CN112275314A - Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof - Google Patents
Manganese-cerium-based molecular sieve SCR denitration catalyst and preparation method thereof Download PDFInfo
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- CN112275314A CN112275314A CN202010959937.7A CN202010959937A CN112275314A CN 112275314 A CN112275314 A CN 112275314A CN 202010959937 A CN202010959937 A CN 202010959937A CN 112275314 A CN112275314 A CN 112275314A
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- molecular sieve
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- scr denitration
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 103
- WYCDUUBJSAUXFS-UHFFFAOYSA-N [Mn].[Ce] Chemical compound [Mn].[Ce] WYCDUUBJSAUXFS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 36
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 30
- 239000000919 ceramic Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims description 41
- 239000011572 manganese Substances 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 18
- 238000005342 ion exchange Methods 0.000 claims description 17
- 229910052878 cordierite Inorganic materials 0.000 claims description 15
- 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 group [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 description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 150000002696 manganese Chemical class 0.000 claims description 8
- 150000000703 Cerium Chemical class 0.000 claims description 6
- 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 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 abstract description 17
- 239000011593 sulfur Substances 0.000 abstract description 17
- 229910001868 water Inorganic materials 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- -1 cerium modified molecular sieve Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical class [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 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
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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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
- B01J37/08—Heat treatment
-
- 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
- B01J37/30—Ion-exchange
-
- 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
- B01D2258/0283—Flue gases
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- Chemical & Material Sciences (AREA)
- 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)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a manganese-cerium-based molecular sieve SCR denitration catalyst, which comprises a porous ceramic carrier and a Mn-Ce-X modified molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the Mn-Ce-X modified molecular sieve is obtained by modifying Mn, Ce and X with an HZSM-5 carrier, the X is one or more selected from W, Mo, Co, Fe and Cr, and the Mn-Ce-X modified molecular sieve comprises the following components in parts by weight: molecular sieve: mn: ce: x1 wt.%: 0.2 wt.% to 10 wt.%: 0.2 wt.% to 10 wt.%: 0.1 wt.% to 10 wt.%. The catalyst obtained by the invention has the advantages of no toxicity and environmental protection, and has higher denitration efficiency under the conditions of low temperature, water content and sulfur content.
Description
Technical Field
The invention relates to an SCR denitration catalyst and a preparation method thereof, in particular to a manganese cerium-based molecular sieve SCR denitration catalyst and a preparation method thereof.
Background
Along with the rapid development of economy, the demand of people on the quality of life level is higher and higher, and health problems are more and more concerned by people. Atmospheric pollution not only brings serious harm to human health, but also has serious influence on the balance of the ecological environment. Our country is a coal burning large country, and 80% of coal is used for combustion to generate heat energy and power. After coal is combusted, a large amount of gas pollutants such as oxynitride, oxysulfide and the like are generated. The control technology of nitrogen oxides can be classified into a catalytic reduction method, a solid adsorption method, a liquid absorption method, a biochemical treatment technology and the like; the method can be divided into denitration before fuel combustion, control of combustion mode and denitration after combustion according to the treatment flow sequence. Among them, Selective Catalytic Reduction (SCR) has become the mainstream technology of denitration in our country because of its high denitration efficiency, good selectivity and high relative cost performance.
At present, vanadium-tungsten-titanium series catalysts are still the most widely applied SCR denitration catalysts in the fifth stage of diesel vehicle China, but the application temperature of the catalysts is higher, and the catalysts are generally required to be controlled at 300-400 ℃. The SCR device is generally installed in front of the desulfurization and dust removal device to avoid secondary heating of flue gas, but the flue gas at this stage has high concentration of sulfur oxides and dust, so that the catalyst is seriously deactivated. Therefore, the development of the low-temperature SCR catalyst has important significance.
Manganese-based denitration catalysts have received wide attention from researchers because of their particular low-temperature denitration activity. The manganese-based denitration catalyst has the advantages of low-temperature denitration activity due to multiple valence states and strong oxidation reduction capability.
In chinese patent application CN110694671A, maxiayu et al disclose a molecular sieve type SCR denitration catalyst synthesized by using natural diatomite, which is composed of active components and a carrier, and is characterized in that: the active components are metal elements Ce and Mn, the carrier is a pure silicon MCM-41 type molecular sieve prepared from natural diatomite, wherein the molar percentage is as follows: 20-30% of active component and 70-80% of carrier, wherein the molar ratio of metal element Ce to Mn in the active component is (0.125-0.25): 1. The denitration efficiency of the catalyst is 74.125% when the flue gas temperature is 175 ℃, and the denitration efficiency of the catalyst is 90.310% when the flue gas temperature is 200 ℃. The denitration efficiency of the catalyst is 92.380% when the flue gas temperature is 225 ℃. This document does not provide data on the high temperature hydrothermal aging regime as well as other temperatures.
Disclosure of Invention
In order to solve the technical problems, the invention provides a manganese-cerium-based molecular sieve SCR denitration catalyst, which comprises a porous ceramic carrier and a Mn-Ce-X modified molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the Mn-Ce-X modified molecular sieve is obtained by modifying an HZSM-5 carrier through Mn, Ce and X, the X is one or more selected from W, Mo, Co, Fe and Cr, and the Mn-Ce-X modified molecular sieve comprises the following components in parts by weight: molecular sieve: mn: ce: x1 wt.%: 0.2 wt.% to 10 wt.%: 0.2 wt.% to 10 wt.%: 0.1 wt.% to 10 wt.%.
Furthermore, the material of the porous ceramic carrier is cordierite, silicon carbide or aluminum silicate.
Further, the coating comprises a Mn-Ce-X modified molecular sieve and an auxiliary agent, and the coating amount of the coating is 30-300 g/L according to the solid content.
The invention also provides a preparation method of the manganese-cerium-based molecular sieve SCR denitration catalyst, which comprises the following steps of:
a. modification of a molecular sieve: adding a molecular sieve into a solution containing Mn, Ce and X, stirring uniformly, regulating the pH value of the mixed solution to be within the range of 2-7, carrying out ion exchange in a reaction kettle for 1-12 hours, washing and drying a solid product to obtain Mn-Ce-X modified molecular sieve powder, wherein X is one or more selected from W, Mo, Co, Fe and Cr;
b. preparing catalyst slurry: uniformly mixing Mn-Ce-X modified molecular sieve powder, alumina gel and deionized water to prepare a mixed solution A, wherein the solid content of the mixed solution A is controlled to be 5-50 wt%, and the solid-phase weight ratio of the alumina gel to the molecular sieve catalyst is controlled to be 0.1-10 wt%;
c. coating of molecular sieve catalyst: and c, coating the mixed solution A prepared in the step B on a porous ceramic carrier according to the coating amount of 30-300 g/L of the solid content to prepare a catalyst B, drying the catalyst B for 0.1-10 hours, and roasting for 0.1-10 hours to obtain the manganese cerium-based molecular sieve SCR denitration catalyst.
Further, the solution containing Mn, Ce and X comprises manganese salt and cerium salt, wherein the manganese salt is one or more of manganese acetate, manganese carbonate and manganese nitrate, and the cerium salt is one or more of cerium acetate, cerium nitrate and cerium sulfate.
Further, ion exchange in the step a is carried out on active components Mn and Ce at the same time, or two active components are subjected to two-step ion exchange, and the exchange sequence is not fixed.
Further, the coating method for coating the mixed solution a on the porous ceramic support in the step c is one or more of a dipping method, a vacuum suction method, and a spraying method.
Further, the roasting temperature in the step c is 400-700 ℃. C
Further, the drying temperature in the step c is 50-200 ℃. C
The invention also provides the cerium-based molecular sieve SCR denitration catalyst prepared by the preparation method of the cerium-based molecular sieve SCR denitration catalyst.
The invention adopts the process parameter control of ion exchange to fill the multi-metal ions in the defect positions of the molecular sieve, thereby obviously improving the stability of the molecular sieve catalyst. Meanwhile, the synergistic effect of the multi-metal active components is utilized, the active temperature window is widened, high activity and high selectivity in a low-temperature region can be realized, the sulfur resistance and water resistance are good, the environment is friendly, the cost is low, the operation is simple and convenient, and the method can be widely applied to the denitration of the tail gas of the diesel vehicle.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the catalyst obtained by the invention has the advantages of no toxicity and environmental protection, and has higher denitration efficiency under the conditions of low temperature, water content and sulfur content.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. The embodiments in the present invention, other embodiments obtained by persons skilled in the art without any inventive work, belong to the protection scope of the present invention.
The invention provides a water-resistant sulfur-resistant manganese-cerium-based molecular sieve SCR denitration catalyst, which comprises a porous ceramic carrier and a Mn-Ce-X modified molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the Mn-Ce-X modified molecular sieve is obtained by modifying an HZSM-5 carrier through Mn, Ce and X, X is one or more selected from W, Mo, Co, Fe and Cr, and the Mn-Ce-X modified molecular sieve comprises the following components in parts by weight: molecular sieve: mn: ce: x1 wt.%: 0.2 wt.% to 10 wt.%: 0.2 wt.% to 10 wt.%: 0.1 wt.% to 10 wt.%. The material of the porous ceramic carrier can be cordierite, silicon carbide or aluminum silicate. The coating comprises a Mn-Ce-X modified molecular sieve and an auxiliary agent, and the coating amount of the coating is 30-300 g/L. The auxiliary agent can be aluminum glue.
The preparation method of the water-resistant sulfur-resistant manganese-cerium-based molecular sieve SCR denitration catalyst comprises the following steps of:
a. modification of a molecular sieve: adding a molecular sieve into a solution containing Mn, Ce and X, stirring uniformly, regulating the pH value of the mixed solution to be within the range of 2-7, carrying out ion exchange in a reaction kettle for 1-12 hours, washing and drying a solid product to obtain Mn-Ce-X modified molecular sieve powder, wherein X is one or more selected from W, Mo, Co, Fe and Cr; the solution containing Mn, Ce and X comprises manganese salt and cerium salt, wherein the manganese salt is one or more of manganese acetate, manganese carbonate and manganese nitrate, and the cerium salt is one or more of cerium acetate, cerium nitrate and cerium sulfate. The ion exchange can be carried out by simultaneously exchanging the active components Mn and Ce, or can be carried out by two-step ion exchange of the two active components without fixing the exchange sequence.
b. Preparing catalyst slurry: uniformly mixing Mn-Ce-X modified molecular sieve powder, aluminum gel and deionized water to prepare a mixed solution A, wherein the content of a cured product of the solution A is controlled to be 5-50 wt%, and the solid-phase weight ratio of the aluminum gel to the molecular sieve catalyst in the cured product is controlled to be 0.1-10;
c. coating of molecular sieve catalyst: and c, coating the mixed solution A prepared in the step B on a porous ceramic carrier according to the coating amount of 30-300 g/L of the solid content to prepare a catalyst B, drying the catalyst B for 0.1-10 hours, and roasting for 0.1-10 hours to obtain the manganese cerium-based molecular sieve SCR denitration catalyst. The coating method used to coat the mixed solution a on the porous ceramic support may be one or more of a dipping method, a vacuum suction method, and a spraying method. The roasting temperature can be 400-700 ℃, and the material can be roasted in a roasting furnace. The drying temperature can be 50-200 deg.C. The invention also discloses a cerium-based molecular sieve SCR denitration catalyst prepared by the preparation method of the cerium-based molecular sieve SCR denitration catalyst.
The molecular sieve HZSM-5 is used as a carrier, and the HZSM-5 molecular sieve carrier is modified in advance by controlling the loading of active components such as manganese (Mn), cerium (Ce) oxide and one or more additives such as Fe, W, Mo, Co and Cr, so that a proper amount of metals such as the active components enter defect positions in the molecular sieve, and the structural stability of the molecular sieve catalyst can be obviously improved.
Example 1
A water-resistant sulfur-resistant manganese cerium-based molecular sieve SCR denitration catalyst comprises a porous ceramic carrier and a modified manganese cerium-based molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the molecular sieve catalyst comprises the following components in parts by weight: HZSM-5, Mn: Ce: 1 wt.% Fe, 5 wt.%: 2 wt.%.
A preparation method of a water-resistant and sulfur-resistant manganese-cerium-based molecular sieve SCR denitration catalyst comprises the following steps:
a. adding a molecular sieve HZSM-5 into a mixed solution containing Mn, Ce and Fe, regulating the pH value of the mixed solution to 10, carrying out ion exchange in a reaction kettle for 12 hours, and washing and drying a solid product to obtain manganese and cerium modified molecular sieve powder;
b. uniformly mixing the modified manganese-cerium-based molecular sieve catalyst powder, alumina gel and deionized water to prepare a mixed solution A with the solid content of 36 wt.%, wherein the weight ratio of the alumina gel to the molecular sieve powder in a cured product is 10, coating the mixed solution A on a porous cordierite carrier by adopting a vacuum suction method, and the coating amount of a catalyst coating is 200g/L according to the solid content.
c. And c, drying the porous cordierite carrier coated with the mixed solution A in the step b at 120 ℃ for 5 hours, and then roasting at 550 ℃ for 3 hours in an air atmosphere to obtain the Mn-Ce-Fe-HZSM-5 molecular sieve catalyst.
Example 2
A water-resistant sulfur-resistant manganese cerium-based molecular sieve SCR denitration catalyst comprises a porous ceramic carrier and a modified manganese cerium-based molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the molecular sieve catalyst comprises the following components in parts by weight: HZSM-5, Mn: Ce: 1 wt.% Mo, 5 wt.% Mo: 2 wt.%.
A preparation method of a water-resistant and sulfur-resistant manganese-cerium-based molecular sieve SCR denitration catalyst comprises the following steps:
a. adding a molecular sieve HZSM-5 into a mixed solution containing Mn, Ce and Mo, regulating the pH value of the mixed solution to 10, carrying out ion exchange in a reaction kettle for 12 hours, and washing and drying a solid product to obtain manganese and cerium modified molecular sieve powder;
b. uniformly mixing the modified manganese-cerium-based molecular sieve catalyst powder, alumina gel and deionized water to prepare a mixed solution A with the solid content of 36 wt.%, wherein the weight ratio of the alumina gel to the molecular sieve powder is 10, coating the mixed solution A on a porous cordierite carrier by adopting a vacuum suction method, and the coating amount of a catalyst coating is 200g/L according to the solid content.
c. And c, drying the porous cordierite carrier coated with the mixed solution A in the step b at 120 ℃ for 5 hours, and then roasting at 550 ℃ for 3 hours in an air atmosphere to obtain the Mn-Ce-Mo-HZSM-5 molecular sieve catalyst.
Example 3
A water-resistant sulfur-resistant manganese cerium-based molecular sieve SCR denitration catalyst comprises a porous ceramic carrier and a modified manganese cerium-based molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the molecular sieve catalyst comprises the following components in parts by weight: HZSM-5, Mn: Ce: w1 wt.% 5 wt.%: 2 wt.%.
A preparation method of a water-resistant and sulfur-resistant manganese-cerium-based molecular sieve SCR denitration catalyst comprises the following steps:
a. adding a molecular sieve HZSM-5 into a mixed solution containing Mn, Ce and W, regulating the pH value of the mixed solution to 10, carrying out ion exchange in a reaction kettle for 12 hours, and washing and drying a solid product to obtain manganese and cerium modified molecular sieve powder;
b. uniformly mixing the modified manganese-cerium-based molecular sieve catalyst powder, alumina gel and deionized water to prepare a mixed solution A with the solid content of 36 wt.%, wherein the weight ratio of the alumina gel to the molecular sieve powder is 10, coating the mixed solution A on a porous cordierite carrier by adopting a vacuum suction method, and the coating amount of a catalyst coating is 200g/L according to the solid content.
c. And c, drying the porous cordierite carrier coated with the mixed solution A in the step b at 120 ℃ for 5 hours, and then roasting at 550 ℃ for 3 hours in an air atmosphere to obtain the Mn-Ce-W-HZSM-5 molecular sieve catalyst.
Example 4
A water-resistant sulfur-resistant manganese cerium-based molecular sieve SCR denitration catalyst comprises a porous ceramic carrier and a modified manganese cerium-based molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the molecular sieve catalyst comprises the following components in parts by weight: HZSM-5, Mn: Ce: 1 wt.% Co, 5 wt.%: 2 wt.%.
A preparation method of a water-resistant and sulfur-resistant manganese-cerium-based molecular sieve SCR denitration catalyst comprises the following steps:
a. adding a molecular sieve HZSM-5 into a mixed solution containing Mn, Ce and Co, regulating the pH value of the mixed solution to 10, carrying out ion exchange in a reaction kettle for 12 hours, and washing and drying a solid product to obtain manganese and cerium modified molecular sieve powder;
b. uniformly mixing the modified manganese-cerium-based molecular sieve catalyst powder, alumina gel and deionized water to prepare a mixed solution A with the solid content of 36 wt.%, wherein the weight ratio of the alumina gel to the molecular sieve powder is 10, coating the mixed solution A on a porous cordierite carrier by adopting a vacuum suction method, and the coating amount of a catalyst coating is 200g/L according to the solid content.
c. And c, drying the porous cordierite carrier coated with the mixed solution A in the step b at 120 ℃ for 5 hours, and then roasting at 550 ℃ for 3 hours in an air atmosphere to obtain the Mn-Ce-Co-HZSM-5 molecular sieve catalyst.
Example 5
A water-resistant sulfur-resistant manganese cerium-based molecular sieve SCR denitration catalyst comprises a porous ceramic carrier and a modified manganese cerium-based molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the molecular sieve catalyst comprises the following components in parts by weight: HZSM-5, Mn: Ce: cr 1 wt.%, 5 wt.%: 2 wt.%.
A preparation method of a water-resistant and sulfur-resistant manganese-cerium-based molecular sieve SCR denitration catalyst comprises the following steps:
a. adding a molecular sieve HZSM-5 into a mixed solution containing Mn, Ce and Cr, regulating the pH value of the mixed solution to 10, carrying out ion exchange in a reaction kettle for 12 hours, and washing and drying a solid product to obtain manganese and cerium modified molecular sieve powder;
b. uniformly mixing the modified manganese-cerium-based molecular sieve catalyst powder, alumina gel and deionized water to prepare a mixed solution A with the solid content of 36 wt.%, wherein the weight ratio of the alumina gel to the molecular sieve powder is 10, coating the mixed solution A on a porous cordierite carrier by adopting a vacuum suction method, and the coating amount of a catalyst coating is 200g/L according to the solid content.
c. And c, drying the porous cordierite carrier coated with the mixed solution A in the step b at 120 ℃ for 5 hours, and then roasting at 550 ℃ for 3 hours in an air atmosphere to obtain the Mn-Ce-Cr-HZSM-5 molecular sieve catalyst.
Comparative example 1
The manganese-based molecular sieve SCR denitration catalyst comprises a porous ceramic carrier and a modified manganese-based molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the molecular sieve catalyst comprises the following components in parts by weight: HZSM-5 Mn 1 wt.% to 5 wt.%.
The preparation method of the manganese-based molecular sieve SCR denitration catalyst comprises the following steps:
a. adding a molecular sieve HZSM-5 into a Mn-containing solution, regulating the pH value of the solution to 10, carrying out ion exchange in a reaction kettle for 12 hours, washing and drying a solid product to obtain manganese-based molecular sieve powder;
b. uniformly mixing the modified manganese-based molecular sieve catalyst powder, alumina gel and deionized water to prepare a mixed solution A with the solid content of 36 wt.%, wherein the weight ratio of the alumina gel to the molecular sieve powder is 10, coating the mixed solution A on a porous cordierite carrier by adopting a vacuum suction method, and the coating amount of a catalyst coating is 200g/L according to the solid content.
c. And c, drying the porous cordierite carrier coated with the mixed solution A in the step b at 120 ℃ for 5 hours, and then roasting at 550 ℃ for 3 hours in an air atmosphere to obtain the Mn-HZSM-5 molecular sieve catalyst.
The partial Mn-Ce-Fe-HZSM-5 molecular sieve catalyst prepared in example 1 and the partial Mn-HZSM-5 molecular sieve catalyst in comparative example 1 were subjected to high temperature hydrothermal aging conditions: aging is carried out for 10 hours at 800 ℃ in an atmosphere of 10% water vapor. The catalytic performance of the catalyst in the fresh state and the aged state was compared, and the specific comparison results are shown in table 1.
Catalyst evaluation conditions: 1300ppm NH3，1300ppm NO，5％O2，10％H2O， 50ppm SO2，N2The space velocity is 30000h for balancing gas-1。
Table 1: comparative data of catalytic performance of catalyst under different states
As can be seen from comparison of NOx conversion data of the catalysts in different states, the molecular sieve catalyst T90 prepared by the method is about 150, and the multi-metal ions are filled in the defect positions of the molecular sieve by controlling the process parameters of ion exchange at the temperature of DEG C, so that the stability of the molecular sieve catalyst is obviously improved. Meanwhile, the synergistic effect of the multi-metal active components is utilized, the active temperature window is widened, the high activity, high selectivity, sulfur resistance and water resistance in a low-temperature region can be realized, and the catalyst still keeps high activity in hydrothermal aging and sulfur aging states.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The manganese-cerium-based molecular sieve SCR denitration catalyst is characterized by comprising a porous ceramic carrier and a Mn-Ce-X modified molecular sieve catalyst coating coated on the porous ceramic carrier, wherein the Mn-Ce-X modified molecular sieve is obtained by modifying Mn, Ce and X with an HZSM-5 carrier, the X is one or more selected from W, Mo, Co, Fe and Cr, and the Mn-Ce-X modified molecular sieve comprises the following components in parts by weight: molecular sieve: mn: ce: x1 wt.%: 0.2 wt.% to 10 wt.%: 0.2 wt.% to 10 wt.%: 0.1 wt.% to 10 wt.%.
2. The SCR denitration catalyst of claim 1, wherein the porous ceramic carrier is cordierite, silicon carbide or aluminum silicate.
3. The catalyst for SCR denitration of a manganese-cerium-based molecular sieve as claimed in claim 1, wherein the coating comprises a Mn-Ce-X modified molecular sieve and an auxiliary agent, and the coating amount of the coating is 30-300 g/L in terms of solid phase content.
4. A preparation method of a manganese-cerium-based molecular sieve SCR denitration catalyst is characterized by comprising the following steps: the method comprises the following steps:
a. modification of a molecular sieve: adding a molecular sieve into a solution containing Mn, Ce and X, stirring uniformly, regulating the pH value of the mixed solution to be within the range of 2-7, carrying out ion exchange in a reaction kettle for 1-12 hours, washing and drying a solid product to obtain Mn-Ce-X modified molecular sieve powder, wherein X is one or more selected from W, Mo, Co, Fe and Cr;
b. preparing catalyst slurry: uniformly mixing Mn-Ce-X modified molecular sieve powder, aluminum gel and deionized water to prepare a mixed solution A, wherein the content of a cured product of the solution A is controlled to be 5-50 wt%, and the solid-phase weight ratio of the aluminum gel to the molecular sieve catalyst in the cured product is controlled to be 0.1-10;
c. coating of molecular sieve catalyst: and c, coating the mixed solution A prepared in the step B on a porous ceramic carrier according to the coating amount of 30-300 g/L of the solid content to prepare a catalyst B, drying the catalyst B for 0.1-10 hours, and roasting for 0.1-10 hours to obtain the manganese cerium-based molecular sieve SCR denitration catalyst.
5. The preparation method of the cerium-based molecular sieve SCR denitration catalyst according to claim 4, wherein the method comprises the following steps: the solution containing Mn, Ce and X comprises manganese salt and cerium salt, wherein the manganese salt is one or more of manganese acetate, manganese carbonate and manganese nitrate, and the cerium salt is one or more of cerium acetate, cerium nitrate and cerium sulfate.
6. The preparation method of the cerium-based molecular sieve SCR denitration catalyst according to claim 4, wherein the method comprises the following steps: and (b) performing ion exchange on the active components Mn and Ce in the step (a) at the same time, or performing two-step ion exchange on the two active components and not fixing the exchange sequence.
7. The preparation method of the cerium-based molecular sieve SCR denitration catalyst according to claim 4, wherein the method comprises the following steps: and c, coating the mixed solution A on the porous ceramic carrier by one or more of a soaking method, a vacuum suction method and a spraying method.
8. The preparation method of the cerium-based molecular sieve SCR denitration catalyst according to claim 4, wherein the calcination temperature in the step c is 400-700 ℃.
9. The preparation method of the cerium-based molecular sieve SCR denitration catalyst according to claim 4, wherein the drying temperature in the step c is 50-200 ℃.
10. The cerium-based molecular sieve SCR denitration catalyst prepared by the preparation method of the cerium-based molecular sieve SCR denitration catalyst according to claims 4 to 9.
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