CN114762827B - Catalyst, preparation method and application thereof in treatment of peroxide-containing PO/CHP wastewater - Google Patents
Catalyst, preparation method and application thereof in treatment of peroxide-containing PO/CHP wastewater Download PDFInfo
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- CN114762827B CN114762827B CN202110053580.0A CN202110053580A CN114762827B CN 114762827 B CN114762827 B CN 114762827B CN 202110053580 A CN202110053580 A CN 202110053580A CN 114762827 B CN114762827 B CN 114762827B
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- titanium oxide
- catalyst
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- wastewater
- peroxide
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- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 17
- 239000011651 chromium Substances 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052788 barium Inorganic materials 0.000 claims abstract description 16
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 88
- 229910052742 iron Inorganic materials 0.000 claims description 44
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000005470 impregnation Methods 0.000 claims description 30
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 26
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 23
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 14
- 235000019253 formic acid Nutrition 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 6
- 159000000009 barium salts Chemical class 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 150000000703 Cerium Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000002715 modification method Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- -1 CHP peroxide Chemical class 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 5
- 229910001422 barium ion Inorganic materials 0.000 description 5
- 238000005842 biochemical reaction Methods 0.000 description 5
- 229910001430 chromium ion Inorganic materials 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- JESIHYIJKKUWIS-UHFFFAOYSA-N 1-(4-Methylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1 JESIHYIJKKUWIS-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003421 catalytic decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- MEUKEBNAABNAEX-UHFFFAOYSA-N hydroperoxymethane Chemical compound COO MEUKEBNAABNAEX-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005502 peroxidation Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
-
- 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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a catalyst for catalytic oxidation of organic peroxide, a preparation method thereof and a method for treating PO/CHP peroxide-containing wastewater by using the catalyst. The carrier of the catalyst is titanium oxide, and the active components comprise copper, chromium, cerium, nickel and barium in the form of oxides. The catalyst has good treatment effect on organic peroxide in POCHP wastewater, can effectively reduce the peroxide concentration and COD (chemical oxygen demand) value in the wastewater, and improves the biochemistry of the wastewater.
Description
Technical Field
The invention belongs to the technical field of chemical engineering and environmental engineering wastewater treatment, and particularly relates to a catalyst for catalyzing and oxidizing peroxide, a preparation method of the catalyst and a treatment method for treating peroxide-containing PO/CHP wastewater.
Background
The CHP (cumene hydroperoxide) process is a very important process for the preparation of propylene oxide and dimethylbenzyl alcohol monomers. The basic literature describing this process is the "new process for the production of dimethylbenzyl alcohol and propylene oxide by the CHP process". The basic process flow of the method is that in the peroxidation stage, air is used as an oxidant to oxidize cumene to cumene peroxide, the peroxide reacts with propylene in the epoxidation stage to form propylene oxide and dimethylbenzyl alcohol, and then the dimethylbenzyl alcohol is dehydrated to form cumene.
A large amount of wastewater is generated in the production process of the device, wherein the water produced by the top condensate of the cumene peroxidation tower contains a large amount of acidic substances, mainly formic acid, acetic acid and a small amount of phenol, and also contains a large amount of peroxide (mainly in the form of methyl hydroperoxide and cumene hydroperoxide). Peroxide has an inactivating effect on organisms, so that the biochemical property of the wastewater is poor, B/C=0 (B/C is a biochemical index, B/C is more excellent when B/C is more than 0.3 and less than 1, and B/C is less than 0.1 and is more difficult to be biochemical).
In order to improve the biodegradability of the wastewater and meet the requirement of biochemical discharge index (B/C is more than 0.3), peroxide in the wastewater needs to be pretreated, and the inactivation to organisms is reduced. The traditional treatment method is to decompose peroxide by reducing agents such as sodium thiosulfate, sodium bisulphite and the like, hydrogen peroxide decomposing enzyme and the like, or adjust the PH to be more than 12, so as to improve the decomposition of the peroxide, and the problems of low decomposition speed, high treatment cost and difficulty in achieving lower water concentration exist in the methods.
Patent US5993673 discloses a method for catalytic decomposition of peroxide, which uses alumina promoted by solid iron as a catalyst to treat peroxide-containing wastewater, uses low-concentration hydrogen peroxide as a peroxidation system, CN110605124 discloses a method for treating peroxide in POSM wastewater, wherein the peroxide is mainly EBHP (ethylbenzene hydroperoxide), and in practice the peroxide in the POCHP wastewater mainly contains cumene hydroperoxide CHP, the peroxide is relatively difficult to decompose, and the concentration of the peroxide can reach about 3.5 wt%.
There is a need to develop a new treatment process for promoting the catalytic decomposition of peroxides with high treatment efficiency and without secondary pollution.
Disclosure of Invention
It is an object of the present invention to provide a catalyst for the catalytic oxidation of organic peroxides which is stable to the peroxide treatment effect.
It is another object of the present invention to provide a process for preparing the catalyst.
It is a further object of the present invention to provide a process for treating peroxide-containing POCHP wastewater with the catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an organic peroxide catalytic oxidation catalyst, which comprises a carrier and an active component, wherein the carrier is titanium oxide; the active component includes copper, chromium, cerium, nickel and barium in the form of oxides.
Preferably, the content of the metal element of the active component is, based on the weight of the carrier:
copper 0.1 to 1wt%, preferably 0.5 to 0.7wt%;
0.2 to 0.8wt% chromium, preferably 0.4 to 0.6wt%;
cerium 0.1 to 1wt%, preferably 0.5 to 0.7wt%;
nickel 0.3 to 0.8wt%, preferably 0.5 to 0.7wt%;
barium 0.1 to 0.8wt%, preferably 0.4 to 0.6wt%.
In the invention, the pretreatment and activation method of the titanium oxide carrier comprises the following steps: grinding titanium oxide raw materialGrinding to 50-60 meshes in a grinding device, placing into a capacity barrel with a filter paper cover, drying at 110-130 ℃ for 5-6 h, cooling to room temperature to obtain titanium oxide coarse powder, mixing the titanium oxide coarse powder with an HCl solution with the mass fraction of 20-22% according to the mass ratio of 1:10, stirring for 20-24 h under a stirrer to obtain mixed liquor, diluting the mixed liquor with distilled water, centrifuging for 5-7 times to neutrality, drying for 5-6 h to obtain treated and activated titanium oxide, roasting at 500-700 ℃ for 2-4 h, and finally molding by a strip extruder to obtain the titanium oxide with the length of 1-2 cm and the specific surface area of 1000-2000 m 2 Support per gram.
As a preferred embodiment, the support is a modified titanium oxide modified by ultrasonic modification and optionally modified by adding Fenton iron mud and/or adding polyaluminum chloride as an auxiliary agent, more preferably, the support is a modified titanium oxide modified by ultrasonic modification and modified by adding Fenton iron mud and adding polyaluminum chloride as an auxiliary agent.
After the carrier mixture is subjected to modification pretreatment by adopting an ultrasonic technology, impurities in the gaps can be effectively removed, the phenomenon that the catalyst forms polymeric granular substances in the pore channels to block the pore channels in the process of oxidizing and decomposing organic matters is avoided, in addition, the specific surface area and the surface functional group property of the carrier can be improved by ultrasonic pretreatment, the adsorption effect of the porous surface of the catalyst on the organic matters is improved, the deactivation time can be prolonged, and the wastewater treatment effect is improved.
The ultrasonic modification method provided by the invention comprises the following steps: the ultrasonic power of the ultrasonic modification is selected to be 100-150W, the ultrasonic frequency is 50-80 Hz, preferably 60-70 Hz, the ultrasonic time is 30-50 min, the ultrasonic modified titanium oxide is obtained by washing the ultrasonic modified titanium oxide with pure water after treatment and drying the ultrasonic modified titanium oxide for 4-6 h at 115-125 ℃.
It is further preferred that the ultrasonically modified titanium oxide is modified with Fenton iron sludge in an amount of 1.0 to 6.0 wt.%, preferably 2.0 to 3.0 wt.%, based on the weight of titanium oxide.
Fenton treatment technology is a common advanced oxidation technology in the wastewater treatment process, and is mainly used for carrying out catalytic decomposition on refractory substances in wastewater by adding hydrogen peroxide and ferrous sulfate so as to achieve the aim of improving biochemistry. The carrier prepared by firing the iron mud according to a certain proportion has high hardness, large porosity and strong alkalinity resistance, and can effectively improve the specific surface area and the structural strength of the carrier.
The method for modifying the titanium oxide modified by ultrasonic waves by using the iron mud comprises the following steps of: the iron mud solution and the titanium oxide modified by ultrasonic are subjected to isovolumetric impregnation, wherein the impregnation time is 50-250 min, preferably 100-150 min; and then drying the obtained solid at 60-150 ℃ for 3-5 h, and roasting at 450-600 ℃ for 3-5 h to obtain the titanium oxide modified by ultrasonic and iron mud addition. The iron mud solution is prepared by dissolving iron mud in pure water, and the concentration of the prepared solution is 0.01-0.02 g of iron mud/mL of pure water.
Still more preferably, the titanium oxide modified with ultrasonic and Fenton iron mud is modified by adding polyaluminium chloride as an auxiliary agent, the content of polyaluminium chloride being 2.0 to 7.0wt%, preferably 4.0 to 5.0wt%, based on the weight of titanium oxide.
The method for modifying titanium oxide modified by ultrasonic and Fenton iron mud by using polyaluminium chloride comprises the following steps: 5.0 to 10 weight percent of polyaluminum chloride aqueous solution and titanium oxide modified by ultrasonic wave and iron mud are subjected to isovolumetric impregnation for 50 to 250 minutes, preferably 100 to 150 minutes; and then drying the obtained solid at 60-150 ℃ for 3-5 h, and roasting at 450-600 ℃ for 3-5 h to obtain the titanium oxide modified by ultrasonic and added with iron mud and added with polyaluminium chloride auxiliary agent.
The preparation method of the catalyst comprises the following steps:
adding a solution containing copper salt, chromium salt, cerium salt, nickel salt and barium salt into a carrier, and carrying out isovolumetric impregnation for 100-250 min, preferably 150-200 min; and then drying the obtained solid at 120-140 ℃ for 2-3 h, and roasting at 550-650 ℃ for 3-5 h to obtain the catalyst.
Preferably, before the isovolumetric impregnation, the carrier is subjected to vacuum pretreatment, wherein the time of the vacuum pretreatment is 40-60 min, the vacuum degree is 96.0-98.0 KPa, and the particulate impurities in the carrier processing process are removed through the vacuum pretreatment, so that the adhesion effect of the active components on the surface of the carrier is improved.
Preferably, the copper, chromium, cerium, nickel and barium salts are derived from one or more of nitrate, acetate and carbonate salts containing the corresponding metal element, respectively, preferably nitrate.
The invention also relates to the use of the catalyst in the treatment of peroxide-containing wastewater.
A method for treating peroxide-containing PO/CHP wastewater comprises the following steps:
(1) Carrying out catalytic oxidation reaction on PO/CHP wastewater containing peroxide;
(2) Performing biochemical treatment on the wastewater obtained in the step (1) and then discharging;
the peroxide-containing PO/CHP wastewater is wastewater generated in the PO/CHP production process, and meets the following conditions: organic peroxide (including hydrogen peroxide and cumene hydroperoxide and methyl hydroperoxide) is less than or equal to 40000mg/L, wherein the cumene hydroperoxide is less than or equal to 35000mg/L; COD (chemical oxygen demand) is less than or equal to 70000mg/L; formic acid is less than or equal to 4000mg/L; acetic acid is less than or equal to 7000mg/L; phenol is less than or equal to 5000mg/L.
After the treatment in the step (1), peroxide in the wastewater is catalyzed and decomposed to generate hydroxyl free radicals with strong oxidability, and the hydroxyl free radicals are contacted with organic matters in the wastewater to decompose and generate carbon dioxide or micromolecular easily-biochemical substances, so that the biodegradability of the wastewater is further improved.
The reaction conditions of step (1) of the present invention include: the reaction temperature is 60-80 ℃ and the airspeed is 0.5-3.5 h -1 Preferably 1.5 to 2.5 hours -1 。
The improvement of the reaction temperature and the reaction time is favorable for the increase of the decomposition efficiency of peroxides and organic matters, but the corresponding operation and investment costs are increased, in addition, as the time and the temperature are increased, a large amount of organic matters are converted into carbon dioxide or small molecular organic matters, and the biochemical property of the small molecular matters is higher, and the reaction is difficult to continue, so that the reaction temperature and the time need an optimized range. Unlike hydrogen peroxide, the organic peroxide, especially methyl hydrogen peroxide in POCHP waste water, has relatively low decomposing efficiency at normal temperature and pressure and no catalyst, and may be decomposed into hydroxyl radical.
Step (2) of the present invention may be carried out in any apparatus known in the art, preferably using a biological aerated filter reactor.
The step (2) mainly removes small-molecule organic matters which are easy to biochemically and are subjected to catalytic oxidation, formic acid, acetic acid and the like contained in raw wastewater, and biochemical conditions comprise: the temperature is 35-45 ℃, preferably 37-42 ℃, and the COD load of the inflow water is 0.5-1.5 Kg/(m) 3 * Day), preferably 0.7 to 1 Kg/(m) 3 * Day), the pH of the inlet water=6 to 8, preferably 6.5 to 7.5.
The invention has the beneficial effects that:
(1) The carrier, the modifier and the metal oxide used in the invention are simple and easy to obtain, and the cost is low.
(2) In the preferred scheme, titanium oxide is modified by ultrasonic treatment and Fenton iron mud addition, and a polyaluminium chloride auxiliary agent is added, so that the loss of active metal can be reduced, the polymerization coking of organic matters in a catalyst pore channel is avoided, the service life of the catalyst is prolonged, the pore channel structure is strengthened, the specific surface area of the catalyst is increased, the contact site of active components and the organic matters is improved, and the inherent adsorption effect of a carrier on the organic matters is improved.
Detailed Description
The technical scheme and effects of the invention are further described by the following specific examples. The following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention using the inventive concept are within the scope of the invention as claimed.
The ultrasonic instrument, model BILON6-180, is available from Shanghai Bilang instruments, inc.;
catalytic oxidation towers, available from Xuzhou city Longtai ozone equipment manufacturing company, inc.;
titanium oxide, available from Shanghai Hui Jing sub-nanometer New Material Co., ltd;
fenton iron mud is taken from a Wanhua chemical smoke table industrial park wastewater treatment device;
polyaluminum chloride, shandong Lu Tongxin chemical Co., ltd;
PO/CHP wastewater containing organic peroxide is produced by a Wanhua chemistry pilot plant.
GC analysis conditions: adopting Agilent HP-5 gas chromatographic column with size of 30m.530 μm.1.5 μm, and heating by: setting the initial temperature to 70 ℃, maintaining for 5min, heating to 300 ℃ at a speed of 5 ℃/min, and maintaining for 10min, so as to analyze the main components of the water quality;
COD analysis: adopts a national standard potassium dichromate oxidation analysis method.
Example 1: preparation of ultrasonic modified titanium oxide
And (3) placing 20g of titanium oxide sample into 200mL of pure water, slowly pouring the titanium oxide sample into an ultrasonic instrument, selecting ultrasonic power of ultrasonic modification to be 150W, selecting ultrasonic frequency to be 80Hz, ultrasonic time to be 50min, washing the treated pure water, and drying the treated pure water at 115 ℃ for 5h to obtain the ultrasonic modified titanium oxide.
Example 2: preparation of catalyst # 0
Placing 20g of titanium oxide sample in an impregnation bottle, and carrying out vacuum pretreatment, wherein the vacuum pretreatment time is 50min, and the vacuum degree is 97.0KPa;
1.0mL of copper nitrate aqueous solution containing 0.10g/mL of copper, 1.0mL of chromium nitrate aqueous solution containing 0.10g/mL of chromium, 1.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium, 1.0mL of nickel nitrate aqueous solution containing 0.10g/mL of nickel and 1.0mL of barium nitrate aqueous solution containing 0.10g/mL of barium are taken and added into ethanol aqueous solution with ethanol concentration of 10wt%, so as to prepare impregnating solution with total volume of 16.4 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the titanium oxide carrier, uniformly mixing, impregnating for 120min, taking out, drying at 130 ℃ for 2h in an oven, and roasting at 600 ℃ for 4h in a muffle furnace to obtain the 0# catalyst.
The content of the metal element of the active component in the obtained catalyst # 0 based on the weight of titanium oxide therein is as follows: 0.5wt% of copper, 0.5wt% of chromium, 0.5wt% of cerium, 0.5wt% of nickel and 0.5wt% of barium.
Example 3: preparation of catalyst # 1
Placing 20g of the titanium oxide solid subjected to ultrasonic treatment in an impregnation bottle, and carrying out vacuum pretreatment, wherein the vacuum pretreatment time is 50min, and the vacuum degree is 97.0KPa;
1.0mL of copper nitrate aqueous solution containing 0.10g/mL of copper, 1.0mL of chromium nitrate aqueous solution containing 0.10g/mL of chromium, 1.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium, 1.0mL of nickel nitrate aqueous solution containing 0.10g/mL of nickel and 1.0mL of barium nitrate aqueous solution containing 0.10g/mL of barium are taken and added into ethanol aqueous solution with ethanol concentration of 10wt%, so as to prepare impregnating solution with total volume of 16.4 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the titanium oxide carrier, uniformly mixing, impregnating for 120min, taking out, drying at 130 ℃ for 2h in an oven, and roasting at 600 ℃ for 4h in a muffle furnace to obtain the No. 1 catalyst.
The content of the metal element of the active component in the obtained catalyst # 1 based on the weight of titanium oxide therein is as follows: 0.5wt% of copper, 0.5wt% of chromium, 0.5wt% of cerium, 0.5wt% of nickel and 0.5wt% of barium.
Example 4: preparation of catalyst # 2
Placing 20g of the titanium oxide solid subjected to ultrasonic modification in the embodiment 1 into an impregnation bottle, and carrying out vacuum pretreatment, wherein the vacuum pretreatment time is 50min, and the vacuum degree is 97.0KPa;
40.0mL of Fenton iron mud water solution containing 0.01g/mL of Fenton iron mud is taken and added into an ethanol water solution with the ethanol concentration of 10wt% to prepare an impregnating solution with the total volume of 80.0 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the titanium oxide solid, uniformly mixing, carrying out equal volume impregnation on the solid, taking out and placing the impregnated solid in an oven to dry for 4 hours at 80 ℃ after 100 minutes of impregnation, and roasting for 5 hours at 550 ℃ in a muffle furnace to obtain the Fenton iron mud modified titanium oxide carrier. The content of Fenton iron mud in the prepared titanium oxide carrier is 2.0wt% based on the weight of titanium oxide.
Placing 20g of the Fenton iron mud modified titanium oxide carrier into an impregnation bottle; 1.0mL of copper nitrate aqueous solution containing 0.10g/mL of copper, 1.0mL of chromium nitrate aqueous solution containing 0.10g/mL of chromium, 1.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium, 1.0mL of nickel nitrate aqueous solution containing 0.10g/mL of nickel and 1.0mL of barium nitrate aqueous solution containing 0.10g/mL of barium are taken and added into ethanol aqueous solution with ethanol concentration of 10wt%, so as to prepare impregnating solution with total volume of 24.4 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the Fenton iron mud modified titanium oxide carrier, uniformly mixing, carrying out isovolumetric impregnation on the Fenton iron mud modified titanium oxide carrier, taking out after 200min of impregnation, drying for 3h at 130 ℃ in an oven, and roasting for 4h at 580 ℃ in a muffle furnace to obtain the No. 2 catalyst.
In the obtained catalyst No. 2, the content of metal elements of the active components based on the weight of the Fenton iron mud modified titanium oxide carrier is as follows: 0.5wt% of copper, 0.5wt% of chromium, 0.5wt% of cerium, 0.5wt% of nickel and 0.5wt% of barium.
Example 5: preparation of catalyst 3#
Placing 20g of the titanium oxide solid subjected to ultrasonic modification in the embodiment 1 into an impregnation bottle, and carrying out vacuum pretreatment, wherein the vacuum pretreatment time is 60min, and the vacuum degree is 96.0KPa;
40.0mL of Fenton iron mud water solution containing 0.01g/mL of Fenton iron mud is taken and added into an ethanol water solution with the ethanol concentration of 10wt% to prepare an impregnating solution with the total volume of 80.0 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the ultrasonic-modified titanium oxide solid, uniformly mixing, carrying out equal volume impregnation on the ultrasonic-modified titanium oxide solid, taking out the impregnated titanium oxide solid after 100min, drying the titanium oxide solid in an oven at 100 ℃ for 4h, and roasting the titanium oxide solid in a muffle furnace at 550 ℃ for 5h to obtain the Fenton iron mud modified ultrasonic-modified titanium oxide solid. The content of Fenton iron mud in the prepared titanium oxide solid modified by ultrasonic is 2.0wt% based on the weight of the titanium oxide solid modified by ultrasonic.
10wt% of polyaluminum chloride aqueous solution and titanium oxide modified by ultrasonic and iron mud are subjected to isovolumetric impregnation for 120min; and then drying the obtained solid at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the carrier modified by ultrasonic and added with the iron mud and added with the polyaluminium chloride auxiliary agent. The content of polyaluminum chloride was 3.0wt% based on the weight of the ultrasonically modified titanium oxide solid.
Placing 20g of the titanium oxide solid carrier modified by the added polyaluminium chloride into an impregnation bottle; 1.0mL of copper nitrate aqueous solution containing 0.10g/mL of copper, 1.0mL of chromium nitrate aqueous solution containing 0.10g/mL of chromium, 1.0mL of cerium nitrate aqueous solution containing 0.10g/mL of cerium, 1.0mL of nickel nitrate aqueous solution containing 0.10g/mL of nickel and 1.0mL of barium nitrate aqueous solution containing 0.10g/mL of barium are taken and added into ethanol aqueous solution with ethanol concentration of 10wt%, so as to prepare impregnation liquid with total volume of 26.2 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the titanium oxide solid carrier modified by the added polyaluminium chloride, uniformly mixing, carrying out equal volume impregnation on the titanium oxide solid carrier modified by the added polyaluminium chloride for 150min, taking out, drying for 2h at 130 ℃ in an oven, and roasting for 4h at 600 ℃ in a muffle furnace to obtain the 3# catalyst.
In the obtained 3# catalyst, the content of the metal elements of the active component based on the weight of the titanium oxide solid carrier modified by polyaluminum chloride is increased is as follows: 0.5wt% of copper, 0.5wt% of chromium, 0.5wt% of cerium, 0.5wt% of nickel and 0.5wt% of barium.
Example 6: preparation of catalyst # 4
Placing 20g of the titanium oxide solid subjected to ultrasonic modification in the embodiment 1 into an impregnation bottle, and carrying out vacuum pretreatment, wherein the vacuum pretreatment time is 60min, and the vacuum degree is 96.0KPa;
40.0mL of Fenton iron mud water solution containing 0.01g/mL of Fenton iron mud is taken and added into an ethanol water solution with the ethanol concentration of 10wt% to prepare an impregnating solution with the total volume of 80.0 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the ultrasonic-modified titanium oxide solid, uniformly mixing, carrying out equal volume impregnation on the ultrasonic-modified titanium oxide solid, taking out the impregnated titanium oxide solid after 100min, drying the titanium oxide solid in an oven at 100 ℃ for 4h, and roasting the titanium oxide solid in a muffle furnace at 550 ℃ for 5h to obtain the Fenton iron mud modified ultrasonic-modified titanium oxide solid. The content of Fenton iron mud in the prepared titanium oxide solid modified by ultrasonic is 2.0wt% based on the weight of the titanium oxide solid modified by ultrasonic.
10wt% of polyaluminum chloride aqueous solution and titanium oxide solid modified by ultrasonic and iron mud are subjected to equal volume impregnation for 120min; and then drying the obtained solid at 120 ℃ for 4 hours, and roasting at 500 ℃ for 4 hours to obtain the carrier modified by ultrasonic and added with the iron mud and added with the polyaluminium chloride auxiliary agent. The content of polyaluminum chloride was 3.0wt% based on the weight of the ultrasonically modified titanium oxide solid.
Placing 20g of the titanium oxide solid carrier modified by the added polyaluminium chloride into an impregnation bottle; 1.0mL of copper nitrate aqueous solution containing 0.15g/mL of copper, 1.0mL of chromium nitrate aqueous solution containing 0.05g/mL of chromium, 1.0mL of cerium nitrate aqueous solution containing 0.15g/mL of cerium, 1.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel and 1.0mL of barium nitrate aqueous solution containing 0.15g/mL of barium are taken and added into ethanol aqueous solution with ethanol concentration of 10wt%, so as to prepare impregnation liquid with total volume of 26.2 mL. Adding the impregnating solution into a vacuum impregnating bottle filled with the titanium oxide solid carrier modified by the added polyaluminium chloride, uniformly mixing, carrying out isovolumetric impregnation, taking out and placing in an oven for drying at 130 ℃ for 2 hours after 150 minutes of impregnation, and roasting at 600 ℃ for 4 hours in a muffle furnace to obtain the No. 4 catalyst.
In the obtained catalyst No. 4, the content of the metal elements of the active components based on the weight of the titanium oxide solid carrier modified by polyaluminum chloride is increased is as follows: copper 0.75wt%, chromium 0.25wt%, cerium 0.75wt%, nickel 0.75wt% and barium 0.75wt%.
In the following examples, the results of sampling analysis of the organic peroxide-containing wastewater are shown in Table 1.
TABLE 1 organic peroxide wastewater composition
Example 7: treatment of POCHP wastewater containing organic peroxide (catalyst # 0)
Step (1), taking the wastewater containing the organic peroxide shown in the table 1, introducing the wastewater into a catalytic oxidation tower, and reacting at the temperature of 80 ℃ and the space velocity of 2h -1 Under the action of a No. 0 catalyst, organic peroxide is decomposed into hydroxyl free radicals with strong oxidability, macromolecular substances in the wastewater are decomposed into small molecular acids, and partial small molecular carboxylic acids are further oxidized into CO 2 And H 2 O, after the reaction, the content of organic peroxide is reduced to 12550mg/L, the content of cumene hydroperoxide is reduced to 8895mg/L, the content of formic acid is reduced to 1150mg/L, the content of acetic acid is reduced to 1200mg/L, phenol is treated to 280mg/L, COD is reduced to 15500mg/L, the decomposition efficiency of the organic peroxide is 65%, the content of cupric ions in water is 0.5mg/L, chromium ions are 0.7mg/L, cerium content is 0.9mg/L, nickel ions are 0.4mg/L, and barium ions are 1.5mg/L.
Step (2), the wastewater containing the organic peroxide after the catalytic oxidation in the step (1) is introduced into a bioreactor, the temperature is 40 ℃, and the COD load of inflow water is 1 Kg/(m) 3 * Day), the pH of the inlet water is=7, the content of the organic peroxide is reduced to 2480mg/L after biochemical reaction treatment, the COD is reduced to 7500mg/L, and formic acid, acetic acid and phenol are not detected.
Example 8: treatment of wastewater containing organic peroxide (catalyst # 1)
Step (1), taking the wastewater containing the organic peroxide shown in the table 1, introducing the wastewater into a catalytic oxidation tower, and reacting at the temperature of 80 ℃ and the space velocity of 2h -1 After the reaction, the content of the organic peroxide is reduced to 8550mg/L, the content of the cumene hydroperoxide is reduced to 6895mg/L, the content of the formic acid is reduced to 950mg/L, the content of the acetic acid is reduced to 1050mg/L, the phenol is treated to 270mg/L, the COD is reduced to 13500mg/L, the decomposition efficiency of the organic peroxide is 76%, the content of the cupric ions in the water is 0.4mg/L, the chromium ions are 0.7mg/L, the cerium content is 0.8mg/L, the nickel ions are 0.5mg/L, and the barium ions are 1.5mg/L.
And (2) introducing the wastewater containing the organic peroxide subjected to catalytic oxidation in the step (1) into a bioreactor, wherein the temperature is 40 ℃, the COD load of inflow water is 1 Kg/(m 3 day), the PH of inflow water is=7, after biochemical reaction treatment, the content of the organic peroxide is reduced to 2120mg/L, the COD is reduced to 6500mg/L, and formic acid, acetic acid and phenol are not detected.
Example 9: treatment of wastewater containing organic peroxide (catalyst # 2)
Step (1), taking the wastewater containing the organic peroxide shown in the table 1, introducing the wastewater into a catalytic oxidation tower, and reacting at the temperature of 80 ℃ and the space velocity of 2h -1 After the reaction, the content of the organic peroxide is reduced to 2550mg/L, the content of the cumene hydroperoxide is reduced to 1580mg/L, the content of the formic acid is reduced to 850mg/L, the content of the acetic acid is reduced to 950mg/L, the phenol is treated to 250mg/L, the COD is reduced to 8600mg/L, the decomposition efficiency of the organic peroxide is 93%, the content of the cupric ions in the produced water is 0.5mg/L, the chromium ions are 0.7mg/L, the cerium content is 0.8mg/L, the nickel ions are 0.4mg/L, and the barium ions are 1.5mg/L.
And (2) introducing the wastewater containing the organic peroxide subjected to catalytic oxidation in the step (1) into a bioreactor, wherein the temperature is 40 ℃, the COD load of inflow water is 1 Kg/(m 3 day), the PH of inflow water is=7, after biochemical reaction treatment, the content of the organic peroxide is reduced to 280mg/L, the COD is reduced to 1650mg/L, and formic acid, acetic acid and phenol are not detected.
Example 10: treatment of wastewater containing organic peroxide (3 # catalyst)
Step (1), taking the wastewater containing the organic peroxide shown in the table 1, introducing the wastewater into a catalytic oxidation tower, and reacting at the temperature of 80 ℃ and the space velocity of 2h -1 After the reaction, the content of the organic peroxide is reduced to 2450mg/L, the content of the cumene hydroperoxide is reduced to 1480mg/L, the content of the formic acid is reduced to 680mg/L, the content of the acetic acid is reduced to 810mg/L, the phenol is treated to 230mg/L, the COD is reduced to 7800mg/L, the decomposition efficiency of the organic peroxide is 93%, the content of the cupric ions in the produced water is 0.04mg/L, the chromium ions are 0.01mg/L, the cerium content is 0.001mg/L, the nickel ions are 0.02mg/L, and the barium ions are 0.02mg/L.
And (2) introducing the wastewater containing the organic peroxide subjected to catalytic oxidation in the step (1) into a bioreactor, wherein the temperature is 40 ℃, the COD load of inflow water is 1 Kg/(m 3 day), the PH of inflow water is=7, after biochemical reaction treatment, the content of the organic peroxide is reduced to 260mg/L, the COD is reduced to 1375mg/L, and formic acid, acetic acid and phenol are not detected.
Example 11: treatment of wastewater containing organic peroxide (catalyst # 4)
Step (1) of introducing the wastewater containing the organic peroxide shown in Table 1 intoCatalytic oxidation tower, reaction temperature 80 ℃ and space velocity 2h -1 After the reaction, the content of the organic peroxide is reduced to 2350mg/L, the content of the cumene hydroperoxide is reduced to 1380mg/L, the content of the formic acid is reduced to 670mg/L, the content of the acetic acid is reduced to 800mg/L, the phenol is treated to 230mg/L, the COD is reduced to 7700mg/L, the decomposition efficiency of the organic peroxide is 94%, the content of the cupric ions in the produced water is 0.04mg/L, the chromium ions are 0.01mg/L, the cerium content is 0.002mg/L, the nickel ions are 0.02mg/L, and the barium ions are 0.03mg/L.
And (2) introducing the wastewater containing the organic peroxide subjected to catalytic oxidation in the step (1) into a bioreactor, wherein the temperature is 40 ℃, the COD load of inflow water is 1 Kg/(m 3 day), the PH of inflow water is=7, the content of the organic peroxide is reduced to 250mg/L after biochemical reaction treatment, the COD is reduced to 1355mg/L, and formic acid, acetic acid and phenol are not detected.
Claims (10)
1. An organic peroxide catalytic oxidation catalyst, characterized in that the catalyst comprises a carrier and an active component; the active component comprises copper, chromium, cerium, nickel and barium in the form of oxides,
the content of the metal elements of the active component based on the weight of the carrier is as follows:
0.1 to 1 weight percent of copper;
0.2 to 0.8 weight percent of chromium;
cerium 0.1-1 wt%;
0.3 to 0.8 weight percent of nickel;
0.1 to 0.8 weight percent of barium;
the carrier is titanium oxide modified by ultrasonic treatment, fenton iron mud addition and polyaluminium chloride addition as an auxiliary agent, and the preparation method comprises the following steps: 5.0 to 10 weight percent of polyaluminum chloride aqueous solution and titanium oxide modified by adding Fenton iron mud are subjected to isovolumetric impregnation for 50 to 250 minutes, then the obtained solid is dried for 3 to 5 hours at the temperature of 60 to 150 ℃, and then baked for 3 to 5 hours at the temperature of 450 to 600 ℃; the content of the polyaluminum chloride is 2.0 to 7.0 weight percent based on the weight of the titanium oxide;
wherein:
the preparation method of the titanium oxide modified by ultrasonic and Fenton iron mud addition comprises the following steps: the Fenton iron mud solution and the titanium oxide modified by ultrasonic are subjected to isovolumetric impregnation for 50-250 min, then the obtained solid is dried for 3-5 h at 60-150 ℃, and then baked for 3-5 h at 450-600 ℃ to obtain the titanium oxide modified by ultrasonic and Fenton iron mud addition; the content of Fenton iron mud is 1.0-6.0 wt% based on the weight of titanium oxide;
the ultrasonic modification method of the ultrasonic modified titanium oxide comprises the following steps: the ultrasonic power is 100-150W, the ultrasonic frequency is 50-80 Hz, the ultrasonic time is 30-50 min, the treated titanium oxide is washed by pure water and dried for 4-6 h at 115-125 ℃ to obtain the titanium oxide modified by ultrasonic.
2. The catalyst according to claim 1, wherein the content of the metal element of the active component, based on the weight of the support, is:
0.5 to 0.7 weight percent of copper;
0.4 to 0.6 weight percent of chromium;
cerium 0.5-0.7wt%;
0.5 to 0.7 weight percent of nickel;
barium 0.4-0.6 wt%.
3. The catalyst of claim 1 wherein the Fenton iron mud is present in an amount of 2.0 to 3.0 wt.% based on the weight of titanium oxide.
4. The catalyst of claim 1 wherein the polyaluminum chloride is present in an amount of 4.0 to 5.0 wt.% based on the weight of the titanium oxide.
5. A method of preparing the catalyst of any one of claims 1-4, comprising: adding a solution containing copper salt, chromium salt, cerium salt, nickel salt and barium salt into a carrier, and carrying out isovolumetric impregnation for 100-250 min; and then drying the obtained solid at 120-140 ℃ for 2-3 h, and roasting at 550-650 ℃ for 3-5 h to obtain the catalyst.
6. The method according to claim 5, wherein the support is subjected to a vacuum pretreatment for 40 to 60 minutes and a vacuum of 96.0 to 98.0KPa before the isovolumetric impregnation.
7. Use of a catalyst according to any one of claims 1-4 for the treatment of peroxide-containing wastewater.
8. A method for treating peroxide-containing PO/CHP wastewater comprises the following steps:
(1) Carrying out catalytic oxidation reaction on PO/CHP wastewater containing peroxide; wherein the catalyst used is the catalyst of any one of claims 1 to 4;
(2) Performing biochemical treatment on the wastewater obtained in the step (1) and then discharging;
the peroxide-containing PO/CHP wastewater meets the following conditions: organic peroxide is less than or equal to 40000mg/L, wherein cumene hydroperoxide is less than or equal to 35000mg/L; COD is less than or equal to 70000mg/L; formic acid is less than or equal to 4000mg/L; acetic acid is less than or equal to 7000mg/L; phenol is less than or equal to 5000mg/L.
9. The method of claim 8, wherein the reaction conditions of step (1) comprise: the reaction temperature is 60-80 ℃ and the airspeed is 0.5-3.5 h -1 。
10. The process of claim 9, wherein the space velocity of step (1) is from 1.5 to 2.5 hours -1 。
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