CN105709813A - Sulfur-resistant SCR (selective catalytic reduction) catalyst and preparation method thereof - Google Patents

Sulfur-resistant SCR (selective catalytic reduction) catalyst and preparation method thereof Download PDF

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Publication number
CN105709813A
CN105709813A CN201610042899.2A CN201610042899A CN105709813A CN 105709813 A CN105709813 A CN 105709813A CN 201610042899 A CN201610042899 A CN 201610042899A CN 105709813 A CN105709813 A CN 105709813A
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Prior art keywords
zsm
catalyst
preparation
scr catalyst
sulfur
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宾峰
李懿君
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LIUZHOU HAIDA NEW MATERIAL TECHNOLOGY Co Ltd
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LIUZHOU HAIDA NEW MATERIAL TECHNOLOGY Co Ltd
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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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/50—Zeolites
    • B01D2255/504—ZSM 5 zeolites
    • 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)
  • Combustion & Propulsion (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of preparation of catalysts and discloses a sulfur-resistant SCR (selective catalytic reduction) catalyst and a preparation method thereof. The sulfur-resistant SCR catalyst comprises ZSM-5 zeolite molecular sieves, copper element, manganese element and zirconium element. The preparation method includes: well mixing cupric nitrate, manganese nitrate and zirconium nitrate solution, impregnating into ZSM-5, and stirring for 24h at the temperature of 75-85 DEG C; drying for 3.5-4.5h at the temperature of 115-125 DEG C; calcining for 3.5-4.5h at the high temperature of 540-560 DEG C; finally naturally cooling to the room temperature to obtain the sulfur-resistant SCR catalyst. The sulfur-resistant SCR catalyst and the preparation method thereof have the advantage that the SCR catalyst is high in reaction activity in a low-temperature range and less prone to sulfur poisoning.

Description

Resistance to SO_2 SCR catalyst and preparation method
Technical field
The present invention relates to catalyst preparation technical field, a kind of low temperature resistance to SO_2 SCR catalyst being applied to purification of diesel tail gas and preparation method.
Background technology
Diesel engine vent gas contains substantial amounts of pm emission (PM) and nitrogen oxides (NOx), so, purification of diesel tail gas processes PM and NO the most exactlyx.At present most it is expected to be applied to NO in vehicle exhaustxOne of purification techniques be SCR technology (selective catalytic Reduction, SCR), almost all of Europe truck manufactures commercial city and uses this SCR technology to reduce NO in truck tail gasxDischarge.This SCR technology refers to that, under the effect of catalyst, the reducing substances in additional reducing agent or tail gas is optionally by NOxIt is reduced to N2, and avoid occurring the technology of the non-selective oxidation reaction of reducing agent.So, the core of SCR technology is exactly catalyst.When the diesel oil that use sulfur content is high, containing SO in engine exhaust2Composition, SO2It is easily oxidized to SO under the effect of catalyst3, generally (namely temperature when engine start) NH temperature ＜ 250 DEG C when3And SO3Easily combine generation (NH4)2SO4And NH4HSO4, (the NH of generation4)2SO4And NH4HSO4Catalyst surface can be deposited on and cover Adsorption, cause the sulfur poisoning of catalyst, thus reduce the SCR reactivity of catalyst.
The catalyst of application is usually with TiO at present2For carrier, with V2O5Or V2O5-WO3、V2O5-MoO3For the vanadium series catalyst of active component, WO3Or MoO3SO can be suppressed2To SO3Convert, can sulfur poisoning-resistant.But this vanadium series catalyst will be at 280 DEG C～about 420 DEG C, NOxTransform level can be only achieved requirement, and the temperature of diesel engine normal exhaust is 250 DEG C～350 DEG C of temperature ranges, so using this vanadium series catalyst SCR reaction effect in the range of 250 DEG C～280 DEG C unsatisfactory；Further, since containing noxious substance vanadium in this catalyst system, easily fall off during long term high temperature uses, enter into and environment has the biggest bio-toxicity, and can be enriched with in vivo.
So needing to find the resistance to SO_2 SCR catalyst preferably can in low temperature range with relatively high reaction activity.
Summary of the invention
A kind of resistance to SO_2 SCR catalyst provided by the present invention and preparation method, it can solve SCR catalyst and have the problem that relatively high reaction activity is not susceptible to again sulfur poisoning simultaneously in low temperature range.
In order to solve the problems referred to above, the technical solution adopted in the present invention is: this resistance to SO_2 SCR catalyst, comprise ZSM-5 zeolite molecular sieve, also comprise 1 %～3% copper accounting for described ZSM-5 mass fraction, account for the manganese element that described ZSM-5 mass fraction is 0.5%～4%, and account for the zr element of described ZSM-5 mass fraction 0.5%～3.5%.
In technique scheme, more specifically technical scheme is it may also is that described copper is mainly with Cu+Form is dispersed in surface and the duct of ZSM-5, and described manganese element is mainly with Mn2+And Mn3+Form is dispersed in surface and the duct of ZSM-5, and described zr element is mainly with ZrO2Presented in cluster in described resistance to SO_2 SCR catalyst.
The preparation method of this resistance to SO_2 SCR catalyst comprises the following steps:
A, copper nitrate, manganese nitrate and zirconium nitrate solution be impregnated in ZSM-5, stir 24 hours at 75 DEG C～85 DEG C；
B, then drying 3.5～4.5 hours at 115 DEG C～125 DEG C；
C, by step B gained high-temperature roasting 3.5～4.5 hours at 540 DEG C～560 DEG C；
D, step C gained is naturally cooled to room temperature and get final product.
Further: in described copper nitrate solution, the quality of copper nitrate is the 2%～6% of ZSM-5 mass, in described manganese nitrate solution, the quality of manganese nitrate is the 2%～15% of ZSM-5 mass, and in described zirconium nitrate solution, the quality of zirconium nitrate is the 1.8%～13% of ZSM-5 mass.
Further: step D gained catalyst powder is broken to 20～40 mesh.
Owing to have employed technique scheme, the present invention compared with prior art has the advantages that
1, molecular sieve catalyst has good absorption property and motility, and in the case of load different metal, the activity of catalyst will occur to change accordingly so that active temperature is controlled.Stronger interaction is there is between ZSM-5 molecular sieve carrier of the present invention and Cu ion, and regulate the Electronic Performance changing active component, active component is caused to be easier to reduction, so Cu/ ZSM-5 catalyst has stronger catalysis reduction effect to low-temperature SCR reaction；And it is main with MnOxThe manganese element that form exists and ZSM-5 molecular sieve carrier there is also stronger interaction, Mn granule is made to be difficult to grow up during reduction reaction, the reunion effectively preventing active component Mn crystallizes, the crystallization making the principal element metal-oxide of SCR reaction decline becomes not exist, and then improves the activity of catalyst.Experiment shows to use this catalyst to carry out SCR reaction, in the range of 180 DEG C～415 DEG C, and NOxMaintain the highest catalytic conversion, conversion ratio is the highest can reach more than 98%.So the catalyst of the present invention has stronger catalysis reduction effect to low-temperature SCR reaction.
2、ZrO2Chemical stability preferable, be that one not only has acidity but also have alkalescence, not only there is oxidisability but also there is particulate metal oxide of reproducibility, its introducing, be conducive to changing catalyst surface Acidity of Aikalinity, reduce sour gas SO2Accumulation, improve catalyst sulfur tolerance.It is again P-type semiconductor simultaneously, it is easily generated hole, stronger interaction can be produced with catalyst activity component Cu, Mn, by it, carrier ZSM-5 zeolite molecular sieve is regulated the effect improved between Cu, Mn and ZSM-5, thus improve Cu, Mn dispersion, grain size and surface composition etc. at ZSM-5, the beneficially raising of catalyst performance.I.e. add ZrO2Afterwards, the catalyst of the present invention can not only sulfur resistive, it is to avoid the generation of sulfur poisoning, moreover it is possible to improve the SCR reactivity of catalyst.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment one:
This resistance to SO_2 SCR catalyst, using ZSM-5 zeolite molecular sieve as carrier, has loaded main with Cu+The copper that form is homodisperse, content is ZSM-5 mass fraction 1%, mainly with Mn2+And Mn3+The manganese element that form is homodisperse, content is ZSM-5 mass fraction 0.5%, and main with ZrO2Presented in cluster, content is the zr element of ZSM-5 mass fraction 0.5%.
Preparation method is as follows:
A, by copper nitrate solution that copper nitrate quality is 2 grams, manganese nitrate quality it is the manganese nitrate solution of 2 grams and the zirconium nitrate solution that zirconium nitrate quality is 1.8 grams impregnated in 100 grams of ZSM-5, stirs 24 hours at 75 DEG C；
B, then about 120 DEG C dry 3.5 hours；
C, by step B gained high-temperature roasting 4.5 hours at 540 DEG C；
D, step C gained is naturally cooled to 15 DEG C～25 DEG C and get final product.
Prepared catalyst powder is broken to 20～40 mesh being used for SCR catalytic NOX reduction is N2, 200 DEG C～400 DEG C of scopes, the conversion ratio of NOx is maintained at more than 98%；And reacting 100 hours at 400 DEG C, the conversion ratio of NOx is held essentially constant.
Embodiment two:
This resistance to SO_2 SCR catalyst, using ZSM-5 zeolite molecular sieve as carrier, has loaded main with Cu+The copper that form is homodisperse, content is ZSM-5 mass fraction 3%, mainly with Mn2+And Mn3+The manganese element that form is homodisperse, content is ZSM-5 mass fraction 4%, and main with ZrO2Presented in cluster, content is the zr element of ZSM-5 mass fraction 3.5%.
Preparation method is as follows:
A, by copper nitrate solution that copper nitrate quality is 6 grams, manganese nitrate quality it is the manganese nitrate solution of 15 grams and the zirconium nitrate solution that zirconium nitrate quality is 13 grams impregnated in 100 grams of ZSM-5, stirs 24 hours at 75 DEG C；
B, then about 120 DEG C dry 3.5 hours；
C, by step B gained high-temperature roasting 4.5 hours at 540 DEG C；
D, step C gained is naturally cooled to 15 DEG C～25 DEG C and get final product.
Prepared catalyst powder is broken to 20～40 mesh being used for SCR catalytic NOX reduction is N2, 180 DEG C～415 DEG C of scopes, the conversion ratio of NOx is maintained at more than 98%；And reacting 100 hours at 400 DEG C, the conversion ratio of NOx is held essentially constant.

Claims (5)

1. a resistance to SO_2 SCR catalyst, including ZSM-5 zeolite molecular sieve, it is characterized in that: also comprise 1 %～3% copper accounting for described ZSM-5 mass fraction, account for the manganese element that described ZSM-5 mass fraction is 0.5%～4%, and account for the zr element of described ZSM-5 mass fraction 0.5%～3.5%.
Resistance to SO_2 SCR catalyst the most according to claim 1, it is characterised in that: described copper is mainly dispersed in surface and the duct of ZSM-5 with Cu+ form, and described manganese element is mainly with Mn2+And Mn3+Form is dispersed in surface and the duct of ZSM-5, and described zr element is mainly with ZrO2Presented in cluster in described resistance to SO_2 SCR catalyst.
3. the preparation method of a resistance to SO_2 SCR catalyst, it is characterised in that comprise the following steps:
A, copper nitrate, manganese nitrate and zirconium nitrate solution be impregnated in ZSM-5, stir 24 hours at 75 DEG C～85 DEG C；
B, then drying 3.5～4.5 hours at 115 DEG C～125 DEG C；
C, by step B gained high-temperature roasting 3.5～4.5 hours at 540 DEG C～560 DEG C；
D, step C gained is naturally cooled to room temperature and get final product.
The preparation method of resistance to SO_2 SCR catalyst the most according to claim 3, it is characterized in that: in described copper nitrate solution, the quality of copper nitrate is the 2%～6% of ZSM-5 mass, in described manganese nitrate solution, the quality of manganese nitrate is the 2%～15% of ZSM-5 mass, and in described zirconium nitrate solution, the quality of zirconium nitrate is the 1.8%～13% of ZSM-5 mass.
5. according to the preparation method of the resistance to SO_2 SCR catalyst described in claim 3 or 4, it is characterised in that: step D gained catalyst powder is broken to 20～40 mesh.
CN201610042899.2A 2016-01-22 2016-01-22 Sulfur-resistant SCR (selective catalytic reduction) catalyst and preparation method thereof Pending CN105709813A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108993580A (en) * 2018-08-10 2018-12-14 上海应用技术大学 A kind of low temperature SCR denitration catalyst and preparation method thereof of anticalcium poisoning

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1401412A (en) * 2002-09-28 2003-03-12 太原理工大学 Nitrogen oxide purifying catalyst and preparation thereof
CN101417237A (en) * 2008-11-27 2009-04-29 中国科学院生态环境研究中心 PtX-Fe-ZSM-5 molecular sieve catalyst for ammine selective catalytic oxidation
CN102247886A (en) * 2011-05-10 2011-11-23 天津大学 Manganese-zirconium dual metal modified selective catalytic reduction catalyst for molecular sieve type diesel engine
CN104801335A (en) * 2015-04-11 2015-07-29 桂林理工大学 Zr-Ce-Mn/ZSM-5 complex oxide catalyst adopting NH3 to reduce NOx at low temperature as well as preparation method of Zr-Ce-Mn/ZSM-5 complex oxide catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1401412A (en) * 2002-09-28 2003-03-12 太原理工大学 Nitrogen oxide purifying catalyst and preparation thereof
CN101417237A (en) * 2008-11-27 2009-04-29 中国科学院生态环境研究中心 PtX-Fe-ZSM-5 molecular sieve catalyst for ammine selective catalytic oxidation
CN102247886A (en) * 2011-05-10 2011-11-23 天津大学 Manganese-zirconium dual metal modified selective catalytic reduction catalyst for molecular sieve type diesel engine
CN104801335A (en) * 2015-04-11 2015-07-29 桂林理工大学 Zr-Ce-Mn/ZSM-5 complex oxide catalyst adopting NH3 to reduce NOx at low temperature as well as preparation method of Zr-Ce-Mn/ZSM-5 complex oxide catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宾峰: ""改性分子筛材料用于选择催化还原柴油机氮氧化物的研究"", 《中国博士学位论文全文数据库工程科技II辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108993580A (en) * 2018-08-10 2018-12-14 上海应用技术大学 A kind of low temperature SCR denitration catalyst and preparation method thereof of anticalcium poisoning

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Application publication date: 20160629