CN105597813A - Manganese-modified molecular sieve SCR catalyst and preparing method - Google Patents

Manganese-modified molecular sieve SCR catalyst and preparing method Download PDF

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Publication number
CN105597813A
CN105597813A CN201610042903.5A CN201610042903A CN105597813A CN 105597813 A CN105597813 A CN 105597813A CN 201610042903 A CN201610042903 A CN 201610042903A CN 105597813 A CN105597813 A CN 105597813A
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Prior art keywords
manganese
scr catalyst
modified molecular
molecular sieve
zsm
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CN201610042903.5A
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Chinese (zh)
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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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Priority to CN201610042903.5A priority Critical patent/CN105597813A/en
Publication of CN105597813A publication Critical patent/CN105597813A/en
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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
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • 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

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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 discloses a manganese-modified molecular sieve SCR catalyst and a preparing method and relates to the technical field of preparation of catalysts. The manganese-modified molecular sieve SCR catalyst is prepared from zeolite molecular sieves and manganese elements. The preparing method comprises the steps that firstly, the ZSM-5 zeolite molecular sieves are steeped into a manganese nitrate solution, and the mixture is stirred for 24 h at 75-85 DEG C; secondly, the mixture is dried for 3.5-4.5 h under 115-125 DEG C; thirdly, the mixture is subjected to high-temperature roasting at 540-560 DEG C; finally, the mixture is naturally cooled to the room temperature, and the manganese-modified molecular sieve SCR catalyst is obtained. By means of the manganese-modified molecular sieve SCR catalyst and the preparing method, catalyzing the reduction of NOx into N2 at low temperature is achieved, the conversion rate of NOx can reach 98% or higher, the reaction speed is higher than that at high temperatures, and the catalyst is safe and free of biotoxicity.

Description

Manganese modified molecular screen SCR catalyst and preparation method
Technical field
The present invention relates to catalyst preparation technical field, especially a kind of manganese modified molecular screen SCR catalyst and preparation method who is applied to SCR denitration technology.
Background technology
SCR technology (selectivecatalyticreduction, SCR) is to be expected at present be applied to nitrogen oxide (NO mostxOne of) out of stock technology. This SCR technology refers to that, under the effect of catalyst, the reducing substances in additional reducing agent or exhaust is optionally by NOxBe reduced to N2, and avoid the technology of the non-selective oxidation reaction that reducing agent occurs. Detailed process is NH3(reducing agent) is under the effect of uniform temperature and catalyst, the NO in exhaustxBe reduced to N2. So the core of SCR technology is exactly catalyst. The catalyst of application is generally with TiO at present2For carrier, with V2O5Or V2O5-WO3、V2O5-MoO3For the vanadium series catalyst of active component, reaction temperature is at 280 DEG C～420 DEG C left and right, at this moment NOxConversion ratio higher, but the initial temperature of 280 DEG C during higher than cold-starting automobile only up to the temperature of 250 DEG C, this lower than the scope of 280 DEG C in NOxLow conversion rate, therefore, there is the defect of active temperature scope relative narrower in this vanadium series catalyst; This defect also produces following deficiency: 1. reaction temperature will be remained on to 280 DEG C～420 DEG C, the each side costs such as consersion unit can be higher; 2. owing to containing noxious material vanadium in this catalyst system, in long term high temperature use procedure, easily come off, enter into environment and there is very large bio-toxicity, and enrichment in vivo.
So be applicable to the catalyst of the safety of low temperature.
Summary of the invention
A kind of manganese modified molecular screen SCR catalyst provided by the present invention and preparation method, solved SCR at low-temperature catalyzed NOxBe reduced to N2Problem, within the scope of 240 DEG C～400 DEG C, NOxConversion ratio can reach more than 98%.
In order to address the above problem, the technical solution adopted in the present invention is: this manganese modified molecular screen SCR catalyst, comprise ZSM-5 zeolite molecular sieve, and also contain the manganese element that accounts for described ZSM-5 zeolite molecular sieve mass fraction 0.6%～10%.
In technique scheme, technical scheme can also be more specifically: described manganese element is mainly with Mn2+And Mn3+Form is dispersed in the surface and duct of ZSM-5.
The preparation method of this manganese modified molecular screen SCR catalyst comprises the following steps:
A, manganese nitrate solution be impregnated in ZSM-5, at 75 DEG C～85 DEG C, stir 24 hours;
B, then at 115 DEG C～125 DEG C, dry 3.5～4.5 hours;
C, by the high-temperature roasting 3.5～4.5 hours at 540 DEG C～560 DEG C of step B gained;
D, step C gained is naturally cooled to room temperature and get final product.
Further: in described manganese nitrate solution, the quality of manganese nitrate is 2%～32.5% of ZSM-5 quality.
Further: step D gained catalyst powder is broken to 20～40 orders.
Owing to having adopted technique scheme, the present invention compared with prior art has following beneficial effect:
1, molecular sieve catalyst has good absorption property and flexibility, and the in the situation that of load different metal, corresponding change will occur the activity of catalyst, makes active temperature controlled. The present invention is mainly with MnOxManganese element and ZSM-5 molecular sieve carrier that form exists exist stronger interaction, make Mn particle be difficult for growing up in the process of reduction reaction, effectively prevent the reunion crystallization of active component Mn, make that SCR reaction declines principal element---the crystallization of metal oxide becomes and does not exist, and then improve the activity of catalyst. Experiment shows within the scope of 240 DEG C～400 DEG C, NOxMaintaining very high catalytic conversion, conversion ratio is the highest can be reached more than 98%. So Mn/ZSM-5 catalyst is to low-temperature SCR, reaction has stronger catalytic reduction effect.
2, under the catalytic reduction effect of catalyst of the present invention, NO under low temperature environmentxThe high energy of conversion rate than the highest conversion rate under hot environment fast 14～17 times.
3, catalyst of the present invention is safer, does not have bio-toxicity.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment mono-:
This manganese modified molecular screen SCR catalyst, taking ZSM-5 zeolite molecular sieve as carrier, also contains the manganese element that accounts for described ZSM-5 zeolite molecular sieve mass fraction 0.6%, and described manganese element is mainly with Mn2+And Mn3+Form is dispersed in the surface and duct of ZSM-5.
Preparation method is as follows:
A, the manganese nitrate solution that is 2 grams by manganese nitrate quality impregnated in 100 grams of ZSM-5, stir 24 hours at 75 DEG C;
B, then about 120 DEG C dry 3.5 hours;
C, by the high-temperature roasting 3.5 hours under 550 DEG C of left and right of step B gained;
D, step C gained is naturally cooled to 15 DEG C～25 DEG C and get final product.
The catalyst powder making is broken to 20～40 orders and is used in SCR catalyzing N OxBe reduced to N2, NO in the time of 240 DEG C, 300 DEG C～400 DEG CxConversion ratio reach 98%; In addition, NO in the time of 240 DEG CxConversion rate be about in the time of 300 DEG C～400 DEG C Mean Speed 14 times.
Embodiment bis-:
This manganese modified molecular screen SCR catalyst, taking ZSM-5 zeolite molecular sieve as carrier, also contains the manganese element that accounts for described ZSM-5 zeolite molecular sieve mass fraction 10%, and described manganese element is mainly with Mn2+And Mn3+Form is dispersed in the surface and duct of ZSM-5.
Preparation method is as follows:
A, the manganese nitrate solution that is 32.5 grams by manganese nitrate quality impregnated in 100 grams of ZSM-5, stir 24 hours at 75 DEG C;
B, then about 120 DEG C dry 3.5 hours;
C, by the high-temperature roasting 3.5 hours under 550 DEG C of left and right of step B gained;
D, step C gained is naturally cooled to 15 DEG C～25 DEG C and get final product.
The catalyst powder making is broken to 20～40 orders and is used in SCR catalyzing N OxBe reduced to N2, NO in the time of 260 DEG C～300 DEG CxConversion ratio reach 98%.

Claims (5)

1. a manganese modified molecular screen SCR catalyst, comprises ZSM-5 zeolite molecular sieve, it is characterized in that: also contain the manganese element that accounts for described ZSM-5 zeolite molecular sieve mass fraction 0.6%～10%.
2. manganese modified molecular screen SCR catalyst according to claim 1, is characterized in that: described manganese element is mainly with Mn2+And Mn3+Form is dispersed in the surface and duct of ZSM-5.
3. a preparation method for manganese modified molecular screen SCR catalyst, is characterized in that: comprise the following steps:
A, manganese nitrate solution be impregnated in ZSM-5, at 75 DEG C～85 DEG C, stir 24 hours;
B, then at 115 DEG C～125 DEG C, dry 3.5～4.5 hours;
C, by the high-temperature roasting 3.5～4.5 hours at 540 DEG C～560 DEG C of step B gained;
D, step C gained is naturally cooled to room temperature and get final product.
4. the preparation method of manganese modified molecular screen SCR catalyst according to claim 3, is characterized in that: in described manganese nitrate solution, the quality of manganese nitrate is 2%～32.5% of ZSM-5 quality.
5. according to the preparation method of the manganese modified molecular screen SCR catalyst described in claim 3 or 4, it is characterized in that: step D gained catalyst powder is broken to 20～40 orders.
CN201610042903.5A 2016-01-22 2016-01-22 Manganese-modified molecular sieve SCR catalyst and preparing method Pending CN105597813A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112547117A (en) * 2019-09-25 2021-03-26 北京化工大学 Normal-temperature NH used under plasma driving condition3Catalyst for selective catalytic reduction of NO and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110047988A1 (en) * 2009-08-31 2011-03-03 General Electric Company Catalyst and method of manufacture
CN103464194A (en) * 2013-09-05 2013-12-25 浙江天蓝环保技术股份有限公司 SCR (Selective catalytic reduction) monolithic honeycombed catalyst for low-temperature flue gas de-nitrification and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110047988A1 (en) * 2009-08-31 2011-03-03 General Electric Company Catalyst and method of manufacture
CN103464194A (en) * 2013-09-05 2013-12-25 浙江天蓝环保技术股份有限公司 SCR (Selective catalytic reduction) monolithic honeycombed catalyst for low-temperature flue gas de-nitrification and preparation method thereof

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性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（电子期刊）》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112547117A (en) * 2019-09-25 2021-03-26 北京化工大学 Normal-temperature NH used under plasma driving condition3Catalyst for selective catalytic reduction of NO and preparation method thereof
CN112547117B (en) * 2019-09-25 2024-03-26 北京化工大学 Normal temperature NH for plasma driving condition 3 Catalyst for selective catalytic reduction of NO and preparation method thereof

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