CN112642494A - Nitrile-containing organic waste gas purification catalyst and preparation method thereof - Google Patents
Nitrile-containing organic waste gas purification catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000007789 gas Substances 0.000 title claims abstract description 25
- 239000010815 organic waste Substances 0.000 title claims abstract description 20
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000746 purification Methods 0.000 title claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 32
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 25
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 9
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 9
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 6
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910020203 CeO Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 239000011572 manganese Substances 0.000 description 10
- 241000264877 Hippospongia communis Species 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000007084 catalytic combustion reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N bismuth(III) nitrate Inorganic materials [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 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 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
A nitrile-containing organic waste gas purification catalyst is characterized in that: the catalyst is formed by coating a first coating, a second coating, a third coating and a fourth coating on cordierite honeycomb ceramic serving as a main carrier, wherein the first coating is Al2O3、SiO2、CeO2、ZrO2、Bi2O3The loading amount is 20 g/L; the second coating is CeO2、ZrO2、La2O3、CuO、MnO2The loading amount is 10 g/L; the third coating is CuO or MnO2The loading amount is 10 g/L; the fourth coating is CuO or MnO2Pt and Pd, the loading amount is 3 g/L. The invention has the advantages of simple preparation process, high catalyst activity and the likeIs characterized in that.
Description
Technical Field
The invention relates to a nitrile-containing organic waste gas purification catalyst and a preparation method thereof, which are particularly suitable for purification treatment of organic waste gases such as acrylonitrile, hydrocyanic acid, acetonitrile and the like, and belong to the technical field of catalysts.
Background
The organic waste gas containing nitrile discharged by the industries of petrochemical industry, pharmaceutical chemical industry, electronic industry and the like has high toxicity, national emission index requirements and national environmental protection emission index requirements, so the pollution treatment problem is a key point of the organic waste gas treatment at present and is also a difficult point. The national environmental protection emission index puts high emission index requirements on organic matters mainly containing CN bonds, for example, the emission index of acrylonitrile is 0.5mg/m3The HCN index is 1.9mg/m3For high-concentration CN bond-containing organic waste gas, the condensation recovery is generally adopted, and then the technologies of adsorption concentration, catalysis, denitration, alkali liquor spraying and the like are selected for further treatment, the technological process is complex, and equipment is adoptedThe investment is large, the operation cost is high, the recovered organic matters generally contain other organic impurities, the recovered substances are difficult to be directly used as raw materials, further purification and separation are needed, and secondary pollution such as dissipation of the recovered substances and the like can be generated, so that the application of the technology is limited to a certain extent. The waste gas with low concentration is generally subjected to thermal incineration or noble metal catalytic oxidation to convert the organic matters containing CN bonds into carbon dioxide and NOxAnd water, then adopting denitration method to make NOxConverting into nitrogen gas, or spraying with ozone-added alkali solutionxConverted into nitrate to achieve the purpose of purification. Although the technology has simple process flow, the prior art generally adopts an independent incinerator, a catalytic reactor, a denitration reactor and an alkali liquor spray tower, and the equipment occupies a large area.
The catalytic oxidation method for purifying organic waste gas is more and more concerned by users due to high organic matter purification efficiency, simple and stable operation and wider application range.
At present, the catalysts used for purifying organic waste gas mainly include two main types, namely granular catalysts and honeycomb catalysts. The granular catalyst is prepared by taking alumina as a carrier and loading active components such as Pd, Pt, Cu, Mn and the like; the honeycomb catalyst is generally prepared by taking cordierite honeycomb ceramics or regular metal-based honeycombs as carriers and loading alumina, a cocatalyst, active components Pd, Pt, Rh, Cu, Mn and the like. The conventional noble metal catalyst has high activity, but most CN bond reactant in nitrile organic waste gas is NOxIs easy to exceed the limit value of national environmental protection emission index, so a denitration reactor is required to be arranged, and a large amount of NH is added3NO emitted after denitrationxCan meet the requirement of environmental emission, NH exists in the process3The escape problem of (2) causes secondary pollution; and the concentration fluctuation of the organic matters can also influence the stable operation of equipment, so the requirement on automatic control is high, the equipment investment is large, and the subsequent larger environmental protection problem is brought, so the noble metal catalyst has certain limitation in the purification of the organic waste gas containing nitrile. To solve this problem, chinese patent CN105605595B discloses aThe integrated purifying method of industrial waste gas of cyanogen, hydrocarbon and NOx includes the following steps: (1) separating free liquid from tail gas containing cyanogen, hydrocarbon and nitrogen oxide pollutants by gas-liquid separation equipment, mixing the free liquid with air sent by an air blower, and preheating by using a heating unit; entering a selective catalytic combustion reactor for selective catalytic combustion reaction, catalyzing in the selective catalytic combustion reactor in two sections, catalyzing the front section by using a supported molecular sieve catalyst, catalyzing the rear section by using a supported noble metal catalyst, entering the selective catalytic combustion reactor, controlling the temperature of the inlet of the selective catalytic combustion reactor to be 280-350 ℃, controlling the temperature of the front section of the catalyst to be 300-550 ℃, controlling the temperature of the rear section to be 500-650 ℃, and converting harmful substances into CO under the condition that the bed layer pressure is 0.5-25 kPa2、H2O and N2Wherein, the front-section load type molecular sieve catalyst is a honeycomb integral or particle package type catalyst, wherein the molecular sieve is one or more of ZSM-5-ZSM-48 series, Beta, Y, MCM-22-MCM-56 series, SAPO-5-SAPO-47 series, SBA-15, SBA-16 and TS-1 molecular sieves, and the load metal ion is one or more of copper, iron, cobalt, manganese, nickel, aluminum, silver and the like; the noble metal catalyst of the rear section adopts cordierite ceramic or metal corrugated plate as a substrate, and the noble metal is two of platinum, palladium, rhodium, silver and ruthenium. However, the use of two different catalysts presents certain difficulties and risks to the design and long-term operation of the plant.
Disclosure of Invention
The invention aims to solve the technical problem of providing an organic waste gas purification catalyst with simple production process, high activity and long service life and a preparation method thereof aiming at the defects of the existing nitrile-containing organic waste gas treatment technology, catalyst and preparation method thereof, and the nitrile-containing organic waste gas can be treated by adopting one catalyst.
The invention takes cordierite honeycomb ceramic as a main carrier and is formed by coating a first coating, a second coating, a third coating and a fourth coating, wherein the first coating is Al2O3、SiO2、CeO2、ZrO2、Bi2O3The loading amount is 20 g/L; the second coating is CeO2、ZrO2、La2O3、CuO、MnO2The loading amount is 10 g/L; the third coating is CuO or MnO2The loading amount is 10 g/L; the fourth coating is CuO or MnO2Pt and Pd, the loading amount is 3 g/L.
The preparation method comprises four steps, wherein in the first step, alumina, silicon dioxide and CeO are mixed2、ZrO2With Bi2O3Calculated Bi (NO)3)3Mixing the solution with water according to the mass ratio of 1: 0.05-0.5: 0.2-0.5: 0.1-0.2, uniformly stirring, uniformly mixing and stirring, ball-milling the solution for 2 hours, adjusting the pH value to 2.0-2.5 by using nitric acid to prepare solution A, coating the solution A on cordierite honeycomb ceramic, blowing off redundant solution on pore channels and the outer wall of a carrier, drying for 1 hour at 120 ℃, heating to 550 ℃, calcining for 2 hours, cooling and taking out; second step of processing CeO2、ZrO2、La2O3Cu (NO) calculated as CuO3)2With MnO2Calculated Mn (NO)3)2Uniformly stirring a solution prepared according to the mass ratio of 1: 0.1-0.5: 1-2: 0.1-1, uniformly mixing with water, uniformly stirring, ball-milling the solution for 2 hours, adjusting the pH value to 2.0-2.5 by using nitric acid to obtain a solution B, coating the solution B on the carrier prepared in the first step, blowing off the redundant solution on the pore channel and the outer wall of the carrier, drying at 120 ℃ for 1 hour, heating to 550 ℃, calcining for 2 hours, cooling and taking out; the third step is to calculate Cu (NO) as CuO3)2Solution, MnO2Calculated Mn (NO)3)2Preparing the solution into a solution according to the mass ratio of 1: 0.1-1, mixing the solution with water, uniformly stirring, adjusting the pH value to 2.0-2.5 by using nitric acid to obtain a solution C, soaking the carrier prepared in the second step into the solution C, blowing off the redundant solution on the pore channel and the outer wall of the carrier, drying at 120 ℃ for 1 hour, heating to 550 ℃, calcining for 2 hours, cooling and taking out; the fourth step is to calculate Cu (NO) as CuO3)2Solution with MnO2Calculated Mn (NO)3)2Solution, platinum nitrate solution calculated by Pt and palladium nitrate solution calculated by Pd in a mass ratio of 1: 0.1-1: 0.05-0.1: 0.05 ∞0.1, uniformly stirring with water, adjusting the pH value to 2.0-2.5 by using nitric acid to obtain a solution D, soaking the carrier prepared in the third step into the solution D, blowing off redundant solution on pore channels and the outer wall of the carrier, drying for 1 hour at 120 ℃, heating to 550 ℃, calcining for 2 hours, cooling and taking out to obtain the catalyst.
The organic waste gas purifying catalyst and the preparation method thereof provided by the invention have the advantages that: the catalyst has simple preparation process, high catalyst activity and long service life, is particularly suitable for the catalytic purification treatment of nitrile-containing organic waste gas, and can effectively remove the nitrile-containing organic waste gas.
Detailed Description
Example 1
Weighing alumina, silica and CeO2、ZrO2With Bi2O3Calculated Bi (NO)3)3133.3g of alumina, 13.33g of silicon dioxide and CeO calculated according to the mass ratio of 1: 0.1: 0.2: 0.12(26.66g)、ZrO2(13.33g)、Bi(NO3)3Solution (containing Bi)2O313.33g), uniformly stirring, uniformly mixing with 1400g of water, uniformly stirring, ball-milling the solution for 2 hours, and adjusting the pH value to 2.0-2.5 by using nitric acid to prepare a solution A; CeO is weighed2、ZrO2、La2O3Cu (NO) calculated as CuO3)2With MnO2Calculated Mn (NO)3)2CeO according to the mass ratio of 1: 0.1: 2: 0.32(28.57g)、ZrO2(2.86g)、La2O3(2.86g)、Cu(NO3)2(containing CuO 57.14g), Mn (NO)3)2(containing MnO)28.57g), mixing with 1500g of water, stirring uniformly, ball-milling the solution for 2 hours, and adjusting the pH value to 2.0-2.5 by using nitric acid to obtain a solution B; weighing Cu (NO)3)2Solution (containing CuO 83.33g), Mn (NO)3)2Solution (containing MnO)216.67g) is prepared into a solution, the solution is mixed with 1500g of water and then stirred evenly, and nitric acid is used for adjusting the pH value to 2.0-2.5 to prepare a solution C; weighing Cu (NO)3)2Solution (containing CuO 25.00g), Mn (NO) in Mn3)2Solution (containing MnO)22.50g), a platinum nitrate solution (containing 1.25g of Pt), and a palladium nitrate solution (containing 1.25g of Pd) were mixed, and after uniformly stirring the mixture with 1470g of water, the pH was adjusted to 2.0 to 2.5 with nitric acid to obtain a solution D.
Taking 10 liters of cordierite honeycomb ceramic carrier, the external dimension is 100 multiplied by 50mm, the open pore number is 200 pores/in2The carrier was purged with 0.05MPa of compressed air to remove powder and dust from the surface, and was kept in reserve after 10 minutes of purging. Firstly, dipping the dedusted cordierite honeycomb ceramic into the solution A, taking out, blowing off redundant solution on a pore channel and the outer wall of a carrier by using compressed air, drying for 1 hour at 120 ℃, heating to 550 ℃, calcining for 2 hours, cooling and taking out; then coating the solution B on the carrier prepared in the first step, blowing off redundant solution on the pore channel and the outer wall of the carrier by using compressed air, drying for 1 hour at 120 ℃, heating to 550 ℃, calcining for 2 hours, cooling and taking out; then dipping the carrier prepared in the second step into the solution C, blowing off redundant solution on the pore channel and the outer wall of the carrier, drying for 1 hour at 120 ℃, heating to 550 ℃, calcining for 2 hours, cooling and taking out; and then soaking the carrier prepared in the third step into the solution D, blowing off redundant solution on the pore channel and the outer wall of the carrier, drying for 1 hour at 120 ℃, heating to 550 ℃, calcining for 2 hours, cooling and taking out to obtain the catalyst. Respectively using the mixed gas of acrylonitrile, benzene, HCN and air as the simulated gas at the airspeed of 15000h-1The conversion of organic substances and the conversion of CN bonds to N were investigated2The selectivity and the catalyst activity evaluation results are shown in Table 1.
Example 2
The same preparation method as in example 1 was used except that the CuO content was increased by 1 time and the contents of the noble metals Pt and Pd were increased by 1 time per liter of the catalyst prepared, the catalyst activity evaluation conditions were the same as in example 1, and the catalyst activity evaluation results are shown in Table 2.
Example 3
The same preparation method as in example 1 was used except that the CuO content per liter of the catalyst prepared was reduced by 50%, the catalyst activity evaluation conditions were the same as in example 1, and the catalyst activity evaluation results are shown in Table 3.
Therefore, the catalyst has the characteristics of high conversion rate of simulated organic waste gas, high selectivity of conversion of CN bonds into N2, good catalytic effect, simple process, high activity of the prepared catalyst and the like, and the catalytic performance of the catalyst in example 2 is superior to that of the other two examples.
Claims (2)
1. A nitrile-containing organic waste gas purification catalyst is characterized in that: the catalyst is formed by coating a first coating, a second coating, a third coating and a fourth coating on cordierite honeycomb ceramic serving as a main carrier, wherein the first coating is Al2O3、SiO2、CeO2、ZrO2、Bi2O3The loading amount is 20 g/L; the second coating is CeO2、ZrO2、La2O3、CuO、MnO2The loading amount is 10 g/L; the third coating is CuO or MnO2The loading amount is 10 g/L; the fourth coating is CuO or MnO2Pt and Pd, the loading amount is 3 g/L.
2. The method for preparing a nitrile-containing organic exhaust gas purifying catalyst according to claim 1, wherein: the preparation steps comprise four steps, wherein in the first step, alumina, silica and CeO are mixed2、ZrO2With Bi2O3Calculated Bi (NO)3)3The solution is mixed according to the mass ratio of 1: 0.05-0.5: 0.2-0.5: 0.1-0.2Uniformly stirring, mixing with water, uniformly stirring, ball-milling the solution for 2 hours, adjusting the pH value to 2.0-2.5 by using nitric acid to obtain a solution A, coating the solution A on cordierite honeycomb ceramic, blowing off redundant solutions on pore channels and the outer wall of a carrier, drying at 120 ℃ for 1 hour, heating to 550 ℃, calcining for 2 hours, cooling and taking out; second step of processing CeO2、ZrO2、La2O3Cu (NO) calculated as CuO3)2With MnO2Calculated Mn (NO)3)2Uniformly stirring a solution prepared according to the mass ratio of 1: 0.1-0.5: 1-2: 0.1-1, uniformly mixing with water, uniformly stirring, ball-milling the solution for 2 hours, adjusting the pH value to 2.0-2.5 by using nitric acid to obtain a solution B, coating the solution B on the carrier prepared in the first step, blowing off the redundant solution on the pore channel and the outer wall of the carrier, drying at 120 ℃ for 1 hour, heating to 550 ℃, calcining for 2 hours, cooling and taking out; the third step is to add Cu (NO)3)2Solution, Mn (NO)3)2Uniformly stirring a solution C prepared by the solution and water according to a mass ratio, adjusting the pH value to 2.0-2.5 by using nitric acid to obtain the solution C, soaking the carrier prepared in the second step into the solution C, blowing off redundant solutions on a pore channel and the outer wall of the carrier, drying for 1 hour at 120 ℃, heating to 550 ℃, calcining for 2 hours, and cooling and taking out; the fourth step is to treat Cu (NO)3)2Solution, Mn (NO)3)2And (2) uniformly stirring the solution, the platinum nitrate solution, the palladium nitrate solution and the solution C prepared by water according to the mass ratio, adjusting the pH value to 2.0-2.5 by using nitric acid to prepare a solution D, soaking the carrier prepared in the third step into the solution D, blowing off the redundant solution of the pore channel and the outer wall of the carrier, drying at 120 ℃ for 1 hour, heating to 550 ℃, calcining for 2 hours, cooling and taking out to obtain the catalyst.
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