CN110801867A - Super-dispersed zero-valent metal solid catalyst for water treatment and preparation method thereof - Google Patents
Super-dispersed zero-valent metal solid catalyst for water treatment and preparation method thereof Download PDFInfo
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- CN110801867A CN110801867A CN201911080145.6A CN201911080145A CN110801867A CN 110801867 A CN110801867 A CN 110801867A CN 201911080145 A CN201911080145 A CN 201911080145A CN 110801867 A CN110801867 A CN 110801867A
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- transition metal
- montmorillonite
- phenol
- metal salt
- borohydride
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 229910001868 water Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011949 solid catalyst Substances 0.000 title abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 97
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000003624 transition metals Chemical class 0.000 claims abstract description 56
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 53
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 42
- -1 transition metal salt Chemical class 0.000 claims abstract description 41
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 5
- 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 claims description 5
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 18
- 229920002907 Guar gum Polymers 0.000 abstract description 10
- 229920002472 Starch Polymers 0.000 abstract description 10
- 239000001913 cellulose Substances 0.000 abstract description 10
- 229920002678 cellulose Polymers 0.000 abstract description 10
- 235000010980 cellulose Nutrition 0.000 abstract description 10
- 239000000665 guar gum Substances 0.000 abstract description 10
- 229960002154 guar gum Drugs 0.000 abstract description 10
- 235000010417 guar gum Nutrition 0.000 abstract description 10
- 229920002401 polyacrylamide Polymers 0.000 abstract description 10
- 230000009467 reduction Effects 0.000 abstract description 10
- 239000008107 starch Substances 0.000 abstract description 10
- 235000019698 starch Nutrition 0.000 abstract description 10
- 230000036284 oxygen consumption Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 150000001768 cations Chemical class 0.000 description 11
- 229920000891 common polymer Polymers 0.000 description 9
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- 239000012028 Fenton's reagent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002332 oil field water Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B01J35/394—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a super-dispersed zero-valent metal solid catalyst for water treatment and a preparation method thereof. The catalyst is prepared by dissolving a transition metal salt in a first solvent; the carboxylic acid (phenol) compound is dissolved or dispersed in a second solvent; mixing a transition metal salt solution and a carboxylic acid (phenol) compound solution to obtain a transition metal complex; adding montmorillonite into the metal complex; adding borohydride, stirring, filtering, washing and drying to obtain the catalyst. The metal catalyst can thoroughly degrade common oil field polymers such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution, the viscosity reduction rate is more than 90%, and the chemical oxygen consumption is reduced by more than 95%.
Description
Technical Field
The invention relates to the technical field of oil field pollutant cleaning, in particular to a preparation method of a super-dispersed zero-valent metal solid catalyst for water treatment.
Background
The petroleum industry is an important component in national economy, and nowadays, most of oil fields at home and abroad use a large amount of various polymers in the oil extraction process, so that the polymer content in the produced sewage of most of the oil fields is higher, and the problem of environmental pollution generated along with the polymer content is urgently solved. If the waste liquid is not treated or is not treated properly, the formation and the ecological environment can be seriously damaged. The existing method for treating sewage mainly selected in the oilfield field is a Fenton oxidation method, and has the advantages of high oxidation activity and H2O2Under certain conditions, the catalyst can be decomposed to form hydroxyl radical with strong oxidizability, and the oxidation-reduction potential of the hydroxyl radical in water is 2.8V and higher than H2O2(1.8V), the hydroxyl radical oxidizes the organic matter into CO through electron transfer and other ways2And H2O, and an excess of H2O2Can be gradually degraded into H2O, the oxidative degradation of the polymer is more thorough; the oxidation degradation product is a small molecular substance which is non-toxic and easy to biodegrade, does not produce secondary pollution and is a clean oxidation system; the medicines needed in the treatment process are cheap and easily available, and the treatment cost is low. At present, the method is widely applied to the oil field water treatment link. However, the activity of the Fenton reagent is still relatively low, and the Fenton reagent is greatly influenced by external conditions, particularly the pH value is higher than 3, namely precipitation is carried out, so that the Fenton reagent can only be used in a weakly acidic environment. However, oilfield operations waste water is typically in a slightly alkaline environment, which results in a very inefficient conventional oxidation system.
Montmorillonite is a non-metal mineral product with montmorillonite as a main mineral component, and the montmorillonite structure is 2: form 1 crystal structure, due to the presence of certain cations, such as Ca, in the layered structure formed by the montmorillonite unit cells2+、Mg2+、Na+、K+And the cations have unstable action with montmorillonite unit cells and are easy to exchange with other cations, so the cation has better ion exchange property. More importantly, a plurality of hexagonal cavities are formed in the middle of the crystal faces of the silicon-oxygen tetrahedron in the montmorillonite, and cations can be separated like bowls so as to achieve a highly dispersed state.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of a super-dispersed zero-valent metal solid catalyst for water treatment. Montmorillonite is a clay mineral with montmorillonite as the main mineral component, and the montmorillonite structure is 2: form 1 crystal structure, due to the presence of certain cations, such as Ca, in the layered structure formed by the montmorillonite unit cells2+、Mg2+、Na+、K+And the function of the cations and montmorillonite unit cells is unstable, and the cations are easy to exchange with other cations, so that the cation has better ion exchange property. And (3) loading other metal ions on the clay through ion exchange, and then reducing by borohydride to obtain the zero-valent metal. Due to the dispersibility of cations in the montmorillonite and the separation effect of ligands in the complex on metal ions, the reduced metal has high dispersibility. Reducing the metal by using a reducing agent in a dispersed state to obtain the highly dispersed zero-valent metal. The catalyst prepared by the invention has the characteristics of high efficiency and wide application range of pH value (range from strong acidity to strong basicity), and can realize effective degradation of organic polymers under mild conditions. The transition metal complex Fenton catalyst is immobilized and reduced by adopting montmorillonite, and the prepared catalyst has the characteristics of high efficiency and wide application range of pH value (range from strong acidity to strong basicity), and can effectively degrade organic polymers under mild conditions.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a super-dispersed zero-valent metal solid catalyst for water treatment comprises the following steps:
firstly, at room temperature, dissolving transition metal salt in a first solvent with 5-30 times of mass of the transition metal salt, wherein the transition metal salt is FeCl with chemical purity and purity higher than the chemical purity2、FeCl3、Fe2(SO4)3、CoCl2、NiCl2、CuCl2、CuSO4And ZnCl2The first solvent is water, methanol or ethanol with chemical purity or higherEthylene glycol, propylene glycol and combinations thereof;
secondly, dissolving or dispersing a carboxylic acid (phenol) compound in a second solvent with the mass 5-30 times of that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is EDTA disodium salt, sodium phthalate, sodium malonate, sodium oxalate and catechol which are chemically pure and above-purity reagents, and the second solvent is water, methanol, ethanol, ethylene glycol, propylene glycol and a composition thereof which are chemically pure and above-purity reagents;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 1:2-3.5, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, montmorillonite with 5-10 times mass of transition metal salt is added into the metal complex obtained in the third step and stirred for 4-12 hours, wherein the montmorillonite is industrial calcium-based montmorillonite or sodium-based montmorillonite;
fifthly, adding borohydride with the amount of 2-4 times of the metal salt into the mixture, and stirring and reacting for 2-4 hours at room temperature, wherein the borohydride is sodium borohydride and potassium borohydride of reagents with chemical purity and higher than the chemical purity;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying at 60-105 ℃ for 4-24 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The invention has the beneficial effects that: the catalyst can catalyze hydrogen peroxide in a pH range of 1-14 to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution, and the viscosity before and after reaction is measured by adopting an Ubbelohde viscometer at 25 ℃ according to a standard measuring method, wherein the viscosity reduction rate is more than 90%; under the condition of sufficient hydrogen peroxide, the COD can be reduced by over 95% by catalysis after the reaction and the determination by a GB11914-89 chemical oxygen demand determination method. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Examples
The invention is further illustrated by the following examples. It should be understood that the method described in the examples is only for illustrating the present invention and not for limiting the present invention, and that simple modifications of the preparation method of the present invention based on the concept of the present invention are within the scope of the claimed invention.
The present invention will be further described with reference to the following examples.
Example 1:
firstly, dissolving transition metal salt in a first solvent with 5 times of mass of the transition metal salt at room temperature, wherein the transition metal salt is chemically pure FeCl2The first solvent is chemically pure methanol;
secondly, dispersing another carboxylic acid (phenol) compound in a second solvent with the mass 5 times that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is chemically pure EDTA disodium salt, and the second solvent is chemically pure methanol;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 1:2, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, montmorillonite with the mass 5 times that of the transition metal salt is added into the metal complex obtained in the third step and stirred for 4 hours, wherein the montmorillonite is industrial calcium-based bentonite;
fifthly, adding borohydride with the amount of 2 times of the metal salt into the mixture, and stirring and reacting for 2 hours at room temperature, wherein the borohydride is chemical pure sodium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying for 24 hours at 60 ℃, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported super-dispersed transition metal catalyst prepared in this example can catalyze hydrogen peroxide to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.15%, the pH value of 5 and the temperature of 45 ℃ for 2 hours, and the viscosity of the 0.5% aqueous solution before and after reaction is measured by a standard measuring method at 25 ℃ by using an Ubbelohde viscometer, and the viscosity reduction rates are 90.5%, 93.6%, 96.4% and 93.4% respectively; under the condition of enough hydrogen peroxide, the COD can be reduced by 98.2%, 99.3%, 96.7% and 96.0% by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 2:
firstly, dissolving transition metal salt in a first solvent with the mass 10 times of that of the transition metal salt at room temperature, wherein the transition metal salt is chemically pure FeCl3The first solvent is deionized water;
secondly, dissolving another carboxylic acid (phenol) compound in a second solvent with the mass being 10 times that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is chemically pure sodium phthalate, and the second solvent is chemically pure ethanol;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 1:2.5, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, taking montmorillonite with 6 times mass of the transition metal salt, adding the montmorillonite into the metal complex obtained in the third step, and stirring for 5 hours, wherein the montmorillonite is industrial-grade sodium-based montmorillonite;
fifthly, adding borohydride with the amount of 4 times that of the metal salt into the mixture, and stirring and reacting for 4 hours at room temperature, wherein the borohydride is chemically pure potassium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying at 70 ℃ for 18 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported ultra-dispersed transition metal catalyst prepared in the embodiment can be used for catalyzing ammonium persulfate to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.2%, the pH value of 7, the temperature of 50 ℃ and the reaction time of 1h, and the viscosity of the 0.3% aqueous solution before and after reaction is measured by adopting an Ubbelohde viscometer at 25 ℃ according to a standard measuring method, wherein the viscosity reduction rates are 96.4%, 97.5%, 92.0% and 95.0% respectively; under the condition of enough ammonium persulfate, COD can be catalytically reduced by 99.1%, 96.7%, 98.5% and 97.5% by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 3:
firstly, dissolving a transition metal salt in a first solvent with the mass 15 times that of the transition metal salt at room temperature, wherein the transition metal salt is analytically pure Fe2(SO4)3The first solvent is analytically pure ethylene glycol;
secondly, dissolving another carboxylic acid (phenol) compound in a second solvent with the mass being 10 times that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is analytically pure sodium malonate, and the second solvent is deionized water;
and step three, mixing the transition metal salt solution prepared in the step one and the carboxylic (phenol) compound solution prepared in the step two according to the mass ratio of 1:3, mixing and stirring uniformly until the transition metal complex is completely dissolved to obtain a transition metal complex;
fourthly, taking montmorillonite with the mass of 8 times of that of the transition metal, adding the montmorillonite into the metal complex obtained in the third step, and stirring for 8 hours, wherein the montmorillonite is industrial-grade calcium-based montmorillonite;
fifthly, adding borohydride with the amount of 3.8 times of that of the metal salt into the mixture, and stirring and reacting for 3.6 hours at room temperature, wherein the borohydride is analytically pure potassium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying at 80 ℃ for 12 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported ultra-dispersed transition metal catalyst prepared in the embodiment can be used for catalyzing sodium persulfate to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.3%, the pH value of 9, the temperature of 40 ℃ and the reaction time of 2 hours, and the viscosity of the 0.3% aqueous solution before and after the reaction is measured by a standard measuring method at the temperature of 25 ℃ by adopting an Ubbelohde viscometer, wherein the viscosity reduction rates are 96.4%, 97.5%, 92.0% and 95.0% respectively; in the case of sufficient sodium persulfate, COD can be reduced by 99.1%, 96.7%, 98.5% and 97.5% in the presence of catalyst after reaction, as determined by GB11914-89 chemical oxygen demand determination method. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 4:
firstly, dissolving a transition metal salt in a first solvent with the mass 20 times that of the transition metal salt at room temperature, wherein the transition metal salt is chemically pure CoCl2The first solvent is analytically pure ethylene glycol;
secondly, dispersing another carboxylic acid (phenol) compound into a second solvent with the mass 15 times that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is chemically pure sodium oxalate, and the second solvent is water and ethylene glycol with the volume ratio of analytical purity of 1: 1;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 2.5, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, taking montmorillonite with the mass being 10 times of that of the transition metal salt, adding the montmorillonite into the metal complex obtained in the third step, and stirring for 12 hours, wherein the montmorillonite is sodium-based montmorillonite;
fifthly, adding borohydride with the amount of 3 times that of the metal salt into the mixture, and stirring and reacting for 3 hours at room temperature, wherein the borohydride is chemically pure potassium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying for 5 hours at 90 ℃, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported ultra-dispersed transition metal catalyst prepared in the embodiment can be used for catalyzing hydrogen peroxide to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.4%, the pH value of 11, the temperature of 40 ℃ and the reaction time of 2 hours, and the viscosity of the 0.3% aqueous solution before and after reaction is measured by a standard measuring method at 25 ℃ by adopting an Ubbelohde viscometer, wherein the viscosity reduction rates are 95.5%, 95.7%, 93.6% and 94.5% respectively; under the condition of enough hydrogen peroxide, COD can be reduced by 96.4%, 96.0%, 95.5% and 98.0% by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 5:
firstly, dissolving a transition metal salt in a first solvent with the mass 5-30 times that of the transition metal salt at room temperature, wherein the transition metal salt is analytically pure NiCl2The first solvent is chemically pure propylene glycol;
dissolving another carboxylic acid (phenol) compound in a second solvent with the mass being 20 times that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is chemically pure catechol, and the second solvent is chemically pure propylene glycol;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 1:3.5, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, taking montmorillonite with the mass being 10 times of that of the transition metal salt, adding the montmorillonite into the metal complex obtained in the third step, and stirring for 12 hours, wherein the montmorillonite is industrial-grade calcium-based montmorillonite;
fifthly, adding borohydride with the amount of 3 times that of the metal salt into the mixture, and stirring and reacting for 4 hours at room temperature, wherein the borohydride is chemical pure sodium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying at 105 ℃ for 4 hours, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported ultra-dispersed transition metal catalyst prepared in the embodiment can be used for catalyzing hydrogen peroxide to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.5% of glue solution, the pH value of 14, the temperature of 35 ℃ and the reaction time of 2 hours, and the viscosity of the 0.4% aqueous solution before and after reaction is measured by a standard measuring method at the temperature of 25 ℃ by using an Ubbelohde viscometer, wherein the viscosity reduction rates are 96.0%, 97.5%, 94.5% and 96.0% respectively; under the condition of enough hydrogen peroxide, COD can be reduced by 98.1%, 97.5%, 97.0% and 98.1% in a catalytic manner by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 6:
firstly, dissolving a transition metal salt in a first solvent with the mass 5-30 times that of the transition metal salt at room temperature, wherein the transition metal salt is chemically pure CuCl2The first solvent is chemical pure ethanol;
dissolving or dispersing another carboxylic acid (phenol) compound in a second solvent with the mass 30 times that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is analytically pure catechol, and the second solvent is analytically pure propylene glycol;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 1:2.2, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, taking montmorillonite with the mass being 10 times of that of the transition metal salt, adding the montmorillonite into the metal complex obtained in the third step, and stirring for 12 hours, wherein the montmorillonite is industrial-grade calcium-based montmorillonite;
fifthly, adding borohydride with the amount of 2.3 times of the metal salt into the mixture, and stirring and reacting for 3 hours at room temperature, wherein the borohydride is analytically pure potassium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying for 4 hours at 100 ℃, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported ultra-dispersed transition metal catalyst prepared in the embodiment can be used for catalyzing potassium persulfate to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.4% of glue solution, the pH value of 13 and the temperature of 35 ℃ for 2 hours, and the viscosity of the 0.2% aqueous solution before and after reaction is measured by a Ubbelohde viscometer at 25 ℃ according to a standard measuring method, wherein the viscosity reduction rates are 93.6%, 94.7%, 92.5% and 96.7% respectively; under the condition of enough potassium persulfate, COD can be reduced by 97.1%, 95.5%, 98.1% and 99.0% in a catalytic manner by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 7:
firstly, dissolving a transition metal salt in a first solvent with the mass 30 times that of the transition metal salt at room temperature, wherein the transition metal salt is chemically pure CuSO4The first solvent is chemically pure methanol;
secondly, dissolving another carboxylic acid (phenol) compound in a second solvent with the mass being 20 times that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is chemically pure EDTA disodium salt, and the second solvent is deionized water;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 1:2, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, taking montmorillonite with the mass of 8 times of that of the transition metal salt, adding the montmorillonite into the metal complex obtained in the third step, and stirring for 5 hours, wherein the montmorillonite is industrial-grade calcium-based montmorillonite;
fifthly, adding borohydride with the amount of 3 times that of the metal salt into the mixture, and stirring and reacting for 3 hours at room temperature, wherein the borohydride is chemically pure potassium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying for 6 hours at 80 ℃, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported ultra-dispersed transition metal catalyst prepared in the embodiment can be used for catalyzing sodium persulfate to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.3% of glue solution, the pH value of 10 and the temperature of 38 ℃ for 1h, and the viscosity of the 0.6% aqueous solution before and after reaction is measured by a Ubbelohde viscometer at 25 ℃ according to a standard measuring method, wherein the viscosity reduction rates are respectively 98.5%, 99.0%, 99.5% and 98.0%; under the condition of enough sodium persulfate, COD can be reduced by 99.0%, 99.5%, 99.6% and 99.1% in a catalytic manner by measuring the chemical oxygen demand by GB11914-89 after the reaction. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Example 8:
firstly, dissolving a transition metal salt in a first solvent with the mass being 18 times that of the transition metal salt at room temperature, wherein the transition metal salt is analytically pure ZnCl2The first solvent is analytically pure ethanol;
secondly, dispersing another carboxylic acid (phenol) compound in a second solvent with the mass 5-30 times of that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is analytically pure sodium phthalate, and the second solvent is chemically pure ethylene glycol;
thirdly, mixing the transition metal salt solution prepared in the first step and the carboxylic (phenol) compound solution prepared in the second step according to the mass ratio of 1:3.5, and uniformly stirring until the transition metal salt solution and the carboxylic (phenol) compound solution are completely dissolved to obtain a transition metal complex;
fourthly, taking montmorillonite with the mass being 7 times of that of the transition metal salt, adding the montmorillonite into the metal complex obtained in the third step, and stirring for 5 hours, wherein the montmorillonite is industrial-grade calcium-based montmorillonite;
fifthly, adding borohydride with the amount of 2.6 times of the metal salt into the mixture, and stirring and reacting for 3 hours at room temperature, wherein the borohydride is analytically pure sodium borohydride;
and sixthly, filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying for 8 hours at 75 ℃, and cooling to room temperature to obtain the supported ultra-dispersed transition metal catalyst.
The supported ultra-dispersed transition metal catalyst prepared in the embodiment can be used for catalyzing potassium persulfate to break molecular chains of common polymers in oil fields such as guar gum, cellulose, starch, polyacrylamide and the like in an aqueous solution at the use level of 0.3% of glue solution, the pH value of 9 and the temperature of 45 ℃ for 0.3h, and the viscosity of the 0.5% aqueous solution before and after reaction is measured by a Ubbelohde viscometer at 25 ℃ according to a standard measuring method, wherein the viscosity reduction rate is respectively 98.1%, 99.2%, 96.8% and 98.4%; under the condition of enough potassium persulfate, COD can be reduced by 98.5%, 95.0%, 98.0% and 97.5% in a catalytic manner after the reaction by using a chemical oxygen demand measuring method of GB 11914-89. The method obviously expands the pH range of the application of the traditional Fenton oxidation system.
Claims (8)
1. A composition characterized by: it contains transition metal complex, montmorillonite and borohydride; wherein the mass of the montmorillonite is 5-10 times of that of the transition metal; the mass of the borohydride is 2-4 times of that of the transition metal.
2. The composition of claim 1, wherein: the transition metal complex is formed by a transition metal salt and a carboxylic acid (phenol) compound; the transition metal salt is selected from FeCl with chemical purity and purity above2、FeCl3、Fe2(SO4)3、CoCl2、NiCl2、CuCl2、CuSO4And ZnCl2One or more of the above; the carboxylic acid (phenol) compound is selected from one or more of EDTA disodium salt, sodium phthalate, sodium malonate, sodium oxalate and catechol which are chemically pure and above pure reagents.
3. The composition of claim 1, wherein: the montmorillonite is industrial calcium-based montmorillonite and/or sodium-based montmorillonite; the borohydride is sodium borohydride and/or potassium borohydride of chemical purity and above.
4. A process for the preparation of a composition according to any one of claims 1 to 3, characterized in that it comprises the following steps:
1) dissolving transition metal salt in a first solvent with 5-30 times of mass at room temperature, wherein the transition metal salt is FeCl with chemical purity and purity higher than chemical purity2、FeCl3、Fe2(SO4)3、CoCl2、NiCl2、CuCl2、CuSO4And ZnCl2The first solvent is chemically pure water, methanol, ethanol, ethylene glycol, propylene glycol andcombinations thereof;
2) dissolving or dispersing a carboxylic acid (phenol) compound in a second solvent with the mass 5-30 times of that of the carboxylic acid (phenol) compound, wherein the carboxylic acid (phenol) compound is EDTA disodium salt, sodium phthalate, sodium malonate, sodium oxalate and catechol which are chemically pure and above-purity reagents, and the second solvent is water, methanol, ethanol, ethylene glycol, propylene glycol and a composition thereof which are chemically pure and above-purity reagents;
3) mixing the transition metal salt solution prepared in the first step and the carboxylic acid (phenol) compound solution prepared in the second step according to the mass ratio of 1:2-3.5, and uniformly stirring until the transition metal salt solution and the carboxylic acid (phenol) compound solution are completely dissolved to obtain a transition metal complex;
4) taking montmorillonite with the mass of 5-10 times of that of the transition metal salt, adding the montmorillonite into the metal complex obtained in the third step, and stirring, wherein the montmorillonite is industrial-grade calcium-based montmorillonite or sodium-based montmorillonite;
5) adding borohydride with the amount of 2-4 times of that of the metal salt into the mixture, and stirring at room temperature, wherein the borohydride is sodium borohydride or potassium borohydride of a chemical purity reagent or more;
6) and (4) filtering the mixture obtained in the fifth step, washing with deionized water until no transition metal ions are detected in the first step, drying for 4-24 times, and cooling to room temperature to obtain the composition.
5. The method of claim 4, wherein: stirring for 4-12 hours in step 4); stirring for 2-4 hours in step 5); drying for 4-24 hours at 60-105 ℃ in step 6).
6. A composition according to any one of claims 1 to 3, characterised in that it is prepared by a process according to claim 4 or 5.
7. A supported ultra-dispersed transition metal catalyst comprising the composition of any of claims 1 to 4 and an adjunct therefor.
8. Use of the composition of any one of claims 1 to 3 or claim 6, the catalyst of claim 7 in petrochemical industry; preferably, the use in catalyzing hydrogen peroxide or persulfate oxidant to reduce viscosity and scavenge Chemical Oxygen Demand (COD) of polymer solutions for oil field applications.
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