CN113842926B - Multiphase wet oxidation catalyst and preparation method and application thereof - Google Patents
Multiphase wet oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN113842926B CN113842926B CN202010601472.8A CN202010601472A CN113842926B CN 113842926 B CN113842926 B CN 113842926B CN 202010601472 A CN202010601472 A CN 202010601472A CN 113842926 B CN113842926 B CN 113842926B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 145
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002351 wastewater Substances 0.000 claims abstract description 58
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 30
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002105 nanoparticle Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012670 alkaline solution Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 7
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 7
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 159000000009 barium salts Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920005862 polyol Polymers 0.000 claims description 3
- 150000003077 polyols Chemical class 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000013049 sediment Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 235000010210 aluminium Nutrition 0.000 claims description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims 4
- 239000004411 aluminium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 36
- 230000010718 Oxidation Activity Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000012018 catalyst precursor Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000669618 Nothes Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B01J35/394—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/301—Detergents, surfactants
Abstract
The invention relates to a multiphase wet oxidation catalyst, a preparation method and application thereof. The catalyst comprises the following components in parts by weight: (a) 0.1 to 99 parts, preferably 50 to 95 parts, of TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the (b) 0.1 to 99 parts, preferably 5 to 50 parts of BaSO 4 The method comprises the steps of carrying out a first treatment on the surface of the (c) 0.01 to 10 parts, preferably 0.05 to 5 parts, of simple substance of platinum group metal; preferably, the platinum group metal element is selected from at least one of Pt, pd, rh, and Ru. The catalyst prepared by the method has high dispersity of the noble metal active components and short preparation flow. When the catalyst is used for treating wastewater containing high-concentration nonionic surfactant, the catalytic oxidation activity is excellent, the COD of the wastewater can be effectively reduced, the residual COD in the wastewater after treatment can be less than 50mg/L, and a better technical effect is achieved.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a multiphase wet oxidation catalyst, a preparation method and application thereof; more particularly relates to a heterogeneous wet oxidation catalyst, a preparation method thereof and application thereof in wastewater treatment containing nonionic surfactant.
Background
Nonionic surfactants are a class of surfactants having R-O- (CH) 2 CH 2 O) n The H-structure compound is widely applied to industries such as cosmetics, foods, dyes, pesticides, petrifaction, washing and the like. The consumption of nonionic surfactant is very huge every year, and the nonionic surfactant enters the water body along with the discharge of wastewater. Because the nonionic surfactant has great damage to organisms and affects the self-cleaning of the water body, the wastewater containing the nonionic surfactant with high concentration is required to be strictly treated and can be discharged into the water body environment.
The treatment technology of the nonionic surfactant wastewater comprises a biological method, an adsorption method and a high-grade oxidation method, wherein the high-grade oxidation method, such as a catalytic wet oxidation method, a Fenton method, an ozone catalytic oxidation method and the like, has the advantages of high reaction efficiency, no secondary pollution, small occupied area of equipment and the like, and is very suitable for treating the medium-high concentration organic wastewater.
CN107311386 discloses a method for treating wastewater with nonionic surfactant, wherein after the wastewater is magnetized and pretreated, the wastewater is adsorbed by activated carbon, and the magnetic induction intensity in the magnetizing treatment device is not less than 100mT. During the magnetizing process, the magnetic field causes advanced oxidation of contaminants in the wastewater. However, the method adopts activated carbon adsorption, and a large amount of waste residues are finally generated.
CN109626675 discloses a method for treating wastewater containing nonionic surfactant, which adopts the coupling treatment of reinforced coagulation and electrochemical oxidation to treat wastewater with the mass concentration of nonionic surfactant of 200-500 mg/L. The aluminum coagulant and coagulant aid are adopted to strengthen coagulation, part of nonionic surfactant and suspended particles are removed, and then electrochemical oxidation reaction is carried out. But the coagulation process generates a large amount of solid waste.
CN1212981 discloses a method for treating wastewater containing nonionic surfactant, which takes scrap iron micro-electrolysis treatment as a core, after the wastewater is regulated to a proper pH, the wastewater enters a micro-electrolysis reactor to carry out scrap iron micro-electrolysis treatment, and the treated wastewater enters a precipitation tank to remove F 2+ And Fe (Fe) 3+ . The method has the advantages that the removal rate of the nonionic surfactant can reach 80 percent, but the waste water needs to be regulated to be acidic before the micro-electrolysis reaction, and the yielding water needs to be further removed with F 2+ And Fe (Fe) 3+ . Therefore, the method has low reaction efficiency and complex operation, and can generate a certain amount of iron mud solid waste.
Catalytic wet oxidation is a platform technology for treating medium-high concentration organic wastewater, which is characterized in that the wastewater is contacted with oxygen at a certain temperature and pressure, and organic pollutants are oxidized into CO in a liquid phase under the action of a catalyst 2 Harmless substances such as water, small molecular organic acids and the like. The catalytic wet oxidation is applied to the treatment of high-concentration nonionic surfactant wastewater, has the advantages of high reaction efficiency, no secondary pollution and the like, and is technically characterized by the development of efficient catalysts.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a multiphase wet oxidation catalyst and a preparation method thereof. The noble metal active component of the catalyst prepared by the method has high dispersity, and when the catalyst is used for treating wastewater containing high-concentration nonionic surfactant, the catalyst has excellent catalytic oxidation activity, high COD removal efficiency and no secondary pollution.
To this end, the first aspect of the present invention provides a heterogeneous wet oxidation catalyst comprising, in parts by weight:
(a) 0.1 to 99 parts, preferably 50 to 95 parts, of TiO 2 ；
(b) 0.1 to 99 parts, preferably 5 to 50 parts of BaSO 4 ；
(c) 0.01 to 10 parts, preferably 0.05 to 5 parts, of simple substance of platinum group metal; preferably, the simple substance of platinum group metal is selected from one or more of Pt, pd, rh and Ru.
In some embodiments of the invention, the TiO 2 The crystal form of (a) is anatase.
In other embodiments of the invention, the simple substance of the platinum group metal is a nanoparticle; preferably, the particle size of the nanoparticle is less than or equal to 5nm.
In some embodiments of the invention, the TiO 2 And BaSO 4 The weight ratio is (1-5): 1, and the BaSO 4 The weight ratio of the catalyst to the platinum group metal simple substance is (0.8-8) 0.01; preferably, the TiO 2 And BaSO 4 The weight ratio is (3-4.5): 1, and the BaSO 4 The weight ratio of the catalyst to the platinum group metal simple substance is (0.9-3) 0.01.
In a second aspect the present invention provides a process for preparing a catalyst according to the first aspect of the invention comprising the steps of:
s1, respectively dissolving soluble barium salt and TiOSO 4 Dissolving in water to prepare a solution A and a solution B;
s2, adding the solution A and the alkaline solution into the solution B, and controlling the pH of the end point to form a precipitate; then the sediment is washed, dried and pulverized to prepare the BaSO-containing liquid 4 And TiO 2 Is a mixture of (a) and (b);
s3, mixing the mixture with a binder and water, extruding to form strips, and drying and roasting to obtain a catalyst carrier;
s4, loading metal salt containing platinum group metal simple substance on a catalyst carrier, and roasting to obtain the heterogeneous wet oxidation catalyst.
In some embodiments of the invention, in step S2, the alkaline solution is selected from at least one of ammonia, urea solution, sodium hydroxide solution, sodium carbonate solution, and sodium bicarbonate solution.
In other embodiments of the present invention, in step S2, the end point pH is controlled to 7 to 11.
In some embodiments of the present invention, in step S3, the binder is selected from at least one of carboxymethyl cellulose, starch, aluminum sol, silica sol, nitric acid, sulfuric acid, oxalic acid, and citric acid.
In other embodiments of the present invention, in step S3, the baking temperature is 400 to 800 ℃ and the baking time is 1 to 6 hours.
In some embodiments of the invention, in step S4, the firing temperature is 200 to 600 ℃ and the firing time is 1 to 12 hours.
In a third aspect, the present invention provides a method for treating wastewater containing a nonionic surfactant, comprising contacting the wastewater, air with a catalyst according to the first aspect of the present invention or a catalyst prepared by the method according to the second aspect, and obtaining treated wastewater after the reaction.
In some embodiments of the invention, the nonionic surfactant in the wastewater comprises polyoxyethylene type, polyol type, and aminoalcohol type; the COD content of the wastewater is 5000-200000 mg/L, preferably 5000-150000 mg/L.
In other embodiments of the invention, the reaction temperature is 150 to 250 ℃, the reaction pressure is 2 to 6MPa, and the reaction time is 10 to 120 minutes.
In some embodiments of the invention, the air is used in an amount of 1.05 to 1.5 times the theoretical COD value.
The beneficial effects of the invention are as follows: the catalyst prepared by the method has high dispersity of the noble metal active components and short preparation flow. When the catalyst is used for treating wastewater containing high-concentration nonionic surfactant, the catalytic oxidation activity is excellent, the COD of the wastewater can be effectively reduced, the residual COD in the wastewater after treatment can be less than 50mg/L, and a better technical effect is achieved.
Drawings
The invention will be further described with reference to the accompanying drawings.
Fig. 1 is a TEM electron micrograph of the catalyst prepared in example 2.
Fig. 2 is a TEM electron micrograph of the catalyst prepared in example 3.
Fig. 3 is a TEM electron microscope image of the catalyst prepared in comparative example 1.
Detailed Description
In the prior art, the composition contains noThe treatment methods of wastewater containing ionic surfactants are mostly electrochemical oxidation, magnetic force and other treatment methods, and these methods are only suitable for treating wastewater containing nonionic surfactants at low concentrations. The invention applies the catalytic wet oxidation to the treatment of the high-concentration nonionic surfactant wastewater, and has the advantages of high reaction efficiency, no secondary pollution and the like. In addition, the inventors of the present application have found through studies that the introduction of Ba element into a catalytic wet oxidation catalyst, thereby enabling TiO in a catalyst preparation process carrier 2 All the crystals are transformed into anatase type carrier TiO 2 After crystal transformation modification, the dispersity of the platinum group metal (such as Pt) serving as an active component is improved, so that the catalytic oxidation activity of the catalyst is improved, the COD of the wastewater can be effectively reduced, and the COD in the wastewater after treatment can be reduced to below 50 mg/L.
To this end, the heterogeneous wet oxidation catalyst according to the first aspect of the present invention comprises the following components in parts by weight:
(a) 0.1 to 99 parts, preferably 50 to 95 parts, of TiO 2 ；
(b) 0.1 to 99 parts, preferably 5 to 50 parts of BaSO 4 ；
(c) 0.01 to 10 parts, preferably 0.05 to 5 parts, more preferably 0.1 to 1 part, of a simple substance of a platinum group metal.
In some preferred embodiments of the present invention, the simple substance of platinum group metal is selected from one or more of Pt, pd, rh and Ru. In a still further preferred embodiment of the present invention, the simple substance of platinum group metal is Pt.
In some embodiments of the invention, the TiO 2 The crystal form of (a) is anatase. TiO in existing catalysts 2 Non-seeding, or partially seeding. Whereas the invention is carried out by introducing BaSO in the catalyst 4 Thereby inhibiting TiO 2 The crystal form of (a) is changed from anatase type with larger specific surface area to rutile type, and TiO is maintained 2 The crystal form is anatase. TiO in catalyst support 2 The crystal form is a pure anatase type, which is more beneficial to improving the dispersity of active components (such as Pt) in the catalyst.
In other embodiments of the invention, the simple substance of the platinum group metal is a nanoparticle; preferably, the particle size of the nanoparticle is less than or equal to 5nm.
In some embodiments of the invention, the TiO 2 And BaSO 4 The weight ratio is (1-5): 1, and the BaSO 4 The weight ratio of the catalyst to the platinum group metal simple substance is (0.8-8) 0.01; preferably, the TiO 2 And BaSO 4 The weight ratio is (3-4.5): 1, and the BaSO 4 The weight ratio of the catalyst to the platinum group metal simple substance is (0.9-3) 0.01.
A second aspect of the invention relates to a process for preparing a catalyst according to the first aspect of the invention, comprising the steps of:
s1, respectively dissolving soluble barium salt and TiOSO 4 Dissolving in water to prepare a solution A and a solution B;
s2, adding the solution A and the alkaline solution into the solution B, and controlling the pH of the end point to form a precipitate; then the sediment is washed, dried and pulverized to prepare the BaSO-containing liquid 4 And TiO 2 Is a mixture of (a) and (b);
s3, mixing the mixture with a binder and water, extruding to form strips, and drying and roasting to obtain a catalyst carrier;
s4, loading metal salt containing platinum group metal simple substance on a catalyst carrier, and roasting to obtain the heterogeneous wet oxidation catalyst.
In the present invention, the soluble barium salt may be BaCl 2 、Ba(NO 3 ) 2 Etc. In some embodiments of the invention, the soluble barium salt may be Ba (NO 3 ) 2 。
In some embodiments of the invention, solution A and alkaline solution are slowly added dropwise to solution B with vigorous stirring at a water bath temperature of 20-80 ℃.
In some embodiments of the invention, in step S2, the alkaline solution is selected from at least one of ammonia, urea solution, sodium hydroxide solution, sodium carbonate solution, and sodium bicarbonate solution. In some preferred embodiments of the invention, the alkaline solution is a sodium carbonate solution.
In other embodiments of the present invention, in step S2, the end point pH is controlled to 7 to 11. In some embodiments of the invention, the endpoint pH is controlled to be 7, 8, 9, 10 or 11. In some preferred embodiments of the invention, the endpoint pH is controlled to be 8 to 10. In a still further preferred embodiment of the invention, the end point pH is controlled to 9.
In some embodiments of the present invention, in step S3, the binder is selected from at least one of carboxymethyl cellulose (CMC), starch, aluminum sol, silica sol, nitric acid, sulfuric acid, oxalic acid, and citric acid.
In other embodiments of the present invention, in step S3, the baking temperature is 400 to 800 ℃ and the baking time is 1 to 6 hours.
In some embodiments of the invention, in step S4, the firing temperature is 200 to 600 ℃ and the firing time is 1 to 12 hours.
In some embodiments of the present invention, in step S4, a metal salt of an elemental platinum group metal is supported on a catalyst carrier by an impregnation method.
In some more specific embodiments of the present invention, the method for preparing the catalyst specifically comprises the steps of:
(1) Respectively adding a certain amount of Ba (NO) 3 ) 2 And TiOSO 4 Dissolving in water to prepare solutions A and B;
(2) Slowly dripping the solution A and a certain amount of alkaline solution into the solution B in a water bath at 20-80 ℃ under the condition of intense stirring, and controlling the final pH value to be 7-11 to form a precipitate; washing, drying and pulverizing the precipitate to obtain a solution containing BaSO 4 And TiO 2 Is a mixture of (a) and (b);
(3) Mixing the mixture, the binder and water in proportion, extruding to form strips, drying and roasting to obtain the catalyst carrier;
(4) The metal salt containing platinum group metal simple substance is loaded on the catalyst carrier by an impregnation method, and the multi-phase wet oxidation catalyst is prepared after roasting.
The method has the characteristics of short preparation flow, high dispersity of the noble metal active components of the prepared catalyst and excellent catalytic oxidation activity.
A third aspect of the present invention relates to a method for treating wastewater containing a nonionic surfactant, comprising contacting the wastewater, air with a catalyst according to the first aspect of the present invention or a catalyst prepared by the method according to the second aspect, and obtaining treated wastewater after the reaction.
In some embodiments of the invention, the nonionic surfactant in the wastewater comprises polyoxyethylene type, polyol type, and aminoalcohol type. The main pollutants in the wastewater are long-chain alcohol and ether compounds which are not easy to be biodegraded, and the COD content of the wastewater is 5000-200000 mg/L, preferably 5000-150000 mg/L.
In other embodiments of the invention, the reaction temperature is 150 to 250 ℃, the reaction pressure is 2 to 6MPa, and the reaction time is 10 to 120 minutes.
In some embodiments of the invention, the reaction is carried out using a reactor selected from any one of a bubbling bed and a trickle bed.
In some embodiments of the invention, the air is used in an amount of 1.05 to 1.5 times the theoretical COD value. The theoretical COD value refers to the COD content in the wastewater to be treated.
Examples
In order that the invention may be more readily understood, the invention will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present invention may be prepared by commercial or conventional methods unless specifically indicated.
[ example 1 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
20g of Ba (NO) 3 ) 2 Dissolving in 200mL of water to obtain solution A, mixing 160g of TiOSO 4 Dissolving in 2L of water to prepare solution B, respectively slowly dripping solution A and ammonia water (ammonia concentration is 25-28 wt%) into solution B at room temperature and stirring speed of 300 r, controlling final pH value of solution to 7.0, continuously stirringStirring for 2h to form a precipitate. Filtering the precipitate, washing with 500mL deionized water for three times, pumping, and drying at 80deg.C for 24 hr to obtain solution containing BaSO 4 And TiO 2 Is a precursor of a catalyst support. 100g of the powdered precursor of the catalyst carrier is uniformly mixed with 5g of CMC, 10g of nitric acid and 30g of water, extruded and molded, dried at room temperature for 48h and roasted at 500 ℃ for 4h to obtain the catalyst carrier.
1.2 Process for preparing catalysts
0.5gH 2 PtCl 6 ·6H 2 O is dissolved in 30g of water, 100g of catalyst carrier is immersed in the solution at room temperature, after 24h of immersion, the catalyst precursor is obtained by drying for 48h at 60 ℃. The catalyst precursor was calcined at 350C under an air atmosphere for 4 hours, a multi-phase wet oxidation catalyst, labeled C-01. The catalyst comprises Pt in parts by weight 0.19 [BaSO 4 ] 18.4 [TiO 2 ] 81.4 。
2. Catalytic wet oxidation process
After mixing the wastewater containing the nonionic surfactant (cod=28400 mg/L, ph=6.59) with air, catalytic wet oxidation was performed at a reaction temperature of 190 ℃ and a pressure of 3.5MPa by a fixed bed reactor filled with 90mL of catalyst. The flow rate of the wastewater is 1.5mL/min, and the flow rate of the air is 160mL/min. The reaction results are shown in Table 1.
[ example 2 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
30g of Ba (NO) 3 ) 2 Dissolving in 200mL of water to obtain solution A, mixing 160g of TiOSO 4 Dissolving in 2L of water to prepare a solution B, slowly dripping the solution A and ammonia water (ammonia concentration is 25-28 wt%) into the solution B at the stirring speed of 300 revolutions at room temperature, controlling the final pH of the solution to be 9.0, and continuously stirring for 2 hours to form a precipitate. The precipitate was filtered, washed three times with 500mL of deionized water, dried at 80 ℃ for 24 hours after pumping, and the precursor of the catalyst carrier was obtained. 100g of powdered precursor of catalyst carrier is uniformly mixed with 5g of CMC, 10g of sulfuric acid and 30g of water, extruded and formed, and dried at room temperature for 48h, roasting at 500 ℃ for 4h to obtain the catalyst carrier.
1.2 Process for preparing catalysts
0.5gH 2 PtCl 6 Dissolving in 30g of water, immersing 100g of catalyst carrier in the solution at room temperature for 24 hours, and drying at 60 ℃ for 48 hours to obtain the catalyst precursor. The catalyst precursor was calcined at 350C under an air atmosphere for 4 hours, a multi-phase wet oxidation catalyst, labeled C-02. The catalyst comprises Pt in parts by weight 0.19 [BaSO 4 ] 25.02 [TiO 2 ] 74.8 . From a TEM electron micrograph, 30 Pt nanoparticles were taken, and the average particle diameter of the Pt nanoparticles was calculated to be 3.2nm. The TEM electron microscope image of the catalyst is shown in FIG. 1.
2. Catalytic wet oxidation process
After mixing the wastewater containing the nonionic surfactant (cod=28400 mg/L, ph=6.59) with air, catalytic wet oxidation was performed at a reaction temperature of 190 ℃ and a pressure of 3.5MPa by a fixed bed reactor filled with 90mL of catalyst. The flow rate of the wastewater is 1.5mL/min, and the flow rate of the air is 160mL/min. The reaction results are shown in Table 1.
[ example 3 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
30g of Ba (NO) 3 ) 2 Dissolving in 200mL of water to obtain solution A, mixing 160g of TiOSO 4 Dissolving in 2L of water to prepare a solution B, slowly dripping the solution A and 1M sodium carbonate solution into the solution B at the stirring speed of 300 revolutions at room temperature, controlling the final pH value of the solution to be 9.0, and continuously stirring for 2 hours to form a precipitate. The precipitate was filtered, washed three times with 500mL of deionized water, dried at 80 ℃ for 24 hours after pumping, and the precursor of the catalyst carrier was obtained. 100g of the powdered precursor of the catalyst carrier is uniformly mixed with 5g of CMC, 10g of sulfuric acid and 30g of water, extruded and molded, dried at room temperature for 48h and baked at 550 ℃ for 4h to obtain the catalyst carrier.
1.2 Process for preparing catalysts
0.5gH 2 PtCl 6 Dissolving in 30g of water in a room100g of catalyst carrier is immersed in the solution at a temperature of 24 hours, and then dried for 48 hours at 60 ℃ to obtain a catalyst precursor. The catalyst precursor was calcined at 400C under an air atmosphere for 4 hours, a multi-phase wet oxidation catalyst, labeled C-03. The catalyst comprises Pt in parts by weight 0.19 [BaSO 4 ] 25.02 [TiO 2 ] 74.8 . From a TEM electron micrograph, 30 Pt nanoparticles were taken, and the average particle diameter of the Pt nanoparticles was calculated to be 2.6nm. The TEM electron microscope image of the catalyst is shown in FIG. 2.
2. Catalytic wet oxidation process
After mixing the wastewater containing the nonionic surfactant (cod=28400 mg/L, ph=6.59) with air, catalytic wet oxidation was performed at a reaction temperature of 190 ℃ and a pressure of 3.5MPa by a fixed bed reactor filled with 90mL of catalyst. The flow rate of the wastewater is 1.5mL/min, and the flow rate of the air is 160mL/min. The reaction results are shown in Table 1.
[ example 4 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
the catalyst support preparation method was essentially the same as in example 3, except that the final pH of the solution was controlled to 8.0.
1.2 Process for preparing catalysts
The catalyst preparation was the same as in example 3, and the heterogeneous wet oxidation catalyst obtained was designated C-04. The catalyst comprises Pt in parts by weight 0.19 [BaSO 4 ] 25.02 [TiO 2 ] 74.8 。
2. Catalytic wet oxidation process
Same as in example 3. The reaction results are shown in Table 1.
[ example 5 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
the catalyst support preparation method was essentially the same as in example 3, except that the final pH of the solution was controlled to 11.
1.2 Process for preparing catalysts
The catalyst preparation was the same as in example 3, and the heterogeneous wet oxidation catalyst obtained was designated C-05. The catalyst comprises Pt in parts by weight 0.19 [BaSO 4 ] 25.02 [TiO 2 ] 74.8 。
2. Catalytic wet oxidation process
Same as in example 3. The reaction results are shown in Table 1.
[ example 6 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
the catalyst support was prepared in the same manner as in example 3.
1.2 Process for preparing catalysts
The catalyst preparation was essentially the same as in example 3, except that 0.1gH was used 2 PtCI 6 The heterogeneous wet oxidation catalyst obtained, marked C-06, was dissolved in 30 water. The catalyst comprises Pt in parts by weight 0.04 [BaSO 4 ] 25.06 [TiO 2 ] 74.9 。
2. Catalytic wet oxidation process
Same as in example 3. The reaction results are shown in Table 1.
[ example 7 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
the catalyst support preparation was substantially the same as in example 3, except that 45g of Ba (NO 3 ) 2 The catalyst support was prepared by dissolving in 200mL of water to prepare solution A.
1.2 Process for preparing catalysts
The catalyst preparation was the same as in example 3, and the heterogeneous wet oxidation catalyst obtained was designated C-07. The catalyst comprises Pt in parts by weight 0.2 [BaSO 4 ] 33.33 [TiO 2 ] 66.47 。
2. Catalytic wet oxidation process
Same as in example 3. The reaction results are shown in Table 1.
[ example 8 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
the catalyst support preparation method was substantially the same as in example 3, except that 20g of Ba (NO 3 ) 2 The catalyst support was prepared by dissolving in 200mL of water to prepare solution A.
1.2 Process for preparing catalysts
The catalyst preparation was the same as in example 3, and the heterogeneous wet oxidation catalyst obtained was designated C-08. The catalyst comprises Pt in parts by weight 0.19 [BaSO 4 ] 18.4 [TiO 2 ] 81.4 。
2. Catalytic wet oxidation process
Same as in example 3. The reaction results are shown in Table 1.
[ comparative example 1 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
100g of Ba (NO) 3 ) 2 Dissolving in 1L of water to prepare a solution A, slowly dripping 1M ammonium sulfate solution into the solution A at the stirring speed of 300 revolutions at room temperature, controlling the final pH value of the solution to be 6.0, and continuously stirring for 2 hours to form a precipitate. The precipitate was filtered, washed three times with 500mL of deionized water, dried at 80 ℃ for 24 hours after pumping, and the precursor of the catalyst carrier was obtained. 100g of the powdered precursor of the catalyst carrier is uniformly mixed with 5g of CMC, 10g of sulfuric acid and 30g of water, extruded and molded, dried at room temperature for 48h and roasted at 500 ℃ for 4h to obtain the catalyst carrier.
1.2 Process for preparing catalysts
0.5gH 2 PtCl 6 Dissolving in 30g of water, immersing 100g of catalyst carrier in the solution at room temperature for 24 hours, and drying at 60 ℃ for 48 hours to obtain the catalyst precursor. The catalyst precursor is baked for 4 hours at 350 ℃ in air atmosphere to obtain the wet oxidation catalyst, which is marked as B-01. From TEM electron microscope pictures, 30 Pt nano particles are takenThe average particle diameter of the nano Pt particles is 8.6nm. TEM electron microscopy of the catalyst is shown in FIG. 3.
2. Catalytic wet oxidation process
After mixing the wastewater containing the nonionic surfactant (cod=28400 mg/L, ph=6.59) with air, catalytic wet oxidation was performed at a reaction temperature of 190 ℃ and a pressure of 3.5MPa by a fixed bed reactor filled with 90mL of catalyst. The flow rate of the wastewater is 1.5mL/min, and the flow rate of the air is 160mL/min. The reaction results are shown in Table 1.
[ comparative example 2 ]
1. Catalytic wet oxidation catalyst preparation
1.1 preparation method of catalyst carrier:
160g of TiOSO 4 Dissolving in 2L of water to prepare a solution A, slowly dripping 1M sodium carbonate solution into the solution A at the stirring speed of 300 revolutions at room temperature, controlling the final pH value of the solution to be 9.0, and continuously stirring for 2 hours to form a precipitate. The precipitate was filtered, washed three times with 500mL of deionized water, dried at 80 ℃ for 24 hours after pumping, and the precursor of the catalyst carrier was obtained. 100g of the powdered precursor of the catalyst carrier is uniformly mixed with 5g of CMC, 10g of sulfuric acid and 30g of water, extruded and molded, dried at room temperature for 48h and roasted at 500 ℃ for 4h to obtain the catalyst carrier.
1.2 Process for preparing catalysts
0.5gH 2 PtCl 6 Dissolving in 30g of water, immersing 100g of catalyst carrier in the solution at room temperature for 24 hours, and drying at 60 ℃ for 48 hours to obtain the catalyst precursor. The catalyst precursor is baked for 4 hours at 350 ℃ in air atmosphere to obtain the wet oxidation catalyst, which is marked as B-02.
2. Catalytic wet oxidation process
After mixing the wastewater containing the nonionic surfactant (cod=28400 mg/L, ph=6.59) with air, catalytic wet oxidation was performed at a reaction temperature of 190 ℃ and a pressure of 3.5MPa by a fixed bed reactor filled with 90mL of catalyst. The flow rate of the wastewater is 1.5mL/min, and the flow rate of the air is 160mL/min. The reaction results are shown in Table 1.
TABLE 1 reaction results
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (12)
1. Use of a heterogeneous wet oxidation catalyst in the treatment of wastewater containing nonionic surfactants, comprising, in parts by weight:
(a) 50-95 parts of TiO 2 ；
(b) 5-50 parts of BaSO 4 ；
(c) 0.05-5 parts of platinum group metal simple substance;
the preparation method of the catalyst comprises the following steps:
s1, respectively dissolving soluble barium salt and TiOSO 4 Dissolving in water to prepare a solution A and a solution B;
s2, adding the solution A and the alkaline solution into the solution B, and controlling the pH of the end point to form a precipitate; then the sediment is washed, dried and pulverized to prepare the BaSO-containing liquid 4 And TiO 2 Is a mixture of (a) and (b);
s3, mixing the mixture with a binder and water, extruding to form strips, and drying and roasting to obtain a catalyst carrier;
s4, loading metal salt containing platinum group metal simple substances on a catalyst carrier, and roasting to obtain the heterogeneous wet oxidation catalyst;
in the step S2, the end point pH is controlled to be 9-10.
2. The use according to claim 1, wherein the simple substance of platinum group metal is selected from at least one of Pt, pd, rh and Ru.
3. The use according to claim 1, characterized in that the TiO 2 The crystal form of (2) is anatase; and/or the platinum group metal simple substance is nano particles.
4. The method according to claim 3, wherein the nanoparticles have a particle diameter of 5nm or less.
5. The use according to any one of claims 1 to 4, wherein the TiO 2 And BaSO 4 The weight ratio is (1-5): 1, and the BaSO 4 The weight ratio of the catalyst to the platinum group metal simple substance is (0.8-8) 0.01.
6. The use according to claim 5, characterized in that the TiO 2 And BaSO 4 The weight ratio of the BaSO4 to the platinum group metal is (3-4.5) 1, and the weight ratio of the BaSO4 to the platinum group metal element is (0.9-3) 0.01.
7. The use according to any one of claims 1 to 4, wherein in step S2, the alkaline solution is selected from at least one of ammonia, urea solution, sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution.
8. The use according to any one of claims 1 to 4, wherein in step S3 the binder is selected from at least one of carboxymethyl cellulose, starch, aluminium sol, silica sol, nitric acid, sulfuric acid, oxalic acid and citric acid.
9. The use according to any one of claims 1 to 4, wherein in step S3, the baking temperature is 400 to 800 ℃ and the baking time is 1 to 6 hours; and/or in the step S4, the roasting temperature is 200-600 ℃, and the roasting time is 1-12 h.
10. The use according to any one of claims 1 to 4, characterized in that the waste water, air, is contacted with the heterogeneous wet oxidation catalyst, after which a treated waste water is obtained, the nonionic surfactants in the waste water comprising polyoxyethylene, polyol and aminoalcohol types; the COD content of the wastewater is 5000-200000 mg/L.
11. The use according to claim 10, characterized in that the COD content of the waste water is 5000-150000 mg/L.
12. The use according to claim 10, wherein the reaction temperature is 150-250 ℃, the reaction pressure is 2-6 mpa, and the reaction time is 10-120 minutes; and/or the air consumption is 1.05-1.5 times of the theoretical COD value.
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