost, high yield of the fulvic acid salt and suitability for agricultural production and popularization, is developed, and has great economic value and social value.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the method for preparing the fulvic acid salt by activating the low-rank coal by the composite photocatalyst, which has the advantages of simple production process and high yield of the fulvic acid salt. The method disclosed by the invention is green and environment-friendly, low in production cost and high in humic acid activation rate in the low-rank coal, and can be used for remarkably improving the yield of fulvic acid salt prepared from the low-rank coal.
The technical scheme of the invention is as follows:
a method for preparing fulvic acid salt by activating low-rank coal through a composite photocatalyst comprises the following steps:
A. uniformly mixing low-rank coal powder and water, adding alkali to adjust the pH value to 8-11, stirring for 1-2h, adding an oxidant, reacting for 1-3h at the temperature of 25-55 ℃, and performing solid-liquid separation to obtain a humate solution;
B. and D, adding a composite photocatalyst into the humate solution obtained in the step A, stirring and reacting for 2-6h under the condition of ultraviolet irradiation, carrying out solid-liquid separation, and evaporating the solution to dryness to obtain a solid fulvate product.
According to the invention, the low-rank coal powder in the step A is prepared by grinding lignite, peat or weathered coal serving as an initial raw material.
According to the present invention, the particle size of the low-rank pulverized coal in the step a is preferably 30 to 60 mesh.
According to the invention, the mass ratio of the low-rank pulverized coal to the water in the step A is preferably 1: 2-6.
Preferably according to the invention, the base in step a is a hydroxide; preferably, the hydroxide is one or a mixture of sodium hydroxide and potassium hydroxide.
Preferably, the oxidizing agent in step a is one of hydrogen peroxide, sodium peroxide or ozone. Preferably, the oxidizing agent is an aqueous solution of hydrogen peroxide having a mass concentration of 30%.
According to the invention, the mass ratio of the oxidant to the low-rank pulverized coal in the step A is 0.15-0.45:1 in terms of pure substances.
Preferably, the mass of the composite photocatalyst in the step B is 0.1-0.7% of that of the low-rank coal powder in the step A.
Preferably, the composite photocatalyst in the step B is a composite photocatalyst of nano TiO2 and nano ZnO.
Preferably, in the composite photocatalyst of nano TiO2 and nano ZnO, the mass ratio of nano TiO2 to nano ZnO is 1: 0.1-0.2.
Preferably, the nano TiO2And nano-ZnO in the composite photocatalyst, nano-TiO2The grain diameter of the nano ZnO is 5nm-100nm, and the grain diameter of the nano ZnO is 20nm-100 nm.
Preferably, the nano TiO2The crystal form of (A) is anatase or a mixed crystal form of anatase and rutile.
Further preferably, in the anatase and rutile mixed crystal type TiO2, the mass ratio of the anatase crystal type TiO2 to the rutile crystal type TiO2 is 4: 1.
Preferably, according to the present invention, the wavelength of the ultraviolet light in step B is 254-365 nm.
According to the invention, the ultraviolet irradiation mode in the step B is interval irradiation; the interval irradiation mode conditions are as follows: after each continuous irradiation for 5-10min, stopping irradiation for 1-3 min.
According to the invention, the fulvic acid salt is one or a mixture of two of potassium fulvate salt and sodium fulvate salt.
Firstly, alkali extraction is carried out on low-rank coal by adopting alkali, so that most of humic acid in the low-rank coal is dissolved in an alkali solution; then adding oxidants such as hydrogen peroxide, decomposing part of macromolecular humic acid in the alkali solution into micromolecular humic acid by the oxidants through an oxidation chain scission mode, and further oxidizing and degrading the humic acid which is not dissolved out in the low-rank coal, thereby further improving the alkali extraction efficiency; then adding a composite photocatalyst into the humate solution obtained after solid-liquid separation, wherein the composite photocatalyst can be attached to the undecomposed macromolecular humate, and the undecomposed macromolecular humate can be further converted into micromolecular fulvate after being irradiated by ultraviolet light; in addition, the preferable intermittent ultraviolet irradiation mode can reduce the decomposition effect of the photocatalyst on the micromolecular fulvic acid salt and improve the yield of the micromolecular fulvic acid salt.
The invention has the beneficial effects that:
1. according to the invention, oxidants such as hydrogen peroxide are added after alkali extraction, so that the alkali extraction efficiency can be further improved while macromolecular humic acid is oxidized.
2. The invention can further effectively oxidize the macromolecular humate into the micromolecular fulvate through the catalytic action of the nanometer titanium dioxide and nanometer zinc oxide composite photocatalyst.
3. The invention can reduce the decomposition effect of the composite photocatalyst on the micromolecular fulvic acid salt and improve the extraction efficiency of the micromolecular fulvic acid salt by an intermittent ultraviolet irradiation mode.
4. According to the invention, the activation rate of humic acid in low-rank coal is effectively improved by a mode of first oxidation and then photocatalysis, and finally the yield of micromolecular fulvic acid salt is effectively improved.
5. The invention has simple preparation process and better repeatability, and can be popularized and used in large-scale agriculture; the preparation process does not use acid, is green and environment-friendly, and has lower cost; in addition, the low-rank coal has high humic acid activation rate, can obviously improve the yield of fulvic acid salt prepared by using the low-rank coal, and is favorable for further realizing large-scale popularization and application of the low-rank coal.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but it should not be construed that the present invention is limited to the examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In the embodiment, the lignite, the peat and the weathered coal are sold by chemical limited corporation of north china of denham, wherein the mass content of humic acid in the lignite is 50.4%, the mass content of humic acid in the peat is 48.9%, and the mass content of humic acid in the weathered coal is 48.7%.
The purities of the ZnO with the three particle sizes are all more than 99.5 percent, and the ZnO with the three particle sizes is sold by an Aladdin reagent company.
Example 1
A method for preparing sodium fulvate by activating low-rank coal through a composite photocatalyst comprises the following steps:
grinding 100g of lignite to powder with the particle size of 30 meshes, adding the powder into 200g of water, then adding solid sodium hydroxide to adjust the pH value to 8, stirring the mixture for 1 hour at room temperature, adding 50g of hydrogen peroxide with the mass fraction of 30%, reacting the mixture for 3 hours at the temperature of 25 ℃, and obtaining a humate solution after centrifugal separation;
adding 0.45g of TiO2 (with purity of more than 99.5%, available from anatase type, Hangzhou Wanjing new nanometer material science and technology Co., Ltd.) with average particle size of 5nm and 0.05g of ZnO with average particle size of 90nm +/-10 nm into the humate solution, under the irradiation condition of 254nm ultraviolet light, stopping irradiation for 1min after continuously irradiating for 8min, stirring and reacting for 2h at room temperature, centrifuging, and evaporating the centrifuged upper solution to dryness to obtain the solid powder A of the micromolecule sodium fulvate.
Example 2
A method for preparing potassium fulvate by activating low-rank coal through a composite photocatalyst comprises the following steps:
grinding 100g of lignite to powder with the particle size of 40 meshes, adding the powder into 400g of water, then adding solid potassium hydroxide to adjust the pH value to 10, stirring the mixture for 2 hours at room temperature, adding 100g of hydrogen peroxide with the mass fraction of 30%, reacting the mixture for 2 hours at the temperature of 40 ℃, and obtaining a humate solution after centrifugal separation;
adding 0.45g of TiO2 (with the purity of more than 99.5 percent, Germany Degussa P25 type titanium dioxide, in a mixed crystal form of anatase and rutile, wherein the weight ratio of anatase to rutile is 80/20) with the average particle size of 21nm and 0.05g of ZnO with the average particle size of 50nm +/-10 nm into the humate solution, stopping irradiating for 2min in the middle after continuously irradiating for 8min under the irradiation of ultraviolet light with the wavelength of 365nm, stirring and reacting for 4h at room temperature, then centrifugally separating, taking the centrifuged upper layer solution and evaporating to dryness, and obtaining the solid powder B of the micromolecule potassium fulvate.
Example 3
A method for preparing sodium fulvate by activating low-rank coal through a composite photocatalyst comprises the following steps:
grinding 100g of lignite to powder with the particle size of 60 meshes, adding the powder into 600g of water, then adding solid sodium hydroxide to adjust the pH value to 11, stirring the mixture at room temperature for 1.5h, adding 150g of hydrogen peroxide with the mass fraction of 30%, reacting the mixture for 1h at the temperature of 55 ℃, and filtering the mixture to obtain a humate solution;
adding 0.085g of TiO2 (with the purity of more than 99.5 percent and the purity of anatase type available from Aladdin reagent company) with the average particle size of 60nm and 0.015g of ZnO with the average particle size of 90nm +/-10 nm into the humate solution, stopping irradiating for 2min after continuously irradiating for 5min under the ultraviolet irradiation condition with the wavelength of 254nm, stirring and reacting for 6h at room temperature, centrifuging, taking the centrifuged upper layer solution, and evaporating to dryness to obtain the solid powder C of the micromolecule sodium fulvate.
Example 4
A method for preparing sodium fulvate by activating low-rank coal through a composite photocatalyst comprises the following steps:
grinding 100g of peat into powder with the particle size of 40 meshes, adding the powder into 400g of water, then adding solid sodium hydroxide to adjust the pH value to 9, stirring and reacting at room temperature for 1.5h, then adding 100g of hydrogen peroxide with the mass fraction of 30%, reacting at the temperature of 45 ℃ for 2h, and filtering to obtain a humate solution;
adding 0.59g of TiO2 (with the average particle size of more than 99.5 percent, anatase type and sold by Aladdin reagent company) with the average particle size of 100nm and 0.11g of ZnO with the average particle size of 30nm +/-10 nm into the humate solution, stopping irradiating for 1min after continuously irradiating for 5min under the condition of 365nm ultraviolet light, stirring and reacting for 4h at room temperature, centrifuging, taking the centrifuged upper layer solution, and evaporating to dryness to obtain the solid powder D of the micromolecular sodium fulvate.
Example 5
A method for preparing potassium fulvate by activating low-rank coal through a composite photocatalyst comprises the following steps:
grinding 100g of weathered coal into powder with the particle size of 40 meshes, adding the powder into 400g of water, then adding solid potassium hydroxide to adjust the pH value to 10, stirring the mixture for 1.5h at room temperature, adding 100g of hydrogen peroxide with the mass fraction of 30%, reacting the mixture for 2h at the temperature of 40 ℃, and filtering the mixture to obtain a humate solution;
adding 0.63g of TiO2 (with the average particle size of more than 99.5 percent, Germany Degussa P25 type titanium dioxide, the purity of which is more than 99.5 percent, and is a mixed crystal form of anatase and rutile, wherein the weight ratio of the anatase to the rutile is 80/20) and 0.063g of ZnO with the average particle size of 30nm +/-10 nm into the humate solution, stopping irradiating for 3min after continuously irradiating for 10min under the condition that the wavelength is 365nm, stirring and reacting for 4h at room temperature, then centrifugally separating, taking the centrifuged upper layer solution and evaporating to dryness, and obtaining the solid powder E of the micromolecular potassium fulvate.
Example 6
A method for preparing potassium fulvate by activating low-rank coal with a composite photocatalyst is as described in example 2, except that: the ultraviolet irradiation condition is continuous irradiation, and the other conditions are the same, so that solid powder B4 of the potassium fulvate salt is obtained.
Comparative example 1
A process for the preparation of potassium fulvate salt as described in example 2, except that: the photocatalyst added into the humate solution is only 0.5g of TiO2 (purity is more than 99.5%, German Degussa P25 type titanium dioxide is a mixed crystal form of anatase and rutile, wherein the weight ratio of the anatase to the rutile is 80/20) with the average grain diameter of 21nm, and ZnO with the average grain diameter of 50nm +/-10 nm is not added; the solid powder B1 of the potassium fulvate salt is obtained under the same other conditions.
Comparative example 2
A process for the preparation of potassium fulvate salt as described in example 2, except that: the photocatalyst added into the humate solution is only 0.5g of ZnO with the average grain diameter of 50nm +/-10 nm, and TiO2 with the average grain diameter of 21nm is not added; the solid powder B2 of the potassium fulvate salt is obtained under the same other conditions.
Comparative example 3
A process for the preparation of potassium fulvate salt as described in example 2, except that: and (3) adding the TiO2 and ZnO composite photocatalyst, and obtaining solid powder B3 of the potassium fulvate salt under the same conditions.
Comparative example 4
A process for the preparation of potassium fulvate salt as described in example 2, except that: no oxidant hydrogen peroxide is added, and other conditions are the same, so that solid powder B5 of the fulvic acid salt is obtained.
Test example 1
The content of the fulvic acid in each of the products of examples 1-6 was determined according to the method in appendix B of HG/T5045-5046-2016 standard, and the activation rate of humic acid was calculated from the finally determined amount of fulvic acid/content of humic acid in low-rank coal, with the following specific results:
TABLE 1 data table of the results of fulvic acid content and humic acid activation rate in the product obtained in the example
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Fulvic acid content (dry basis) | 20.2g | 22.2g | 20.7g | 21.3g | 21.1g | 20.8 |
| Activation rate of humic acid | 40.08％ | 44.05％ | 41.07％ | 43.56％ | 43.33％ | 41.27％ |
The products in comparative examples 1-4 were tested for fulvic acid content by referring to the method in appendix B of HG/T5045-5046-2016 standard, and the activation rate of humic acid was calculated from the finally measured fulvic acid amount/humic acid content in low-rank coal, with the following specific results:
TABLE 2 data sheet of results of fulvic acid content and humic acid activation rate in the product obtained by comparative example
As can be seen from the table 1, the humic acid activation rates of the lignite, the peat and the weathered coal can reach more than 40% by means of alkali extraction pre-oxidation and composite photocatalytic activation, which shows that the oxidation composite photocatalytic system has good activation capability on humic acid in low-rank coal, and can effectively improve the yield of fulvic acid salt; as can be seen from examples 2 and 6, the ultraviolet interval irradiation mode is superior to the continuous irradiation; in addition, as can be seen from table 2, the humic acid activation rate of the composite photocatalyst of the present invention is superior to that of a single photocatalyst, and the humic acid activation rate of the oxidation composite photocatalytic system is superior to that of a single oxidation or composite photocatalytic manner.
Claims (9)
1. A method for preparing fulvic acid salt by activating low-rank coal through a composite photocatalyst comprises the following steps:
A. uniformly mixing low-rank coal powder and water, adding alkali to adjust the pH value to 8-11, stirring for 1-2h, adding an oxidant, reacting for 1-3h at the temperature of 25-55 ℃, and performing solid-liquid separation to obtain a humate solution; the oxidant is one of hydrogen peroxide, sodium peroxide or ozone; the mass ratio of the low-rank coal powder to water is 1: 2-6;
B. adding a composite photocatalyst into the humate solution obtained in the step A, stirring and reacting for 2-6h under the condition of ultraviolet irradiation, carrying out solid-liquid separation, and evaporating the solution to dryness to obtain a solid fulvate product; the composite photocatalyst is nano TiO2And a composite photocatalyst of nano ZnO; the nano TiO2And nano-ZnO in the composite photocatalyst, nano-TiO2The mass ratio of the nano ZnO to the nano ZnO is 1: 0.1-0.2; the nano TiO2And nano ZIn the nO composite photocatalyst, nano TiO2The grain diameter of the nano ZnO is 5nm-100nm, and the grain diameter of the nano ZnO is 20nm-100 nm; the wavelength of the ultraviolet light is 254-365 nm; the ultraviolet light irradiation mode is interval irradiation; the interval irradiation mode conditions are as follows: after each continuous irradiation for 5-10min, stopping irradiation for 1-3 min.
2. The method for preparing the fulvic acid salt by activating the low-rank coal through the composite photocatalyst according to claim 1, wherein the low-rank coal powder in the step A is prepared by grinding lignite, peat or weathered coal serving as an initial raw material; the particle size of the low-rank coal powder is 30-60 meshes.
3. The method for preparing the fulvic acid salt by activating the low-rank coal through the composite photocatalyst as claimed in claim 1, wherein the alkali in the step A is hydroxide.
4. The method for preparing the fulvic acid salt by activating the low-rank coal through the composite photocatalyst as claimed in claim 3, wherein the hydroxide is one or a mixture of two of sodium hydroxide and potassium hydroxide.
5. The method for preparing the fulvic acid salt through activation of the low-rank coal by the composite photocatalyst according to claim 1, wherein the oxidant in the step A is a 30% aqueous hydrogen peroxide solution.
6. The method for preparing the fulvic acid salt by activating the low-rank coal through the composite photocatalyst according to claim 1, wherein the mass ratio of the oxidant to the low-rank coal powder in the step A is 0.15-0.45:1 in terms of pure substances.
7. The method for preparing the fulvic acid salt by activating the low-rank coal through the composite photocatalyst according to claim 1, wherein the mass of the composite photocatalyst in the step B is 0.1-0.7% of that of the low-rank coal powder in the step A.
8. The method for preparing fulvic acid salt from low-rank coal activated by composite photocatalyst as claimed in claim 1, wherein the nano TiO is2The crystal form of (A) is anatase or a mixed crystal form of anatase and rutile.
9. The method for preparing fulvic acid salt by activating low-rank coal through composite photocatalyst according to claim 8, wherein the TiO in anatase and rutile mixed crystal form2TiO of medium anatase crystal type and rutile crystal type2The mass ratio of (A) to (B) is 4: 1.
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| CN109400911A (en) * | 2018-11-13 | 2019-03-01 | 安徽富里馨生物科技有限公司 | A kind of agricultural potassium fulvate and preparation method thereof |
| CN109553501B (en) * | 2019-01-21 | 2021-09-21 | 宁夏然尔特工业产业研究院（有限公司） | Method for preparing active silicon-active humic acid compound fertilizer from low-grade coal and compound fertilizer obtained by method |
| CN110314647A (en) * | 2019-06-28 | 2019-10-11 | 咸阳职业技术学院 | A kind of complex coal adsorbing material and preparation method thereof |
| CN111393487B (en) * | 2020-04-03 | 2022-01-07 | 太原师范学院 | Preparation method of polymorphic fulvic acid nano material |
| CN113182079B (en) * | 2021-04-28 | 2022-11-29 | 郑州大学 | Method for producing mineralized metallurgical medicament by using low-rank coal for quality improvement, mineralized metallurgical medicament and application |
| CN115304785A (en) * | 2022-08-26 | 2022-11-08 | 安徽富里馨生物科技有限公司 | Method for extracting fulvic acid from weathered coal |
| JP7454303B1 (en) | 2023-04-05 | 2024-03-22 | 海賀 信好 | Water purification system, water purification method, and fulvic acid decomposition treatment method |
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