CN111318284A - Ozone oxidation catalyst and preparation method and application thereof - Google Patents
Ozone oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN111318284A CN111318284A CN201811543266.5A CN201811543266A CN111318284A CN 111318284 A CN111318284 A CN 111318284A CN 201811543266 A CN201811543266 A CN 201811543266A CN 111318284 A CN111318284 A CN 111318284A
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- catalyst
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- ozone oxidation
- oxidation catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000003647 oxidation Effects 0.000 title claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002270 dispersing agent Substances 0.000 claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 230000008569 process Effects 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 229920000858 Cyclodextrin Polymers 0.000 claims description 18
- 239000001116 FEMA 4028 Substances 0.000 claims description 18
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical group OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 18
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 18
- 229960004853 betadex Drugs 0.000 claims description 18
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 229910052723 transition metal Inorganic materials 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000010949 copper Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000006385 ozonation reaction Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000008262 pumice Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 32
- 239000010865 sewage Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 19
- 238000005470 impregnation Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 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 8
- 230000000052 comparative effect Effects 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution 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
- B01J23/83—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 rare earths or actinides
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an ozone oxidation catalyst, a preparation method and application thereof. The raw materials of the ozone oxidation catalyst comprise a carrier, soluble salts of active components, soluble salts of a cocatalyst, a dispersion aid and a bonding aid, wherein the dispersion aid is an organic dispersion aid capable of being removed in the roasting process, and the bonding aid is a volatile alkaline solvent. The ozone oxidation catalyst has better catalytic activity and stability. And due to the action of the auxiliary dispersing agent and the auxiliary binding agent, the catalyst provided by the invention is prepared by adopting a simple and convenient process of dipping, drying and roasting, so that the preparation process is greatly simplified, and the production cost is reduced. The catalyst is applied to the advanced treatment of chemical comprehensive sewage and has the characteristics of complex sewage treatment capacity, high COD removal rate and the like.
Description
Technical Field
The invention relates to the technical field of catalysts, and mainly relates to an ozone oxidation catalyst and a preparation method thereof.
Background
The chemical comprehensive sewage is formed by gathering various chemical sewages, and the water quality is complex and the characteristic pollutants are various according to the source diversity. In recent years, the environmental awareness of people is gradually strengthened, and in order to control water pollution, protect the good state of ground water and underground water quality of rivers, lakes, reservoirs, oceans and the like, ensure human health and maintain ecological balance, chemical comprehensive sewage can be discharged after being purified. The existing chemical comprehensive sewage treatment method has two treatment modes for organic pollutants in sewage, wherein one treatment mode is physicochemical treatment, and the other treatment mode is biochemical treatment. In order to realize the standard discharge of the final effluent of the sewage plant, the effluent after biochemical treatment needs to be subjected to advanced treatment. However, the organic matter and organic matter residue remaining in the effluent after biochemical treatment become more complicated, which brings a certain difficulty to advanced treatment.
Ozone is an allotrope of oxygen, has an oxidation-reduction potential of 2.07V in a standard state, is a very strong oxidant, and is widely applied to the fields of domestic sewage treatment and industrial sewage treatment. In order to overcome the problems of selective oxidation, large ozone consumption and high energy consumption of the single ozone oxidation technology, a catalyst is introduced into a reaction system. Under the action of the catalyst, the efficiency of ozone oxidation can be greatly improved, and the using amount of ozone is reduced. Furthermore, catalytic ozonation is non-selective. The advantages make the ozone catalytic oxidation technology become an important chemical comprehensive advanced sewage treatment technology.
The traditional homogeneous catalysis ozone oxidation technology has the problems that the catalyst cannot be recovered, secondary pollution is introduced, and the treatment cost is high. The reaction system of the heterogeneous catalytic ozonation technology has three phases of solid, liquid and gas, the catalyst is solid, reactants and products are liquid or gaseous, the separation and reutilization of the catalyst are convenient, secondary pollution of effluent is not caused, and the heterogeneous catalytic ozonation technology becomes a mainstream technology of a sewage deep treatment technology.
The invention patent CN102941084A discloses a preparation method of a supported bi-component metal oxide ozone catalytic oxidation catalyst, which is characterized by comprising the following steps: mixing gamma-Al2O3After the microspheres are activated, the microspheres are dipped in a mixed solution of manganese nitrate and cerium nitrate, and then the supported manganese-cerium bi-component composite catalyst is prepared after drying and roasting. The catalyst belongs to a general type for wastewater treatment.
The invention patent 200710032553.5 discloses a preparation method of a ceramsite catalyst for ozone catalytic oxidation, which comprises the following processes of preparation of a ceramsite raw material core, coating of the ceramsite raw material core by the catalyst and roasting: the catalyst is coated on the ceramsite raw material core by MnO and MnO2、TiO2、CoO、Co3O4、Fe2O3One or more composite catalyst active ingredients in FeO are crushed into particles with the particle size of 0.1-1mm, and the particles are mixed with the raw materials for producing the ceramsite, and the mixture is loaded on the ceramsite raw material core to generate the catalyst-coated ceramsite with the particle size of 3-4 mm; the ceramsite catalyst for catalytic oxidation by ozone is prepared.
The invention patent 201010539704.8 discloses a preparation method of an ozone catalytic oxidation catalyst for treating cyanide-containing wastewater, which comprises the following steps: amorphous alumina is used as a carrier, active components of copper, iron and tin are sprayed in a granulator in the form of solution, and the catalyst is prepared after maintenance, drying and roasting.
However, the currently available ozone oxidation catalysts suffer from the following drawbacks: the preparation process is complicated, such as by the spray dispersion process described above; the catalyst prepared by the conventional impregnation and dispersion process has poor activity, and the combination stability between the active component and the cocatalyst and the carrier is poor, so that the stability of the catalyst is poor. For the above reasons, further research on the existing heterogeneous catalytic ozonation technology is needed to solve the above problems in the prior art.
Disclosure of Invention
In order to solve the problems, the invention aims to provide an ozone oxidation catalyst and a preparation method thereof, the catalyst has simple preparation process and high catalytic activity and stability, and has the characteristics of complex sewage treatment capability, high COD removal rate and low preparation cost when being applied to the advanced treatment of chemical comprehensive sewage.
In order to achieve the above object, according to one aspect of the present invention, there is provided an ozone oxidation catalyst whose raw materials include a carrier, a soluble salt of an active component, a soluble salt of a promoter, a co-dispersant, and a co-binder, wherein the co-dispersant is an organic dispersant that can be removed during calcination, and the co-binder is a volatile basic solvent.
Further, the carrier is selected from one or more of the group consisting of an alumina carrier, a silica gel carrier, an activated carbon carrier, pumice and diatomite; preferably, the support is a modified gamma-activated alumina.
Further, the specific surface area of the modified gamma-activated alumina is 230-350 m2Per g, preferably 323m2(ii)/g; the pore volume of the modified gamma-activated alumina is 0.35-0.65 mL/g, preferably 0.53 mL/g; the particle size of the modified gamma-activated alumina is 2-4 mm.
Furthermore, the auxiliary dispersant is β -cyclodextrin, preferably β -cyclodextrin, which is added in the form of an aqueous solution with the mass concentration of 0.05-1.5%.
Further, the auxiliary binding agent is ammonia water.
Further, the active component is an oxide of a transition metal element; preferably, the transition metal element is selected from one or more of manganese, copper and iron; more preferably, the molar ratio of the transition metal element to ammonia in the ammonia water is 2-4: 1.
Further, the catalyst promoter is an oxide of a rare earth element; preferably, the rare earth element is cerium.
Further, the molar ratio of the transition metal element to the rare earth element is 8-14: 1.
According to another aspect of the present invention, there is also provided a method for preparing an ozone oxidation catalyst, comprising the steps of: s1, dipping the carrier into a solution containing soluble salts of the active components, soluble salts of the promoters, the dispersion promoters and the binder promoters to obtain a catalyst precursor; wherein the auxiliary dispersant is an organic dispersant which can be removed in the roasting process, and the auxiliary binding agent is a volatile alkaline solvent; and S2, drying and roasting the catalyst precursor in sequence to obtain the ozone oxidation catalyst.
Furthermore, the soluble salt of the active component is nitrate, and the soluble salt of the cocatalyst is nitrate.
Further, the drying process comprises a first stage drying and a second stage drying which are sequentially carried out, wherein the first stage drying lasts for 3-5 hours at normal temperature and normal pressure; the second stage of drying is continued for 4-6 h at 110-130 ℃.
Further, the roasting process comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, wherein in the first-stage roasting, the temperature is increased to 280-320 ℃ at the temperature increase rate of 8-20 ℃/min, and the roasting is carried out for 1-3 h; in the second stage of roasting, the temperature is raised to 390-510 ℃ at the temperature rise rate of 3-8 ℃/min, and roasting is carried out for 3-12 h.
According to another aspect of the invention, the invention also provides an application of the ozone oxidation catalyst in chemical wastewater treatment.
The invention provides an ozone oxidation catalyst, which comprises a carrier, soluble salts of active components, soluble salts of a cocatalyst, a dispersion aid and a bonding aid, wherein the dispersion aid is an organic dispersant which can be removed in the roasting process, and the bonding aid is a volatile alkaline solvent. The auxiliary dispersing agent is utilized to be beneficial to improving the dispersibility of the soluble salt of the cocatalyst and the soluble salt of the auxiliary dispersing agent on the surface of the carrier in the impregnation process, so that the dispersibility of the final active component on the surface of the carrier can be improved. The alkaline solvent is used as the auxiliary binding agent, so that the acid strength distribution on the surface of the carrier can be improved, the binding strength of the active component, the auxiliary agent and the carrier is improved, and the stability of the catalyst is further improved. And the auxiliary dispersing agent and the auxiliary binding agent can be removed in a decomposition reaction or volatilization mode in the drying and roasting processes after impregnation, and cannot remain in the final catalyst.
The catalytic activity and stability of the ozone oxidation catalyst can be effectively improved due to the two reasons, and the catalyst provided by the invention is prepared by adopting a simple and convenient process of dipping, drying and roasting due to the functions of the auxiliary dispersing agent and the auxiliary binding agent, so that the preparation process is greatly simplified, and the production cost is reduced. The catalyst is applied to the advanced treatment of chemical comprehensive sewage and has the characteristics of complex sewage treatment capacity, high COD removal rate and the like.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As mentioned in the background section, the existing ozone oxidation catalysts cannot combine the following properties: 1. the preparation process is simple; 2. the catalytic activity is high; 3. the catalyst has high stability.
In order to solve the above problems, an aspect of the present invention provides an ozone oxidation catalyst, the raw materials of which include a carrier, a soluble salt of an active component, a soluble salt of a promoter, a dispersion aid and a binder aid, wherein the dispersion aid is an organic dispersant capable of being removed during calcination, and the binder aid is a volatile alkaline solvent. The auxiliary dispersing agent is utilized to be beneficial to improving the dispersibility of the soluble salt of the cocatalyst and the soluble salt of the auxiliary dispersing agent on the surface of the carrier in the impregnation process, so that the dispersibility of the final active component on the surface of the carrier can be improved. The alkaline solvent is used as the auxiliary binding agent, so that the acid strength distribution on the surface of the carrier can be improved, the binding strength of the active component, the auxiliary agent and the carrier is improved, and the stability of the catalyst is further improved. And the auxiliary dispersing agent and the auxiliary binding agent can be removed in a decomposition reaction or volatilization mode in the drying and roasting processes after impregnation, and cannot remain in the final catalyst.
The catalytic activity and stability of the ozone oxidation catalyst can be effectively improved due to the two reasons, and the catalyst provided by the invention is prepared by adopting a simple and convenient process of dipping, drying and roasting due to the functions of the auxiliary dispersing agent and the auxiliary binding agent, so that the preparation process is greatly simplified, and the production cost is reduced. The catalyst is applied to the advanced treatment of chemical comprehensive sewage and has the characteristics of complex sewage treatment capacity, high COD removal rate and the like.
In a preferred embodiment, the carrier is one or more selected from the group consisting of an alumina carrier, a silica gel carrier, an activated carbon carrier, pumice, and diatomaceous earth. More preferably, the carrier is modified gamma-activated alumina, and the modified gamma-activated alumina has higher specific surface area and pore volume, so that the dispersibility of the active component and the cocatalyst can be further improved, and the catalytic activity of the ozone oxidation catalyst can be further improved.
In a preferred embodiment, the specific surface area of the modified gamma-activated alumina is 230 to 350m2(ii) in terms of/g. In one embodiment, the modified gamma-activated alumina has a specific surface area of 323m2(ii) in terms of/g. In one embodiment, the modified gamma-activated alumina has a pore volume of 0.35 to 0.65 mL/g. In one embodiment, the modified gamma-activated alumina has a pore volume of 0.53 mL/g. The particle size is 2-4 mm. The porous property, high dispersity and high surface area of the activated alumina can be utilized to obtain the characteristics required by the catalytic action, such as adsorption performance, surface activity, excellent thermal stability and the like, and simultaneously, the dispersity of the active component and the catalytic assistant on the activated alumina can be improved, so that the catalytic activity of the catalyst is improved.
In a preferred embodiment, the co-dispersant is β -cyclodextrin, β -cyclodextrin, and a certain amount of the co-dispersant is beneficial to effectively improving the distribution uniformity of active components and the co-catalyst on the surface of a carrier, improving the utilization rate of the active components and a catalytic assistant and further improving the catalytic activity of the catalyst.
In the actual preparation process, β -cyclodextrin can be directly added into the dipping solution as a dipping raw material, more preferably β -cyclodextrin is added in the form of an aqueous solution with the mass concentration of 0.05-1.5%, in one embodiment, the mass concentration of β -cyclodextrin is 0.05%, in one embodiment, the mass concentration of β -cyclodextrin is 0.5%, in one embodiment, the mass concentration of β -cyclodextrin is 1.5%, the addition in the form of the solution with the concentration can be mixed with other raw materials more quickly, and meanwhile, the balance between better dispersing effect and cost can be provided, and of course, the usage amount of the auxiliary dispersing agent can be adjusted through experiments to achieve the best effect.
The catalyst in the ozone heterogeneous catalytic oxidation process also comprises a binding assistant. In a preferred embodiment, the co-binder is ammonia. The ammonia water can more effectively adjust the acidity distribution of the surface of the carrier so as to further improve the bonding strength of the final active component and the cocatalyst with the surface of the carrier. Another advantage of using ammonia as the co-binder is that ammonia can be more fully volatilized in the drying and calcining steps, thus having no effect on the final components of the catalyst.
The active component can be of a type commonly used in the art, and in a preferred embodiment, the active component is an oxide of a transition metal element, and the transition metal element has a vacant electron orbit and is easy to accept an electron pair, so that an intermediate can be formed with lower energy, and the catalytic activity can be further improved. More preferably, the active component is an oxide of a transition metal element; preferably, the transition metal element is selected from one or more of manganese, copper and iron. More preferably, the molar ratio of the transition metal element to ammonia in the ammonia water is 2-4: 1, and the use amounts of the transition metal element and the ammonia in the ammonia water are controlled in the above range, so that the stability of the catalyst is further improved.
In a preferred embodiment, the promoter is an oxide of a rare earth element. Preferably, the rare earth element is cerium. The catalyst in the ozone heterogeneous catalytic oxidation process utilizes the relatively cheap transition metal elements and the rare earth elements with relatively rich reserves, thereby reducing the preparation cost of the catalyst. In addition, the composition of transition metal elements and rare earth elements, particularly copper and cerium can obviously improve the thermal stability and catalytic activity of the catalyst. The copper is dispersed on the surface of the carrier containing cerium, so that the catalytic activity of the copper can be greatly improved. In a preferred embodiment, the molar ratio of the transition metal element to the rare earth element is 8 to 14: 1.
According to another aspect of the present invention, there is also provided a method for preparing an ozone oxidation catalyst, comprising the steps of: s1, dipping the carrier into a solution containing soluble salts of the active components, soluble salts of the promoters, the dispersion promoters and the binder promoters to obtain a catalyst precursor; wherein the auxiliary dispersant is an organic dispersant which can be removed in the roasting process, and the auxiliary binding agent is a volatile alkaline solvent; and S2, drying and roasting the catalyst precursor in sequence to obtain the ozone oxidation catalyst.
In the preparation process, a dispersion aid and a bonding aid are added in the dipping process, wherein the dispersion aid is an organic dispersion aid capable of being removed in the roasting process, and the bonding aid is a volatile alkaline solvent. The auxiliary dispersing agent is utilized to be beneficial to improving the dispersibility of the soluble salt of the cocatalyst and the soluble salt of the auxiliary dispersing agent on the surface of the carrier in the impregnation process, so that the dispersibility of the final active component on the surface of the carrier can be improved. The alkaline solvent is used as the auxiliary binding agent, so that the acid strength distribution on the surface of the carrier can be improved, the binding strength of the active component, the auxiliary agent and the carrier is improved, and the stability of the catalyst is further improved. And the auxiliary dispersing agent and the auxiliary binding agent can be removed in a decomposition reaction or volatilization mode in the drying and roasting processes after impregnation, and cannot remain in the final catalyst. The catalytic activity and stability of the ozone oxidation catalyst can be effectively improved due to the two reasons, and the catalyst provided by the invention is prepared by adopting a simple and convenient process of dipping, drying and roasting due to the functions of the auxiliary dispersing agent and the auxiliary binding agent, so that the preparation process is greatly simplified, and the production cost is reduced. The catalyst is applied to the advanced treatment of chemical comprehensive sewage and has the characteristics of complex sewage treatment capacity, high COD removal rate and the like.
In a preferred embodiment, the soluble salt of the active component is a nitrate and the soluble salt of the promoter is a nitrate. In the actual operation process, an impregnation solution is prepared, and specifically, a soluble salt solution of the active component, a soluble salt solution of the cocatalyst, the dispersion aid and the binder are mixed to form the impregnation solution. More preferably, the mass content of the transition metal element in the soluble solution of the active component is 1-3%. It is understood that when the concentration of the active component is too high and the molar ratio thereof to the co-catalyst is too high, the transition metal oxide is liable to aggregate on the surface to form clusters, which in turn leads to a decrease in the activity of the catalyst. The relative content of both is within the above range, and when within the above range, cost and efficiency can be further considered.
In a preferred embodiment, the drying process comprises a first stage drying and a second stage drying which are sequentially carried out, wherein the first stage drying lasts for 3-5 hours at normal temperature and normal pressure; the second stage of drying is continued for 4-6 h at 110-130 ℃. The first stage of drying is carried out at a cool and ventilated place under the conditions of normal temperature and normal pressure, so that the distribution of the active component on the carrier is favorably improved, and the bonding force between the active component and the carrier is further favorably realized. And the second stage of drying is carried out in a forced air oven at the temperature of 110-130 ℃, so that moisture in the residual impregnation liquid can be evaporated quickly, and the bonding force between the active component and the carrier can be further facilitated.
More preferably, the roasting process comprises a first-stage roasting and a second-stage roasting which are sequentially carried out, wherein in the first-stage roasting, the temperature is increased to 280-320 ℃ at the temperature increase rate of 8-20 ℃/min, and the roasting is carried out for 1-3 h; in the second stage of roasting, the temperature is raised to 390-510 ℃ at the temperature rise rate of 3-8 ℃/min, and roasting is carried out for 3-12 h.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1 preparation of modified support
Using gamma-Al2O3As a carrier, it has a specific surface area of about 177m2The grain diameter is 2mm to 4mm, and the pore volume is 0.40 mL/g. 1000mL of alumina was put into a 3000mL beaker, and washed 3 times with distilled water to remove fly ash. Soaking with 1200mL of 0.1mol/L citric acid at 80 ℃ for 4h, draining residual liquid, air-drying at room temperature in a ventilated place away from light, putting the air-dried carrier into an air-blast drying oven, and drying at 120 ℃ for 5h to obtain modified gamma-Al2O3A support having a specific surface area of about 323m2The grain diameter is 2mm to 4mm, and the pore volume is 0.53 mL/g.
EXAMPLE 2 preparation of catalyst C1
Preparing a steeping liquor by using analytically pure copper nitrate, analytically pure cerium nitrate, analytically pure ammonia water and analytically pure β -cyclodextrin, wherein the molar concentration of the copper nitrate is 0.6mol/L, the molar ratio of Cu to Ce is 10 to 1, and the molar ratio of Cu to NH3The modified gamma-Al prepared in comparative example 1 was added to a solution of 3:1, β -cyclodextrin at a mass concentration of 0.5%2O3300mL of the carrier was immersed in 400mL of the immersion liquid and stirred every 0.5 h. And (3) after dipping for 4h, draining residual liquid, airing at a ventilation place at room temperature in a dark place, putting the aired carrier into an air-blast drying oven, and drying at 120 ℃ for 6h to obtain the catalyst precursor. And (3) putting the catalyst precursor into a muffle furnace, heating and roasting, quickly heating to 300 ℃ from room temperature at the heating rate of 20 ℃/min, roasting at constant temperature for 2h, heating to 450 ℃ at the heating rate of 5 ℃/min, and roasting at constant temperature for 4h to obtain the catalyst C1.
EXAMPLE 3 preparation of catalyst C2
The difference from example 2 is that the molar ratio of Cu to Ce in the impregnation solution is 14:1, yielding finished catalyst C2.
EXAMPLE 4 preparation of catalyst C3
The difference from example 2 is that the molar ratio of Cu to Ce in the impregnation solution is 8:1, yielding finished catalyst C3.
EXAMPLE 5 preparation of catalyst C4
The difference from the example 2 is that the mass concentration of the co-dispersant β -cyclodextrin in the impregnation liquid is 0.05%, and the finished catalyst product C4 is obtained.
EXAMPLE 6 preparation of catalyst C5
The difference from the example 2 is that the mass concentration of the co-dispersant β -cyclodextrin in the impregnation solution is 1.5%, and the finished catalyst product C5 is obtained.
EXAMPLE 7 preparation of catalyst C6
The difference from the embodiment 2 is that the catalyst precursor is put into a muffle furnace to be heated and roasted, the temperature is rapidly raised to 280 ℃ from the room temperature at the heating rate of 20 ℃/min, the catalyst precursor is roasted for 2 hours at the constant temperature, and then the temperature is raised to 450 ℃ at the heating rate of 5 ℃/min, and the catalyst finished product C6 is obtained after the catalyst precursor is roasted for 4 hours at the constant temperature.
EXAMPLE 8 preparation of catalyst C7
The difference from the embodiment 2 is that the catalyst precursor is put into a muffle furnace to be heated and roasted, the temperature is rapidly raised to 300 ℃ from the room temperature at the heating rate of 20 ℃/min, the catalyst precursor is roasted for 2 hours at the constant temperature, and then the temperature is raised to 400 ℃ at the heating rate of 5 ℃/min, and the catalyst finished product C7 is obtained after the catalyst precursor is roasted for 4 hours at the constant temperature.
Comparative example 1 preparation of catalyst D1 without Co-dispersant
Preparing an impregnating solution by using analytically pure copper nitrate, analytically pure cerium nitrate and analytically pure ammonia water, wherein the molar concentration of the copper nitrate is 0.6mol/L, the molar ratio of Cu to Ce to 10 to 1, and the molar ratio of Cu to NH33: 1. Modified gamma-Al from example 12O3300mL of the carrier was immersed in 400mL of the immersion liquid and stirred every 0.5 h. And (3) after dipping for 4h, draining residual liquid, airing at a ventilation place at room temperature in a dark place, putting the aired carrier into an air-blast drying oven, and drying at 120 ℃ for 6h to obtain the catalyst precursor. And putting the catalyst precursor into a muffle furnace for heating and roasting. Heating to 300 ℃ from room temperature at the heating rate of 20 ℃/min, roasting at constant temperature for 2h, heating to 450 ℃ at the heating rate of 5 ℃/min, and roasting at constant temperature for 4h to obtain the catalyst D1.
Comparative example 2 preparation of Binderless catalyst D2
Preparing an impregnating solution by using analytically pure copper nitrate, analytically pure cerium nitrate and analytically pure β -cyclodextrin, wherein the molar concentration of the copper nitrate is 0.6mol/L, the molar ratio of Cu to Ce is 10:1, and the mass concentration of β -cyclodextrin is 0.5 percent, and taking the modified gamma-Al prepared in example 12O3300mL of the carrier was immersed in 400mL of the immersion liquid and stirred every 0.5 h. After 4h of immersion, the residual liquid was drained off and the reaction solution was left to standAnd (3) drying the warm ventilated place in a dark place, putting the dried carrier into a blast drying oven, and drying at 120 ℃ for 6 hours to obtain the catalyst precursor. And putting the catalyst precursor into a muffle furnace for heating and roasting. Heating to 300 ℃ from room temperature at the heating rate of 20 ℃/min, roasting at constant temperature for 2h, heating to 450 ℃ at the heating rate of 5 ℃/min, and roasting at constant temperature for 4h to obtain the catalyst D2.
Evaluation of catalyst Performance
100mL of each of the catalysts C1-C7 prepared in examples 2-8 and the catalysts D1-D2 prepared in comparative examples 1-2 were used to conduct comparative experiments for evaluating the activity.
The effluent of biochemical reaction (COD is 75.2mg/L) of a sewage plant is used as a water source, and continuous reaction is adopted to carry out activity evaluation. The ozone concentration in the aeration mixed gas is 2.0 mg/L. Activity evaluation was carried out for 24h, sampling analysis every 4 h.
The evaluation results are shown in Table 1.
TABLE 1 catalyst evaluation results
As can be seen from Table 1, the average effluent COD and the average COD removal rate of the catalyst prepared by the method of the invention are superior to those of the comparative example. The method of the invention realizes that the catalyst with complex sewage treatment capacity and high COD removal rate can be obtained at lower cost, and specifically comprises the following steps:
(1) the catalyst carrier in the ozone heterogeneous catalytic oxidation process has important influence on the catalytic efficiency. In the invention, the modified gamma-activated alumina is used as a carrier, and the characteristics of adsorption performance, surface activity, excellent thermal stability and the like are provided by utilizing the porosity, high dispersity and high surface area of the modified gamma-activated alumina, and meanwhile, the dispersity of active components and catalytic auxiliaries on the modified gamma-activated alumina is improved, so that the catalytic activity of the catalyst is improved.
(2) The invention adopts β -cyclodextrin as the co-dispersant, improves the distribution uniformity of the active component and the auxiliary agent on the surface of the carrier, improves the utilization rate of the active component and the auxiliary agent, and further improves the catalytic activity of the catalyst.
(3) An amount of the co-binder may improve the acid strength distribution on the surface of the support. According to the invention, ammonia water solution is used as a bonding assistant, the alkalescence of the ammonia water solution is utilized to improve the acid strength distribution on the surface of the carrier, the bonding strength of the active component, the assistant and the carrier is improved, and the stability of the catalyst is further improved. In addition, the ammonia water can be volatilized in the drying and roasting links, so that the final components of the catalyst are not influenced.
In conclusion, the modified gamma-activated alumina is used as a carrier, and the co-dispersant and the co-binder are introduced, so that the preparation process of the catalyst is improved, the activity and the stability of the catalyst are improved, and the effective balance between the cost and the catalytic activity is obtained.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The ozone oxidation catalyst is characterized in that raw materials of the ozone oxidation catalyst comprise a carrier, soluble salts of active components, soluble salts of a cocatalyst, a dispersion aid and a binder aid, wherein the dispersion aid is an organic dispersant which can be removed in a roasting process, and the binder aid is a volatile alkaline solvent.
2. The ozonation catalyst of claim 1, wherein the support is one or more selected from the group consisting of an alumina support, a silica gel support, an activated carbon support, pumice, diatomaceous earth; preferably, the support is a modified gamma-activated alumina.
3. The ozonation catalyst according to claim 2, wherein the modified gamma-activated alumina has a specific surface area of 230 to 350m2Per g, preferably 323m2(ii)/g; the pore volume of the modified gamma-activated alumina is 0.35-0.65 mL/g, preferably 0.53 mL/g; the particle size of the modified gamma-activated alumina is 2-4 mm.
4. The ozone oxidation catalyst as claimed in any one of claims 1 to 3, wherein the dispersion aid additive is β -cyclodextrin, preferably β -cyclodextrin is added as an aqueous solution having a mass concentration of 0.05-1.5%.
5. The ozonation catalyst of any one of claims 1 to 3, wherein the co-binder is ammonia.
6. The ozone oxidation catalyst according to claim 5, wherein the active component is an oxide of a transition metal element; preferably, the transition metal element is selected from one or more of manganese, copper and iron; more preferably, the molar ratio of the transition metal element to ammonia in the ammonia water is 2-4: 1.
7. The ozone oxidation catalyst of claim 6, wherein the promoter is an oxide of a rare earth element; preferably, the rare earth element is cerium.
8. The ozonation catalyst according to claim 7, wherein a molar ratio of the transition metal element to the rare earth element is 8 to 14: 1.
9. A method of preparing the ozone oxidation catalyst according to any one of claims 1 to 8, comprising the steps of:
s1, dipping the carrier into a solution containing soluble salts of the active components, soluble salts of the promoters, the dispersion promoters and the binder promoters to obtain a catalyst precursor; the auxiliary dispersing agent is an organic dispersing agent which can be removed in the roasting process, and the auxiliary binding agent is a volatile alkaline solvent;
and S2, drying and roasting the catalyst precursor in sequence to obtain the ozone oxidation catalyst.
10. The method according to claim 9, wherein the soluble salt of the active component is a nitrate and the soluble salt of the promoter is a nitrate.
11. The preparation method of claim 9, wherein the drying process comprises a first stage drying and a second stage drying which are sequentially performed, wherein the first stage drying lasts for 3-5 hours at normal temperature and pressure; and the second stage of drying lasts for 4-6 hours at the temperature of 110-130 ℃.
12. The preparation method of claim 11, wherein the roasting process comprises a first stage roasting and a second stage roasting which are sequentially performed, wherein in the first stage roasting, the temperature is increased to 280-320 ℃ at a temperature increase rate of 8-20 ℃/min, and the roasting is performed for 1-3 h; in the second stage of roasting, the temperature is increased to 390-510 ℃ at the temperature increase rate of 3-8 ℃/min, and roasting is carried out for 3-12 h.
13. Use of an ozone oxidation catalyst according to any one of claims 1 to 8 in chemical wastewater treatment.
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