CN110721736A - Preparation method and application of sulfur-resistant composite catalyst for removing nitric oxide in motor vehicle exhaust - Google Patents
Preparation method and application of sulfur-resistant composite catalyst for removing nitric oxide in motor vehicle exhaust Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 12
- 239000011593 sulfur Substances 0.000 title claims abstract description 12
- 239000002131 composite material Substances 0.000 title claims description 41
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 53
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052802 copper Inorganic materials 0.000 claims abstract description 49
- 239000010949 copper Substances 0.000 claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 24
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical group [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 21
- 239000007789 gas Substances 0.000 abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010457 zeolite Substances 0.000 abstract description 7
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001000 nickel titanium Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002779 inactivation Effects 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
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01D2251/00—Reactants
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- B01D2251/2062—Ammonia
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Abstract
The invention discloses a method for selective catalytic reduction of Nitrogen Oxides (NO) by ammonia under the condition of sulfur in tail gas of a motor vehiclex) A method for preparing the catalyst. The invention utilizes the sol precursor of the metal oxide component to compound on the copper-containing zeolite molecular sieve catalyst by an impregnation method to obtain the copper-containing molecular sieve-metal oxide compound catalyst. The catalyst is applied to the selective catalytic reduction reaction of ammonia gas, realizes the high-efficiency catalytic reduction of nitrogen oxides into harmless nitrogen gas in a wide temperature window, has better sulfur dioxide poisoning resistance, and has simple preparation method and good application prospect.
Description
Technical Field
The invention relates to a preparation and application of a sulfur-resistant catalyst for selectively reducing nitrogen oxides by ammonia gas, in particular to a catalyst for efficiently reducing nitrogen oxides by ammonia gas to generate nitrogen gas after a copper-containing zeolite molecular sieve is compounded with metal oxides under the condition of sulfur in tail gas of a motor vehicle.
Background
Nitrogen Oxides (NO)x) Is one of the main pollutants in the atmosphere, can not only cause acid rain, photochemical smog and ozone layerDamage and the like, and can seriously harm the life and health on the earth. NOxThe generation mechanism of (1) is mainly high-temperature combustion of nitrogen-containing species, and the sources are natural sources and artificial sources. Artificial sources can be divided into stationary sources and mobile sources according to the discharge pattern: the fixed source is mainly combustion of fuel of industrial boilers and coal-fired power plants; the mobile source is mainly the tail gas emission of various motor vehicles with fuel engines. How to effectively remove NO generated by the two types of emission sourcesxHas become a global issue. The most effective method for removing nitrogen oxides at present is the selective catalytic reduction method of ammonia gas (English NH)3-Selective Catalytic Reduction, NH3-SCR)
Vanadium-based NH most widely applied in the fourth and fifth stages of China3The SCR catalyst has poor low-temperature catalytic performance, low nitrogen selectivity and the problem that vanadium has biotoxicity, is easy to cause environmental pollution and the like, and is difficult to reach the six-emission standard to be implemented. For this case, zeolite molecular sieve NH loaded with metal ions3SCR catalysts have become a research hotspot. The copper-exchanged zeolite molecular sieve catalyst is reported in patents and literatures, and a Chinese patent (CN109126862A) in 2019 reports that a CHA zeolite molecular sieve loaded with copper is applied to an ammonia selective catalytic reduction reaction, so that the NO conversion rate of the catalyst can reach 100% at 200 ℃, but the NO conversion rate is lower than 50% at a low temperature range of 100-150 ℃. In practical application, the temperature of an automobile engine is low during cold start, and the activity of the Cu-CHA catalyst is difficult to meet the requirement of removing NOx at the stage. In another aspect, the metal oxide is applied to NH3SCR reactions have been reported in many documents. For example: 2011 of a chinese patent (CN103182312A) reports that when manganese-based transition metal oxide catalyzes the reaction, the NO conversion rate can reach 70% at 80 ℃, and the low-temperature reaction performance is very excellent. However, the high temperature activity of manganese-based metal oxides is poor (catalysis today, 2011, 175: 147-156), and the catalyst is rapidly deactivated in the presence of trace amounts of sulfur.
Although the sulfur content of current motor vehicle fuels is low (less than 10ppm) after the six standards of the state of imminent implementation, very little SO is generated after combustion2Can be aligned after long-time operation accumulationMultiple SCR catalysts cause strong poisoning. The study by Zhou et al found that Cu-SSZ-13 zeolite is responsible for SO2Extremely sensitive, only 10ppm SO at 155 deg.C2The NO conversion rate of the Cu-SSZ-13 catalyst is reduced from 100 percent to 40 percent within 30 hours, and SO is generated2The higher the concentration, the faster the inactivation (ChemCatchem,2018, 10: 5182-. There are reports in the literature that metal oxide catalysts have better SO resistance2Properties, e.g. Co-or Ni-doped MnOx-CeO2The catalyst was heated at 175 ℃ with 150ppm SO2The activity decreased from 100% to about 80%, but the high temperature activity was still very low (chemical engineering Journal,2017, 317: 20-31).
In conclusion, the Cu-SSZ-13 has better reaction performance at present, but has the defects of low-temperature activity and SO resistance2The problem of poor poisoning performance; the doped metal oxide catalyst has a certain sulfur resistance, but the high-temperature activity is not good enough. Thus, an environmentally friendly process was developed with high NH over a wide temperature window3SCR catalytic performance and good SO resistance2Poisoning performance of catalysts is a difficult point of current research.
Disclosure of Invention
The invention relates to a method for selective catalytic reduction of Nitrogen Oxides (NO) by ammonia under the condition of sulfur in motor vehicle exhaustx) Preparation method of copper-containing molecular sieve-metal oxide composite catalyst and application of copper-containing molecular sieve-metal oxide composite catalyst in selective catalytic reduction reaction of nitrogen oxide by ammonia gas, and catalyst is used for efficiently catalytically reducing Nitrogen Oxide (NO) in wide temperature windowx) And the temperature of the wide temperature window is 100-650 ℃.
The invention utilizes the sol precursor of the metal oxide component to compound on the copper-containing zeolite molecular sieve catalyst by an impregnation method to obtain the copper-containing molecular sieve-metal oxide compound catalyst. The catalyst is applied to the selective catalytic reduction reaction of ammonia gas, realizes the high-efficiency catalytic reduction of nitrogen oxides into harmless nitrogen gas in a wide temperature window, has better sulfur dioxide poisoning resistance, and has simple preparation method and good application prospect.
The invention provides a method for efficiently catalyzing and reducing Nitrogen Oxide (NO) in a wide temperature windowx) And has better resistance to sulfur dioxide (SO)2) The preparation method of the copper-containing molecular sieve-metal oxide composite catalyst comprises the steps of preparing metal oxide by using metal salt as a precursor, and compounding the metal oxide and a copper-containing molecular sieve according to the mass ratio of 1 (3-7) to prepare the copper-containing molecular sieve-metal oxide composite catalyst.
According to the above technical solution, preferably, the catalyst is a copper-containing molecular sieve-metal oxide composite catalyst, and the metal salt precursor is a metal nitrate, including: manganese nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, etc.; in the process of preparing the metal oxide by using the metal salt precursor, a titanium source reagent is used, and the titanium source reagent is tetraethyl titanate, tetrabutyl titanate, titanium isopropoxide and the like.
According to the technical scheme, the catalyst is preferably a copper-containing molecular sieve-metal oxide composite catalyst, the copper content of the copper-containing molecular sieve is 1-3% by mass, and the structure of the copper-containing molecular sieve is CHA, MFI, BEA type molecular sieve and the like.
According to the technical scheme, the catalyst is preferably a copper-containing molecular sieve-metal oxide composite catalyst, and the composite catalyst is prepared by a precipitation method, a sol-impregnation method, a mechanical mixing method and the like.
According to the technical scheme, the catalyst is preferably a copper-containing molecular sieve-metal oxide composite catalyst, and the preparation process of the composite catalyst comprises a roasting process, wherein the roasting temperature is 420-600 ℃, the time is 5-24 hours, and the pressure is 10-1 × 105Pa。
According to the above technical solution, preferably, the catalyst is a copper-containing molecular sieve-metal oxide composite catalyst, and the preparation method of the composite catalyst comprises the following steps:
(1) dissolving metal nitrate and a titanium source in a molar ratio of 1: 5-10 of metal elements to titanium elements in an ethanol/water mixed solution, adding acid to adjust the pH value to 1-4, and stirring at 15-30 ℃ for 4-12 hours to prepare metal oxide sol;
wherein the volume ratio of ethanol to water in the ethanol/water mixed solution is 1: 5-10;
(2) performing ion exchange on 0.01-0.1 mol/L copper acetate solution and a molecular sieve carrier at 30-70 ℃ for 2-6 h, performing suction filtration and washing, drying at 80-110 ℃ for 20-24 h, and then roasting at 400-600 ℃ for 5-8 h to obtain a copper-containing molecular sieve;
(3) and (2) soaking the metal oxide sol prepared in the step (1) on the copper-containing molecular sieve prepared in the step (2) according to the mass ratio of oxides 1 to 3 to 7, drying at 80 to 110 ℃ for 20 to 24 hours, and then roasting at 400 to 600 ℃ for 5 to 8 hours to obtain the copper-containing molecular sieve-metal oxide composite catalyst.
The invention also relates to the application of the copper-containing molecular sieve-metal oxide composite catalyst prepared by the method in the selective catalytic reduction reaction of ammonia.
According to the technical scheme, the composite catalyst containing the copper molecular sieve and the metal oxide is preferably applied to the selective catalytic reduction reaction of ammonia, and further comprises a pretreatment process, wherein the treatment atmosphere is one of argon, nitrogen, helium and air, the treatment temperature is 180-600 ℃, the treatment time is 2-6 h, and the temperature programming rate is 5-15 ℃/min.
According to the technical scheme, the copper-containing molecular sieve-metal oxide composite catalyst is preferably applied to the selective catalytic reduction reaction of ammonia gas, and the reaction gas components are NO and NH3(NO and NH)3In a molar ratio of 1: 1) the volume fraction of oxygen is 5-10%, H22-5% of O by volume and CO20-15% of SO 20 to 50 ppm.
According to the above technical solution, preferably, the NO, NH3And the amount of the catalyst is 1 mol: 1 mol: (0.05-1 g).
According to the technical scheme, the copper-containing molecular sieve-metal oxide composite catalyst is preferably subjected to selective catalytic reduction in ammonia gasThe application in the reaction is that the reaction temperature is 100-650 ℃, and preferably 150-600 ℃; the reaction pressure is 0.1-0.5 MPa, preferably 0.1-0.3 MPa; the airspeed is 20000-160000 h-1Preferably 50000-100000 h-1。
The application conditions of the catalyst of the invention are as follows: adopting air, nitrogen, argon or helium for pretreatment, wherein the treatment temperature is 180-600 ℃, the treatment time is 2-6 h, and the programmed heating rate is 5-15 ℃/min; the reaction gas has NO and NH components3NO and NH3The molar ratio of (A) to (B) is 1, the volume fraction of oxygen is 5-10%, and H is22-5% of O by volume and CO20-15% of SO2The volume fraction is 0-50 ppm. The reaction temperature is 100-650 ℃, and preferably 150-600 ℃; the reaction pressure is 0.1-0.5 MPa, preferably 0.1-0.3 MPa; the airspeed is 20000-160000 h-1Preferably 50000-100000 h-1。
The invention has the following advantages:
from the catalyst preparation aspect: the catalyst is simple in preparation method, easy to operate and good in application prospect.
From the application aspect in the selective catalytic reduction reaction of ammonia: the catalyst has the reaction advantages of both copper-containing molecular sieve and metal oxide catalyst, and has high reaction activity, N2Optionally, 50ppm SO in simulated motor vehicle exhaust2After long-time operation, the NO removal rate is still over 71 percent, and the stability and the sulfur resistance of the catalyst are excellent.
Drawings
Fig. 1 is an XRD spectrum of a composite catalyst composed of different oxide species.
Fig. 2 shows the reactivity of a composite catalyst composed of different oxide species.
FIG. 3 shows SO resistance of composite catalysts composed of different oxide species2Poisoning action.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Examples
As described in detail below with respect to the whole process by way of examples, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
1. Preparation of copper-containing molecular sieve-metal oxide composite catalyst
Example 1
0.25g of copper acetate is taken and dissolved in 50ml of deionized water, then 2.5g H-SSZ-13 molecular sieve (CHA structure, provided by catalyst works of southern Kaiki university) is added, ion exchange is carried out for 4h at 40 ℃, then the obtained sample is filtered, washed by deionized water, dried for 24h at 110 ℃, finally, the sample is put into a muffle furnace and roasted for 5h at 550 ℃, and the Cu-SSZ-13 molecular sieve is obtained. The copper mass content measured by ICP was 2.0%, and the XRD spectrum in FIG. 1 shows that the Cu-SSZ-13 molecular sieve has good CHA structure and crystallinity.
Example 2
0.144g of manganese nitrate tetrahydrate is dissolved in 0.2ml of ethanol and is uniformly stirred, 1.95ml of n-butyl titanate is uniformly stirred with 1ml of ethanol and 1ml of deionized water, nitric acid is added to adjust the pH value to 2, and the mixture is continuously stirred to form sol. The sol was then impregnated into 2.5g of the Cu-SSZ-13 molecular sieve catalyst prepared in example 1, dried at 110 ℃ for 24 hours, and calcined at 540 ℃ for 5 hours to obtain a copper-containing molecular sieve-metal oxide composite catalyst, designated as ex-1-MnTi, whose XRD spectrum is shown in FIG. 1, where only the characteristic diffraction peak of the CHA structure was observed, indicating that the metal oxide component was uniformly dispersed on the Cu-SSZ-13 molecular sieve.
Example 3
0.167g of cobalt nitrate hexahydrate is dissolved in 0.2ml of ethanol and stirred uniformly, 1.95ml of n-butyl titanate is stirred uniformly with 1ml of ethanol and 1ml of deionized water, nitric acid is added to adjust the pH value to 2, and stirring is continued to form sol. The sol was then impregnated into 2.5g of the Cu-SSZ-13 molecular sieve catalyst prepared in example 1, dried at 110 ℃ for 24 hours, and calcined at 560 ℃ for 5 hours to obtain a copper-containing molecular sieve-metal oxide composite catalyst, designated as ex-2-CoTi, whose XRD spectrum is shown in FIG. 1, where only the characteristic diffraction peak of the CHA structure was observed, indicating that the metal oxide component was uniformly dispersed on the Cu-SSZ-13 molecular sieve.
Example 4
0.167g of nickel nitrate hexahydrate is dissolved in 0.2ml of ethanol and is evenly stirred, 1.95ml of n-butyl titanate is evenly stirred with 1ml of ethanol and 1ml of deionized water, nitric acid is added to adjust the pH value to 2, and the mixture is continuously stirred to form sol. The sol was then impregnated into 2.5g of the Cu-SSZ-13 molecular sieve catalyst prepared in example 1, dried at 110 ℃ for 24 hours, and calcined at 540 ℃ for 5 hours to obtain a copper-containing molecular sieve-metal oxide composite catalyst, designated as ex-3-NiTi, whose XRD spectrum is shown in FIG. 1, where only the characteristic diffraction peak of the CHA structure was observed, indicating that the metal oxide component was uniformly dispersed on the Cu-SSZ-13 molecular sieve.
Example 5
0.171g of zinc nitrate hexahydrate is dissolved in 0.2ml of ethanol and is uniformly stirred, 1.95ml of n-butyl titanate is uniformly stirred with 1ml of ethanol and 1ml of deionized water, nitric acid is added to adjust the pH value to 2, and the stirring is continued to form sol. And then dipping the sol into 2.5g of the Cu-SSZ-13 molecular sieve catalyst prepared in the previous step, drying for 24h at 110 ℃, and roasting for 5h at 560 ℃ to obtain the copper-containing molecular sieve-metal oxide composite catalyst, which is marked as ex-4-ZnTi, wherein an XRD (X-ray diffraction) spectrum of the copper-containing molecular sieve-metal oxide composite catalyst is shown in figure 1, and only a characteristic diffraction peak of a CHA structure can be observed, which indicates that the metal oxide component is uniformly dispersed on the Cu-SSZ-13 molecular sieve.
2. Application of copper-containing molecular sieve-metal oxide composite catalyst in selective catalytic reduction reaction of ammonia gas all reaction examples are carried out in a normal-pressure miniature fixed bed reactor, and the device is provided with a gas distribution system and an online nitrogen oxide analyzer. Except where otherwise specified, NO and NH3Has a concentration of 500ppm and an oxygen proportion of 10%, H2The O content was 5%. Nitrogen oxide concentration analysis was measured using a german mock S710 and switzerland ECO analyzer.
Example 6
Catalytic evaluation experiment of Cu-SSZ-13 prepared in example 1 was carried out in a fixed bed reactor under normal pressure, in which 0.1g of the catalyst was weighed out and N was added2Heating to 300 deg.C at 2 deg.C/min, purging for 2 hr, cooling to room temperature, and introducingReactor, 0.15MPa, airspeed 80000h-1And the reaction outlet line is kept at a constant temperature of 150 ℃, and all the collected nitric oxide is detected. The temperature is raised to 150-600 ℃ for reaction, and the result is shown in FIG. 2. anti-SO2At the time of performance test, at N2Heating to 300 deg.C at 2 deg.C/min, purging for 2 hr, cooling to room temperature, and introducing reaction gases NO and NH3Each 500ppm, 10% by volume of oxygen, H2Volume fraction of O5%, CO2Volume fraction of 10%, SO250ppm, 0.15MPa, space velocity 80000h-1And the outlet of the reaction line was thermostated at 250 ℃ and all the nitric oxide collected was detected, the results being shown in FIG. 3.
Example 7
Experiment for evaluating ex-2-MnTi catalyst prepared in example 2 in a fixed bed reactor at normal pressure, 0.1g of the catalyst was weighed out in N2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, introducing into the reactor at 0.15MPa and at an airspeed of 80000h-1And the reaction outlet line is kept at a constant temperature of 150 ℃, and all the collected nitric oxide is detected. The temperature is raised to 150-600 ℃ for reaction, and the result is shown in FIG. 2. anti-SO2At the time of performance test, with N2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, and introducing reaction gases NO and NH3Each 500ppm, 10% by volume of oxygen, H2Volume fraction of O5%, CO2Volume fraction of 10%, SO250ppm, 0.15MPa, space velocity 80000h-1And the outlet of the reaction line was thermostated at 250 ℃ and all the nitric oxide collected was detected, the results being shown in FIG. 3.
Example 8
Experiment for evaluating ex-3-CoTi catalyst in example 3 in a fixed bed reactor under normal pressure, 0.1g of the catalyst was weighed out and used as N2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, introducing into the reactor at 0.15MPa and at an airspeed of 80000h-1And the reaction outlet line is kept at a constant temperature of 150 ℃, and all the collected nitric oxide is detected. The temperature is raised to 150-600 ℃ for reaction, and the result is shown in FIG. 2. anti-SO2At the time of performance test, with N2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, and introducing reaction gases NO and NH3Each 500ppm, 8% by volume of oxygen, H2 O volume fractionNumber 4%, CO2Volume fraction of 12%, SO250ppm, 0.15MPa, space velocity 80000h-1And the outlet of the reaction line was thermostated at 250 ℃ and all the nitric oxide collected was detected, the results being shown in FIG. 3.
Example 9
Example 4 Ex-4-NiTi catalytic evaluation test in the preparation of a fixed bed reactor under normal pressure, 0.1g of the catalyst was weighed out and N was added2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, introducing into the reactor at 0.15MPa and at an airspeed of 80000h-1And the reaction outlet line is kept at a constant temperature of 150 ℃, and all the collected nitric oxide is detected. The temperature is raised to 150-600 ℃ for reaction, and the result is shown in FIG. 2. anti-SO2At the time of performance test, with N2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, and introducing reaction gases NO and NH3500ppm of (C), oxygen volume fraction of 8%, H2 O volume fraction 4%, CO2Volume fraction of 12%, SO250ppm, 0.15MPa, space velocity 80000h-1And the outlet of the reaction line was thermostated at 250 ℃ and all the nitric oxide collected was detected, the results being shown in FIG. 3.
Example 10
Experiment for catalytic evaluation of ex-5-ZnTi obtained in example 5 in a fixed bed reactor at atmospheric pressure, using N2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, introducing into the reactor at 0.15MPa and at an airspeed of 80000h-1And the reaction outlet line is kept at a constant temperature of 150 ℃, and all the collected nitric oxide is detected. The temperature is raised to 150-600 ℃ for reaction, and the result is shown in FIG. 2. anti-SO2At the time of performance test, with N2Heating to 300 ℃ at 2 ℃/min, purging for 2h, cooling to room temperature, and introducing reaction gases NO and NH3500ppm of (C), oxygen volume fraction of 8%, H2 O volume fraction 4%, CO2Volume fraction of 12%, SO250ppm, 0.15MPa, space velocity 80000h-1And the outlet of the reaction line was thermostated at 250 ℃ and all the nitric oxide collected was detected, the results being shown in FIG. 3.
As can be seen from FIG. 2, the NO conversion rate of the copper-containing molecular sieve-metal oxide composite catalyst is greater than 70% in the wide temperature window range of 150-550 ℃, and good effect in the wide temperature window is achievedNH of (2)3-SCR catalytic activity. As shown in FIG. 3, 50ppm SO was introduced into the copper-containing molecular sieve-metal oxide composite catalyst at 250 deg.C2After 20h of poisoning, the NO conversion rate of the Cu-SSZ-13 is reduced from 100% to 66%, and the final NO conversion rates of the composite catalysts are all over 71%. The combination of reactivity (FIG. 2) and sulfur resistance (FIG. 3) in the whole temperature window is considered to obtain Cu-SSZ-13-ZnTiOxThe catalytic performance of (2) is optimal. This indicates that the composite catalyst is indeed capable of increasing the SO resistance2Poisoning properties. Therefore, the copper-containing molecular sieve-metal oxide composite catalyst can have high NH in a wide temperature window3SCR activity and better SO resistance2The performance is expected to replace the existing catalytic system, and the application prospect is good.
Claims (10)
1. The preparation method of the sulfur-resistant copper-containing molecular sieve-metal oxide composite catalyst for catalytic reduction of nitrogen oxides in motor vehicle exhaust is characterized by preparing metal oxide by using metal salt as a precursor, and compounding the metal oxide and a copper-containing molecular sieve according to a mass ratio of 1: 3-7 to prepare the copper-containing molecular sieve-metal oxide composite catalyst.
2. The method according to claim 1, wherein the metal salt precursor is a metal nitrate; in the process of preparing the metal oxide by using the metal salt precursor, the used titanium source is tetraethyl titanate, tetrabutyl titanate or titanium isopropoxide, and the used solvent is a mixed solution of ethanol and water.
3. The method of claim 1, wherein the copper-containing molecular sieve has a copper content of 1-3% by mass and a structure of CHA, MFI or BEA type molecular sieve.
4. The method according to claim 1, wherein the composite catalyst is prepared by a precipitation method, a sol-impregnation method, or a mechanical mixing method.
5. As claimed in claim 1The preparation method is characterized in that the preparation process of the composite catalyst comprises a roasting process, wherein the roasting temperature is 420-600 ℃, the time is 5-24 hours, and the pressure is 10-1 multiplied by 105Pa。
6. The method of claim 1, comprising the steps of:
(1) dissolving metal nitrate and a titanium source in a molar ratio of 1: 5-10 of metal elements to titanium elements in an ethanol/water mixed solution, adding acid to adjust the pH value to 1-4, and stirring at 15-30 ℃ for 4-12 hours to prepare metal oxide sol;
wherein the volume ratio of ethanol to water in the ethanol/water mixed solution is 1: 5-10;
(2) performing ion exchange on 0.01-0.1 mol/L copper acetate solution and a molecular sieve carrier at 30-70 ℃ for 2-6 h, performing suction filtration and washing, drying at 80-110 ℃ for 20-24 h, and then roasting at 400-600 ℃ for 5-8 h to obtain a copper-containing molecular sieve;
(3) and (2) soaking the metal oxide sol prepared in the step (1) on the copper-containing molecular sieve prepared in the step (2) according to the mass ratio of oxides contained in the metal oxide sol to obtain a copper-containing molecular sieve-metal oxide composite catalyst, drying the copper-containing molecular sieve sol at the temperature of 80-110 ℃ for 20-24 h, and roasting the dried copper-containing molecular sieve sol at the temperature of 400-600 ℃ for 5-8 h.
7. The use of the composite catalyst containing copper molecular sieve-metal oxide of claim 1 in ammonia selective catalytic reduction of nitrogen oxides.
8. The application of claim 7, wherein the composite catalyst further comprises a pretreatment process, the treatment atmosphere is one of argon, nitrogen, helium and air, the treatment temperature is 180-600 ℃, the treatment time is 2-6 h, and the temperature rise rate is 5-15 ℃/min.
9. The use according to claim 7, wherein the reaction gas components NO and NH3In a molar ratio of 1: 1, oxygen volume fraction of 5-10%, H2Volume of O2-5% of CO20-15% of SO2The volume fraction is 0-50 ppm.
10. The method of claim 7, wherein the reaction temperature is 100-650 ℃, the reaction pressure is 0.1-0.5 MPa, and the space velocity is 20000-160000 h-1。
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