CN105709812A - Cobalt-modified ZSM-5 zeolite molecular sieve catalyst and method for preparing same - Google Patents

Cobalt-modified ZSM-5 zeolite molecular sieve catalyst and method for preparing same Download PDF

Info

Publication number
CN105709812A
CN105709812A CN201610042906.9A CN201610042906A CN105709812A CN 105709812 A CN105709812 A CN 105709812A CN 201610042906 A CN201610042906 A CN 201610042906A CN 105709812 A CN105709812 A CN 105709812A
Authority
CN
China
Prior art keywords
zeolite molecular
zsm
molecular sieve
cobalt
sieve catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610042906.9A
Other languages
Chinese (zh)
Inventor
宾峰
李懿君
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LIUZHOU HAIDA NEW MATERIAL TECHNOLOGY Co Ltd
Original Assignee
LIUZHOU HAIDA NEW MATERIAL TECHNOLOGY Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LIUZHOU HAIDA NEW MATERIAL TECHNOLOGY Co Ltd filed Critical LIUZHOU HAIDA NEW MATERIAL TECHNOLOGY Co Ltd
Priority to CN201610042906.9A priority Critical patent/CN105709812A/en
Publication of CN105709812A publication Critical patent/CN105709812A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20746—Cobalt
    • 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
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/65—Catalysts not containing noble metals
    • 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
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a cobalt-modified ZSM-5 zeolite molecular sieve catalyst and a method for preparing the same, and relates to the field of technologies for preparing catalysts. The cobalt-modified ZSM-5 zeolite molecular sieve catalyst comprises ZSM-5 zeolite molecular sieves and cobalt elements. The method includes impregnating cobalt nitrate solution in the ZSM-5 zeolite molecular sieves and stirring the cobalt nitrate solution and the ZSM-5 zeolite molecular sieves at the temperature of 75-85 DEG C for 24 hours to obtain mixtures; drying the mixtures at the temperature of 115-125 DEG C for 3.5-4.5 hours; calcining the mixtures at the high temperature of 540-560 DEG C for 3.5-4.5 hours; naturally cooling the mixtures until the temperature of the mixtures reaches the room temperature so as to obtain the cobalt-modified ZMS-5 zeolite molecular sieve catalyst. The cobalt-modified ZMS-5 zeolite molecular sieve catalyst and the method have the advantages that NOx can be catalytically reduced to obtain N2 by the aid of the cobalt-modified ZSM-5 zeolite catalyst in low-temperature environments, and the cobalt-modified zeolite molecular sieve catalyst is high in NOx conversion ratio and free of biological toxicity, is high in reaction speed as compared with high-temperature environments and is safe.

Description

Co-containing ZSM-5 zeolite molecular sieve catalyst and preparation method
Technical field
The present invention relates to catalyst preparation technical field, a kind of Co-containing ZSM-5 zeolite molecular sieve catalyst being applied to SCR denitration technology and preparation method.
Background technology
SCR technology (selective catalytic Reduction, SCR) it is at present most to be expected to be applied to nitrogen oxides (NOxOne of) out of stock technology.This SCR technology refers to that, under the effect of catalyst, the reducing substances in additional reducing agent or aerofluxus is optionally by NOxIt is reduced to N2, and avoid occurring the technology of the non-selective oxidation reaction of reducing agent.Detailed process is NH3(reducing agent) under the effect of uniform temperature and catalyst, the NO in aerofluxusxIt is reduced to N2.So, the core of SCR technology is exactly 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, reaction temperature at 280 DEG C～about 420 DEG C, at this moment NOxConversion ratio higher, but the initial temperature of 280 DEG C higher than cold-starting automobile time be only up to the temperature of 250 DEG C, this less than 280 DEG C in the range of NOxConversion ratio low, therefore, there is the defect of active temperature range relative narrower in this vanadium series catalyst；The each side costs such as this defect also produces following deficiency: 1. reaction temperature is maintained at 280 DEG C～420 DEG C, consersion unit can be higher；2., owing to this catalyst system containing noxious substance vanadium, 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 the catalyst of the wider safety being especially suitable for low temperature of active temperature range to be found.
Summary of the invention
A kind of Co-containing ZSM-5 zeolite molecular sieve catalyst provided by the present invention and preparation method, it can solve to be catalyzed NO at low ambient temperaturesxIt is reduced to N2Problem, NOxConversion ratio is higher.
In order to solve the problems referred to above, the technical solution adopted in the present invention is: this Co-containing ZSM-5 zeolite molecular sieve catalyst, including ZSM-5 zeolite molecular sieve, possibly together with the cobalt element accounting for described ZSM-5 zeolite molecular sieve mass fraction 0.5%～12.5%.
In technique scheme, more specifically technical scheme is it may also is that described cobalt element is uniformly dispersed in ZSM-5 zeolite molecular sieve surface or duct.
The preparation method of this Co-containing ZSM-5 zeolite molecular sieve catalyst comprises the following steps:
A, cobalt 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 cobalt nitrate solution, the quality of cobalt nitrate is the 1.5%～39% 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.In the present invention, the cobalt element of free state can well be supported on ZSM-5 zeolite molecular sieve carrier, wherein part Co2+Intersect on position with ZSM-5 molecular sieve neutral body and H in passage+Exchanging, enter ZSM-5 framing structure, residue Co ion is with CoOxPresented in, both of which is NH3Selective catalysis reduction NOxActive component；First it is the O in air2With Co2+Redox reaction is occurred to generate Co3+；Work as NOxWith O2When coexisting, with Co3+Generate the Co of adsorbed state3+-NOx, then Co3+-NOxWith NH3Reaction generates N2And H2O, simultaneously Co3+It is reduced to Co2+；Wherein it is in the Co on exchange position2+Generally within the temperature range of 180 DEG C～300 DEG C, play catalytic action, NOxConversion ratio can reach 99%, and remain with CoOxPresented in Co ion within the temperature range of more than 300 DEG C, generally play catalytic action, NOxConversion ratio can reach 99.1%.So Co-containing ZSM-5 zeolite molecular sieve catalyst of the present invention plays, to be catalyzed the active temperature range of out of stock effect wider, can make NO within the temperature range of less than 300 DEG CxConversion ratio keep higher level.
2, under the catalysis reduction of the catalyst of the present invention, NO at low ambient temperaturesxConversion rate can be faster than the highest conversion rate under hot environment 14～17 times.
3, the 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 one:
This Co-containing ZSM-5 zeolite molecular sieve catalyst, with ZSM-5 zeolite molecular sieve as carrier, it is uniformly dispersed in ZSM-5 zeolite molecular sieve surface or duct with free state as active component, cobalt element containing the cobalt element accounting for described ZSM-5 zeolite molecular sieve mass fraction 0.5%.
Preparation method is as follows:
A, the cobalt nitrate solution that cobalt nitrate quality is 15 grams be impregnated in 1000 grams of ZSM-5, stir 24 hours at 75 DEG C；
B, then about 120 DEG C dry 3.5 hours；
C, by step B gained high-temperature roasting 3.5 hours under about 550 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 and is used in SCR catalysis NOxIt is reduced to N2, at about 230 DEG C NOxConversion ratio reach peak 94%.
Embodiment two:
This Co-containing ZSM-5 zeolite molecular sieve catalyst, with ZSM-5 zeolite molecular sieve as carrier, it is uniformly dispersed in ZSM-5 zeolite molecular sieve surface or duct with free state as active component, cobalt element containing the cobalt element accounting for described ZSM-5 zeolite molecular sieve mass fraction 12.5%.
Preparation method is as follows:
A, the cobalt nitrate solution that cobalt nitrate quality is 39 grams be 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 step B gained high-temperature roasting 3.5 hours under about 550 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 and is used in SCR catalysis NOxIt is reduced to N2, at about 170 DEG C NO of low temperature part (less than 300 DEG C)xConversion ratio reach peak 97%；And at about 440 DEG C NO of high-temperature part (more than 300 DEG C)xConversion ratio also reach peak 96%.It addition, when 170 DEG C NOxConversion rate be about when 440 DEG C 15 times.

Claims (5)

1. a Co-containing ZSM-5 zeolite molecular sieve catalyst, including ZSM-5 zeolite molecular sieve, it is characterised in that: possibly together with the cobalt element accounting for described ZSM-5 zeolite molecular sieve mass fraction 0.5%～12.5%.
Co-containing ZSM-5 zeolite molecular sieve catalyst the most according to claim 1, it is characterised in that: described cobalt element is uniformly dispersed in ZSM-5 zeolite molecular sieve surface or duct.
3. the preparation method of a Co-containing ZSM-5 zeolite molecular sieve catalyst, it is characterised in that: comprise the following steps:
A, cobalt 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 Co-containing ZSM-5 zeolite molecular sieve catalyst the most according to claim 3, it is characterised in that: in described cobalt nitrate solution, the quality of cobalt nitrate is the 1.5%～39% of ZSM-5 mass.
5. according to the preparation method of the Co-containing ZSM-5 zeolite molecular sieve catalyst described in claim 3 or 4, it is characterised in that: step D gained catalyst powder is broken to 20～40 mesh.
CN201610042906.9A 2016-01-22 2016-01-22 Cobalt-modified ZSM-5 zeolite molecular sieve catalyst and method for preparing same Pending CN105709812A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610042906.9A CN105709812A (en) 2016-01-22 2016-01-22 Cobalt-modified ZSM-5 zeolite molecular sieve catalyst and method for preparing same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610042906.9A CN105709812A (en) 2016-01-22 2016-01-22 Cobalt-modified ZSM-5 zeolite molecular sieve catalyst and method for preparing same

Publications (1)

Publication Number Publication Date
CN105709812A true CN105709812A (en) 2016-06-29

Family

ID=56153806

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610042906.9A Pending CN105709812A (en) 2016-01-22 2016-01-22 Cobalt-modified ZSM-5 zeolite molecular sieve catalyst and method for preparing same

Country Status (1)

Country Link
CN (1) CN105709812A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582794A (en) * 2016-11-18 2017-04-26 天津大学 Catalyst based on modified molecular sieve and hydrotalcite derived oxides and applied to diesel engine, preparation and application
BE1027253B1 (en) * 2019-08-15 2020-11-30 North China Electric Power Univ Baoding Device and process for the catalytic oxidation of magnesium sulfite, cobalt nitrate catalyst / zsm-5 molecular sieve and process for the preparation thereof
CN114669321A (en) * 2022-04-21 2022-06-28 杭州电子科技大学 Cobalt-containing zeolite catalyst and preparation method and application 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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582794A (en) * 2016-11-18 2017-04-26 天津大学 Catalyst based on modified molecular sieve and hydrotalcite derived oxides and applied to diesel engine, preparation and application
CN106582794B (en) * 2016-11-18 2019-07-26 天津大学 Use for diesel engine catalyst and preparation and application based on modified molecular screen and hydrotalcite Derived Oxides
BE1027253B1 (en) * 2019-08-15 2020-11-30 North China Electric Power Univ Baoding Device and process for the catalytic oxidation of magnesium sulfite, cobalt nitrate catalyst / zsm-5 molecular sieve and process for the preparation thereof
CN114669321A (en) * 2022-04-21 2022-06-28 杭州电子科技大学 Cobalt-containing zeolite catalyst and preparation method and application thereof

Similar Documents

Publication Publication Date Title
US10675586B2 (en) Hybrid binary catalysts, methods and uses thereof
Pu et al. Low-temperature selective catalytic reduction of NOx with NH3 over zeolite catalysts: A review
JP5837088B2 (en) Use of metal-doped zeolites and zeotypes for catalytic improvement of nitrogen oxides
CN109174173A (en) A kind of molecular sieve SCR catalyst preparation method and its catalyst of preparation
EP2308596A1 (en) Cu/zeolite SCR catalyst for NOx reduction in exhaust gases and manufacture method thereof
EP3388392B1 (en) Copper-containing zeolites having a low alkali metal content, method of making thereof, and their use as scr catalysts
CN101428212B (en) Selective catalysis reduction denitrate catalyst for composite carrier flue gas and preparation method thereof
EP2949391B1 (en) Method for producing an iron-chabazite exhaust gas purification catalyst
CN105013467A (en) Low-temperature SO2-resistant MnxSby/PG-type SCR denitration catalyst and preparation method thereof
CN111036280B (en) Preparation method of Fe/Cu-SSZ-13 molecular sieve
CN105709812A (en) Cobalt-modified ZSM-5 zeolite molecular sieve catalyst and method for preparing same
CN105833901A (en) PrOx-MnOx/SAPO-34 low-temperature SCR smoke denitration catalyst and preparation method and application thereof
Martinovic et al. Composite Cu-SSZ-13 and CeO2-SnO2 for enhanced NH3-SCR resistance towards hydrocarbon deactivation
KR20160129030A (en) Scr catalysts having improved low temperature performance, and methods of making and using the same
He et al. SO2-tolerant NOx reduction over SO42--coordinated Cu-SAPO-34 catalysts via protecting the reduction and re-oxidation of Cu sites
GB2547288A (en) Catalyst for oxidising ammonia
EP3096874B1 (en) Scr catalytic converter
CN105597808A (en) Cobalt modified SBA-15 molecular sieve catalyst and preparation method
CN107570205B (en) Preparation method of modified Beta molecular sieve catalyst
CN103816916A (en) Preparation method of catalyst suitable for low-temperature denitration of composite oxide
CN105562069A (en) Copper-modification molecular sieve SCR catalyst and preparing method
CN105597813A (en) Manganese-modified molecular sieve SCR catalyst and preparing method
CN105536859A (en) Nickel-modified molecular sieve SCR catalyst and preparation method thereof
EP2193843B1 (en) Zeolite catalyst for removing nitrogen oxides, method for preparing the same, and method of removing nitrogen oxides using the same
CN102179252A (en) Cu/CeOx-TiO2 for selective catalytic oxidization of ammonia and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20160629

WD01 Invention patent application deemed withdrawn after publication