CN102451749A - Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof - Google Patents

Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof Download PDF

Info

Publication number
CN102451749A
CN102451749A CN201010522956XA CN201010522956A CN102451749A CN 102451749 A CN102451749 A CN 102451749A CN 201010522956X A CN201010522956X A CN 201010522956XA CN 201010522956 A CN201010522956 A CN 201010522956A CN 102451749 A CN102451749 A CN 102451749A
Authority
CN
China
Prior art keywords
molecular sieve
catalyst
ssz
temperature
preparation
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
CN201010522956XA
Other languages
Chinese (zh)
Inventor
包信和
李鹏
张维萍
韩秀文
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.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
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 Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN201010522956XA priority Critical patent/CN102451749A/en
Publication of CN102451749A publication Critical patent/CN102451749A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Landscapes

  • Catalysts (AREA)

Abstract

The invention relates to a catalyst for preparing olefin by conversion of methanol and a preparation method thereof. According to the invention, a cerium modified microporous silicon-aluminum molecular sieve SSZ-13 is used in a reaction for preparing olefin by conversion of methanol, and the stability of the catalyst is obviously improved, and the problem that the microporous molecular sieve is rapidly inactivated in the conversion reaction of methanol in a fixed bed reactor can be solved.

Description

A kind of catalyst and preparation and application that is used for methanol conversion system alkene
Technical field
The present invention relates to a kind of catalyst and preparation and application that is used for methanol conversion system alkene.
Background technology
Ethene and propylene are basic raw material for chemical industry.The production route of traditional ethene and propylene comprises the cracking and the FCC catalytic cracking process of naphtha, and petroleum path is occupied an leading position.Along with the rising of International Crude Oil and the minimizing day by day of petroleum resources in recent years, route production ethene and the propylene of developing new non-oil resource seem particularly important.Methyl alcohol be from coal and natural gas can mass preparation chemicals, the ten minutes that just shows from the status of the methyl alcohol chemistry of the large chemical products of methyl alcohol preparation is important.Therefore preparing low carbon olefinic hydrocarbon with methanol is from the up-and-coming process route of non-oil resource.The basic research of methanol-to-olefins and industrial applications are the research focuses of academia and industrial quarters.
In the methanol conversion system olefine reaction, small pore molecular sieve shows excellent selectivity of light olefin.The aperture is little but there is catalyst in small pore molecular sieve, is prone to coking, and problems such as rapid deactivation need to solve a short difficult problem of small pore molecular sieve catalyst life-span.SSZ-13 is a kind of aperture Si-Al molecular sieve, is used for the present Research of methanol conversion system olefine reaction at present:
Zhu etc. have synthesized the SSZ-13 molecular sieve of different Si/Al ratios, have studied the influence of sour amount to propylene and ethene ratio, find sour amount can not with C 3 =/ C 2 =Ratio interrelated, temperature 598K methyl alcohol weight space velocity 0.5h -1Condition under, methanol conversion keeps 100% on SSZ-13 (Si/Al=67) molecular sieve in 5h.(Microporous?Mesoporous?and?Materials?112(2008)153)。
Zhu etc. have synthesized the SSZ-13 molecular sieve of different Si/Ga ratios, show the excellent ethene and the selectivity of propylene, temperature 598K methyl alcohol weight space velocity 0.5h in the methanol conversion reaction -1Condition under, methanol conversion can keep 100% in 2h.(Microporous?Mesoporous?and?Materials116(2008)253)。
Zhu etc. have synthesized B-SSZ-13 and Fe-SSZ-13, temperature 673K methyl alcohol weight space velocity 0.5h -1Under the condition, during reaction time 30min, methanol conversion is 80% on the Fe-SSZ-13 molecular sieve, and reaction time 2h, methanol conversion are 20%, and catalysqt deactivation is very fast.(CatalysisCommunications?10(2009)447)。
Usefulness NaOH solution such as Sommer remove the method for molecular sieve upper skeleton silicon and make mesopore at the SSZ-13 molecular sieve, 350 ℃ of methyl alcohol weight space velocities of temperature 6.2h -1Condition under, reaction time 1h, methanol conversion are 100%, reaction time 2h, methanol conversion are 30%, rapid deactivation.The mesoporous stability that does not improve the SSZ-13 catalyst that produces on the molecular sieve surface, along with the increase of alkaline concentration, the stability of SSZ-13 catalyst further descends.(Microporous?Mesoporous?and?Materials132(2010)384)。
Summary of the invention
Problem to be solved by this invention is aperture Si-Al molecular sieve poor catalyst stability in fixed bed reactors methanol conversion system olefin hydrocarbon, is prone to coking, and the problem of rapid deactivation provides a kind of catalyst and preparation and application of methanol-to-olefins.
In order to solve the problems of the technologies described above, the scheme that the present invention adopts is following:
A kind of catalyst that is used for methanol conversion system alkene is cerium modified SSZ-13 molecular sieve.
The SSZ-13 molecular sieve is the octatomic ring small pore molecular sieve with CHA topological structure, and its component is SiO 2, Al 2O 3And Na 2O, the Si/Al of molecular sieve is 1～100 than scope.
The quality percentage composition that Ce elements accounts for the SSZ-13 molecular sieve is 0.005～40%.
Preparation of catalysts may further comprise the steps:
1. the octatomic ring small pore molecular sieve SSZ-13 that will have the CHA topological structure; Silica alumina ratio (Si/Al) be 1～100 be selected from ammonium nitrate, ammonium chloride; A kind of in the hydrochloric acid is condition refluxed 1～5h of 25～100 ℃ in temperature, and the concentration of acid solution is 0.1～5mol/L, filters, after the washing, oven dry; At 300～600 ℃ of roasting 1～6h of temperature, obtain the SSZ-13 molecular sieve of Hydrogen.
With the Hydrogen SSZ-13 that obtains in the step 1 be selected from cerous nitrate, cesium formate, cerous carbonate; A kind of in the sulfuric acid decorations calculates with the quality percentage composition of cerium, and the content that cerium accounts for molecular sieve is 0.005～40%; Ratio 1: 1～1 according to solid-liquid: 20g/mL; Fully mixing, is 25～80 ℃ in temperature, and vacuum is 10 -1～10 -4 Flood 12～24h under the Pa condition.
3. be under 80～120 ℃ with the molecular sieve that obtains in the step 2 in temperature, oven dry 12～24h is under 300～600 ℃ in temperature, roasting 1～6h.Be prepared into required cerium modified SSZ-13 molecular sieve.
Use the catalyst of the inventive method preparation to be used for methanol conversion system olefine reaction, the stability with catalyst significantly improves, the characteristics that yield of light olefins is high.
Through embodiment the present invention is done further elaboration below.
Description of drawings
Methanol conversion on the different cerium content SSZ-13 of Fig. 1 molecular sieve;
Dimethyl ether selectivity on the different cerium content SSZ-13 of Fig. 2 molecular sieve;
The different cerium content SSZ-13 of Fig. 3 go up the selectivity of triolefin (ethene, propylene and butylene);
Figure 45 Ce-SSZ-13 is used for the estimation of stability of methanol conversion reaction;
Figure 57 Ce-SSZ-13 is used for the estimation of stability of methanol conversion reaction.
The specific embodiment
[comparative example 1]
With silica alumina ratio (Si/Al) is 13 sodium type SSZ-13, adopt the ammonium nitrate exchange after, filter, washing and oven dry back be the SSZ-13 that 550 ℃ of following roasting 3h obtain Hydrogen in temperature.
[embodiment 1-3]
With silica alumina ratio is 13 sodium type SSZ-13, is under 80 ℃ in temperature, and the volume liquid-solid ratio is that exchange 2h after filtration, washing and the drying, exchanges twice continuously in 10: 1 the 0.4mol/L ammonium nitrate solution, and step is the same, and fully dry back is at 550 ℃ of following roasting 3h.The Hydrogen SSZ-13 molecular sieve that obtains after the roasting according under 10: 1 the condition of liquid-solid ratio, is fully mixed with the aqueous solution of cerous nitrate.Wherein cerium calculates with weight percentage, and the weight percentage ratio that cerium accounts for molecular sieve is 3%, 5%, 7%.With the dipping molecular sieve at room temperature place 12h after, be 10 at vacuum condition -1Pa, temperature is under 50 ℃, impregnation drying 12h.110 ℃ of baking ovens, dry 12h are put in taking-up.Under 550 ℃, under the air atmosphere, roasting 3h obtains the molecular sieve of cerium modified SSZ-13 with dried molecular sieve.
[embodiment 4]
The comparative example 1 and the modified molecular screen of embodiment 1-4 preparation are used for the reaction of methanol conversion system alkene, are raw material with methyl alcohol, and the bed temperature of evaluate catalysts is 400 ℃, and reaction pressure is 0.1MPa, and the weight space velocity of methyl alcohol is 2h -1, methyl alcohol is through behind the beds, and on-line chromatograph detects product and forms.Reaction result is listed among Fig. 1-3.
Fig. 1, methanol conversion descends with the increase in reaction time fast on the SSZ-13 molecular sieve, and during reaction time 7h, methanol conversion is 22%.And the stability of cerium modified SSZ-13 molecular sieve significantly improves, and during reaction time 7h, methanol conversion is 84% on the 7Ce-SSZ-13 molecular sieve.This stability that shows cerium modified SSZ-13 molecular sieve methanol conversion reacting middle catalyst significantly improves.Fig. 2, the selectivity of DME significantly increases than the sample after the Ce modification behind reaction time 4h on the SSZ-13 molecular sieve.Fig. 3, behind the 4h on the cerium modified SSZ-13 molecular sieve triolefin selectivity still comparatively stable, and the beginning on the SSZ-13 molecular sieve obviously descends.
Embodiment 5-6
With the sample among embodiment 3 and the embodiment 4, under 400 ℃ of temperature, the air speed of methyl alcohol is 2h -1, reaction pressure is 0.1MPa, estimates the stability of its catalyst, and the result lists among Fig. 4 and Fig. 5, and Fig. 4 is 5Ce-SSZ-13, and Fig. 5 is 7Ce-SSZ-13.Wherein 5Ce and 7Ce represent the quality percentage composition of Ce respectively.
The result shows that on the 5Ce-SSZ-13 molecular sieve, reaction time 15h, methanol conversion are 69%.On the 7Ce-SSZ-13 molecular sieve, reaction time 24h, methanol conversion are 68%.With the result's contrast on the SSZ-13 molecular sieve among Fig. 1, can find out that on the SSZ-13 molecular sieve, reaction time 5h, methanol conversion are 46%, and SSZ-13 molecular sieve rapid deactivation, methanol conversion descends with the increase in reaction time fast.This shows that not only cerium modified SSZ-13 catalyst shows higher stability in methanol conversion reaction, and along with the increase of cerium content, the stability of this catalyst further improves.

Claims (8)

1. catalyst that is used for methanol conversion system alkene, it is characterized in that: said catalyst is cerium modified SSZ-13 molecular sieve.
2. according to the said catalyst of claim 1, it is characterized in that: the SSZ-13 molecular sieve is the octatomic ring small pore molecular sieve with CHA topological structure, and its component is SiO 2, Al 2O 3And Na 2O, the Si/Al of molecular sieve is 1～100 than scope.
3. according to the said catalyst of claim 1, it is characterized in that: the quality percentage composition that Ce elements accounts for the SSZ-13 molecular sieve is 0.005～40%.
4. the small pore molecular sieve described in the claim 2, it is characterized in that: the aperture is 0.2～0.5nm.
5. said Preparation of catalysts method of claim 1 is characterized in that:
1) with a kind of with in the acid solution ammonium nitrate of concentration 0.1～5mol/L, ammonium chloride, the hydrochloric acid of the SSZ-13 molecular sieve of sodium type, is 25～100 ℃ of refluxed 1～5h, filters in temperature; Washing; After the oven dry,, obtain the SSZ-13 molecular sieve of Hydrogen at 300～600 ℃ of following roasting 1～6h of temperature;
2) form of cerium with salting liquid is impregnated on the SSZ-13 molecular sieve of Hydrogen; The temperature of dipping preparation catalyst is 25～80 ℃, and pressure is 10 -1～10 6Pa, dip time are 0～24h;
3) catalyst behind the dipping is to dry 0～24h under 25～140 ℃ of conditions in temperature, is 300～600 ℃ of following roasting 1～6h in temperature then.
6. according to the described preparation method of claim 5, it is characterized in that: said cerium salt is cerous nitrate, cesium formate, a kind of in the cerous carbonate, sulfuric acid decorations.
7. according to the described preparation method of claim 5, it is characterized in that: the catalyst solid quality was 1: 1～1: 20 with the ratio of dipping salting liquid when said dipping prepared catalyst, and the measurement unit of ratio is g/mL.
8. the said catalyst of claim 1 can be used in the reaction of methanol conversion system alkene.
CN201010522956XA 2010-10-27 2010-10-27 Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof Pending CN102451749A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010522956XA CN102451749A (en) 2010-10-27 2010-10-27 Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010522956XA CN102451749A (en) 2010-10-27 2010-10-27 Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof

Publications (1)

Publication Number Publication Date
CN102451749A true CN102451749A (en) 2012-05-16

Family

ID=46035676

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010522956XA Pending CN102451749A (en) 2010-10-27 2010-10-27 Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof

Country Status (1)

Country Link
CN (1) CN102451749A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103846102A (en) * 2014-03-17 2014-06-11 南开大学 Catalyst for preparing propylene by directly converting ethylene, and application method thereof
WO2014173229A1 (en) * 2013-04-25 2014-10-30 武汉凯迪工程技术研究总院有限公司 Fischer-tropsch synthesis catalyst for syngas to low carbon olefins, modified molecular sieve carrier and preparation method thereof
CN104437607A (en) * 2014-11-06 2015-03-25 南开大学 Tin-containing molecular sieve catalyst used for preparing ethylene glycol by hydrating ethylene oxide and application method
EP2908946A4 (en) * 2012-10-19 2016-06-29 Basf Corp 8-ring small pore molecular sieve as high temperature scr catalyst
CN106824262A (en) * 2015-12-03 2017-06-13 中国石油化工股份有限公司 SSZ-13/SCM-9 composite molecular sieve catalysts, preparation method and its usage
CN106925340A (en) * 2015-12-31 2017-07-07 中国石油天然气股份有限公司 Catalyst for preparing olefin from methanol and preparation method thereof
CN109092287A (en) * 2017-06-21 2018-12-28 中国石油化工股份有限公司 Selective acetylene hydrocarbon hydrogenation catalyst
CN109833905A (en) * 2017-11-29 2019-06-04 中国科学院大连化学物理研究所 Molecular sieve catalyst and its preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1467155A (en) * 2002-07-10 2004-01-14 中国石油化工股份有限公司 Method for preparing aluminium silicophosphate molecular sieve
US20080159936A1 (en) * 2006-12-27 2008-07-03 Chevron U.S.A. Inc. Treatment of cold start engine exhaust
US20090110621A1 (en) * 2004-11-30 2009-04-30 Lun-Teh Yuen Treatment of engine exhaust using boron-containing molecular sieve cha
CN101730575A (en) * 2007-04-26 2010-06-09 约翰逊马西有限公司 transition metal/zeolite scr catalysts

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1467155A (en) * 2002-07-10 2004-01-14 中国石油化工股份有限公司 Method for preparing aluminium silicophosphate molecular sieve
US20090110621A1 (en) * 2004-11-30 2009-04-30 Lun-Teh Yuen Treatment of engine exhaust using boron-containing molecular sieve cha
US20080159936A1 (en) * 2006-12-27 2008-07-03 Chevron U.S.A. Inc. Treatment of cold start engine exhaust
CN101730575A (en) * 2007-04-26 2010-06-09 约翰逊马西有限公司 transition metal/zeolite scr catalysts

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2908946A4 (en) * 2012-10-19 2016-06-29 Basf Corp 8-ring small pore molecular sieve as high temperature scr catalyst
US10220375B2 (en) * 2013-04-25 2019-03-05 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Catalyst for fischer-tropsch synthesis and method for preparing the same, and method for preparing modified molecular sieve carrier
WO2014173229A1 (en) * 2013-04-25 2014-10-30 武汉凯迪工程技术研究总院有限公司 Fischer-tropsch synthesis catalyst for syngas to low carbon olefins, modified molecular sieve carrier and preparation method thereof
US20160045903A1 (en) * 2013-04-25 2016-02-18 Wuhan Kaidi Engineering Technology Research Institute Co., Ltd. Catalyst for fischer-tropsch synthesis and method for preparing the same, and method for preparing modified molecular sieve carrier
CN103846102B (en) * 2014-03-17 2016-05-11 南开大学 Directly transform for ethene catalyst and the application process of preparing propylene
CN103846102A (en) * 2014-03-17 2014-06-11 南开大学 Catalyst for preparing propylene by directly converting ethylene, and application method thereof
CN104437607A (en) * 2014-11-06 2015-03-25 南开大学 Tin-containing molecular sieve catalyst used for preparing ethylene glycol by hydrating ethylene oxide and application method
CN106824262A (en) * 2015-12-03 2017-06-13 中国石油化工股份有限公司 SSZ-13/SCM-9 composite molecular sieve catalysts, preparation method and its usage
CN106824262B (en) * 2015-12-03 2019-02-19 中国石油化工股份有限公司 SSZ-13/SCM-9 composite molecular sieve catalyst, preparation method and its usage
CN106925340A (en) * 2015-12-31 2017-07-07 中国石油天然气股份有限公司 Catalyst for preparing olefin from methanol and preparation method thereof
CN109092287A (en) * 2017-06-21 2018-12-28 中国石油化工股份有限公司 Selective acetylene hydrocarbon hydrogenation catalyst
CN109833905A (en) * 2017-11-29 2019-06-04 中国科学院大连化学物理研究所 Molecular sieve catalyst and its preparation method and application
WO2019104778A1 (en) * 2017-11-29 2019-06-06 中国科学院大连化学物理研究所 Molecular sieve catalyst, preparation method therefor and application thereof
RU2753413C1 (en) * 2017-11-29 2021-08-16 Далянь Инститьют Оф Кемикал Физикс, Чайниз Академи Оф Сайэнс Catalyst based on molecular sieve, method for production and application thereof
US11247198B2 (en) 2017-11-29 2022-02-15 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Molecular sieve catalyst, preparation method therefor and application thereof

Similar Documents

Publication Publication Date Title
CN102451749A (en) Catalyst for preparing olefin by conversion of methanol as well as preparation and application thereof
JP6778821B2 (en) Method for producing lower olefin by direct conversion of catalyst and syngas
JP6523549B2 (en) Production method of methyl acetate
CN106345514A (en) Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof
CN101745414B (en) Catalyst for producing light olefins through methanol and preparation method thereof
CN104056652B (en) A kind of hud typed ZSM-5 molecular sieve pellet catalyst
CN103506150B (en) The catalyst of preparing gasoline by methanol and method for making thereof and application is used for by steam modification
CN109939728A (en) A kind of method that supported catalyst and synthesis gas directly convert producing light olefins
CN109939667A (en) A kind of method that catalyst and synthesis gas directly convert producing light olefins
CN101722033A (en) Core-shell type aromatic conversion catalyst, preparation method and application thereof
CN109967118A (en) A kind of Method in situ modification of the HZSM-5 molecular sieve catalyst for methanol conversion for preparing arene
CN104056653B (en) A kind of catalyst for producing propylene with methanol
CN104437601B (en) A kind of ZSM-5 Type Zeolites agent and its application for preparing propylene from methanol
CN109890782A (en) Produce the single-stage process of butadiene
CN104056654A (en) ZSM-5 molecular sieve composition, preparation method and application thereof
CN104588011A (en) Alkane dehydrogenation catalyst and preparation method thereof
CN104248952A (en) Catalyst for preparation of glycol by oxalate hydrogenation and preparation method thereof
CN102553632A (en) Low carbon alkane dehydrogenation catalyst, preparation method and application thereof
CN103769207A (en) Catalyst used for production of isobutene via isomerization of n-butene skeleton and combined production of propylene, and preparation method and applications thereof
CN116514626B (en) Method for preparing trimerization product by high-selectivity oligomerization of isobutene
CN103058807B (en) Method for producing arene by utilizing methanol
CN114588934B (en) Silicon-modified indium-based oxide-molecular sieve composite material and preparation method and application thereof
CN105772071A (en) Core-shell-structured catalyst for light olefin disproportionation, and preparation method and application thereof
CN104549247A (en) Hydrocarbon material selective hydrogenation catalyst and preparation method thereof
CN102267853A (en) Method for producing 1-butene through 2-butene isomerization

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20120516