CN109745965A - A method of the catalyst and co hydrogenation of the oxide containing CeZr directly convert producing light olefins - Google Patents

A method of the catalyst and co hydrogenation of the oxide containing CeZr directly convert producing light olefins Download PDF

Info

Publication number
CN109745965A
CN109745965A CN201711089864.5A CN201711089864A CN109745965A CN 109745965 A CN109745965 A CN 109745965A CN 201711089864 A CN201711089864 A CN 201711089864A CN 109745965 A CN109745965 A CN 109745965A
Authority
CN
China
Prior art keywords
catalyst
component
oxide
cezr
low
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.)
Granted
Application number
CN201711089864.5A
Other languages
Chinese (zh)
Other versions
CN109745965B (en
Inventor
潘秀莲
焦峰
包信和
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 CN201711089864.5A priority Critical patent/CN109745965B/en
Publication of CN109745965A publication Critical patent/CN109745965A/en
Application granted granted Critical
Publication of CN109745965B publication Critical patent/CN109745965B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to co hydrogenations directly to prepare low-carbon alkene, a kind of method for directly converting producing light olefins more particularly to the catalyst and co hydrogenation of oxide containing CeZr, it is using synthesis gas as reaction raw materials, conversion reaction is carried out in fixed bed or moving bed, the catalyst that this method uses is combined by component A and B component, its component A is metal composite oxide CexZr (1-x) O2, B component is molecular sieve, and metal oxide and molecular sieve physics mode have mixed catalytic action.Weight ratio range 0.1-20 between component A and B component, reaction process has very high product yield and selectivity, especially stability is preferable, the selectivity that the selectivity of low-carbon alkene still can maintain low-carbon alkene after 650h can be maintained to react can achieve 65-73%, byproduct methane is selectively extremely low (< 15%), has a good application prospect.

Description

The catalyst and co hydrogenation of a kind of oxide containing CeZr directly convert low-carbon processed The method of alkene
Technical field
The invention belongs to co hydrogenations to prepare low-carbon alkene, and in particular to a kind of catalyst and co hydrogenation are straight The method of switching through producing light olefins.
Background technique
Low-carbon alkene refers to the alkene that carbon atom number is less than or equal to 4.Using ethylene, propylene as the low-carbon alkene right and wrong of representative Often important basic organic chemical industry raw material, with the rapid growth of China's economy, for a long time, low-carbon alkene market is not for answering It asks.Currently, the petrochemical industry route that the production of low-carbon alkene mainly uses lighter hydrocarbons (ethane, naphtha, light diesel fuel) to crack, due to The long-term run at high level of growing lack and crude oil price of Global Oil resource develops low-carbon alkene industry and relies solely on petroleum light hydrocarbon Increasing raw material problem can be encountered for the tube cracking furnace technique of raw material, low-carbon alkene production technology and raw material must be polynary Change.It selects synthesis gas producing olefinic hydrocarbons technique that can widen raw material sources, will be with crude oil, natural gas, coal and recyclable materials Raw material produces synthesis gas, provides alternative solution for the steam cracking technology aspect based on high cost feedstocks such as naphtha.Synthesis gas The direct preparing low-carbon olefins of one-step method be exactly carbon monoxide and hydrogen under the action of catalyst, by Fischer-Tropsch synthesis directly be made The process of low-carbon alkene of the carbon atom number less than or equal to 4, the technique are not necessarily to as indirect method technique from synthesis gas through methanol Or dimethyl ether, alkene is further prepared, simplification of flowsheet greatly reduces investment.
Synthesis gas passes through the direct preparing low-carbon olefins of F- T synthesis, it has also become the research hotspot of fischer-tropsch synthetic catalyst exploitation One of.In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with the Group IIAs alkali metal oxide such as MgO Or iron-Mn catalyst system that silica-rich zeolite molecular sieve (or phosphorus aluminium zeolite) supports, auxiliary agent is made with highly basic K or Cs ion, is being closed It is 1.0~5.0MPa at gas reaction for preparing light olefins pressure, at 300~400 DEG C of reaction temperature, can get higher activity (CO Conversion ratio 90%) and selectivity (selectivity of light olefin 66%).The patent ZL031095852 that Beijing University of Chemical Technology is declared In, use vacuum impregnation technology to prepare manganese, copper, zinc silicon, potassium etc. anti-for preparation of low carbon olefines by synthetic gas for the Fe/C catalyst of auxiliary agent It answers, under conditions of no unstripped gas recycles, CO conversion ratio 96%, selectivity 68% of the low-carbon alkene in hydrocarbon.Most Closely, Dutch Utrecht university de Jong professor team uses SiC, the Fe and Na, S of the load of the inert carriers such as carbon nano-fiber Etc. addition agent modified Fe catalyst, the selectivity of light olefin that progress very well obtains 61% is achieved, but conversion ratio increases When, selectivity reduces.The catalyst of above-mentioned report is to use metallic iron or cementite for active component, and reaction follows metal watch The chain propagation reaction mechanism in face, the selectivity of product low-carbon alkene is lower, and the selectivity of especially single product such as ethylene is lower than 30%, meanwhile, methane content is higher than 15%.
Nearest Dalian Inst of Chemicophysics, Chinese Academy of Sciences's packet letter and academician and Pan Xiulian researcher report aluminium oxide The ZnCr of load2O4Spinel oxide and the compound bifunctional catalyst of multi-stage porous SAPO-34 molecular sieve, realize CO conversion ratio When 17%, the selectivity of low-carbon alkene 80%, wherein low-carbon alkanes are selectively 14, and the ratio (ethylenic alkoxy rate) of alkene and alkane reaches To 5.7.But the space that the stability of catalyst is still improved, especially the selectivity of low-carbon alkene is bright after 760h reaction Aobvious decline, only 60% or so.
Summary of the invention
In view of the above-mentioned problems, the catalyst and co hydrogenation the present invention provides a kind of oxide containing CeZr directly turn Change the method for producing light olefins, especially stability is preferable, and the selectivity of low-carbon alkene still can after 650h can be maintained to react Maintain the selectivity of low-carbon alkene in the product up to 65~73%, methane selectively is lower than 15%.
The technical solution of the present invention is as follows:
A kind of catalyst of the oxide containing CeZr, the oxide catalyst containing CeZr is by component A and B component with physics side Formula mixing, the active ingredient of component A are metal composite oxide, and the metal composite oxide is CexZr (1-x) O2, B component For molecular sieve, x value range is 0.6-0.98, preferably 0.8-0.98.Sample in preferred scope remains to after long-time is reacted Show more preferably olefine selective and lower methane selectively.
The pattern that the metal composite oxide is observed under a scanning electron microscope is bar-like or spherical, preferably stick Shape.Rod-like samples expose more active crystal faces compared to spherical sample, better modulation reaction atmosphere lower surface Ce4+/Ce3+ Ion ratio, and then modulation surface oxygen vacancies makes the generation for being more advantageous to alkene, and methane is inhibited to generate.
The catalyst B component is the molecular sieve with CHA, AEI topological structure, 8 annulus ducts and suitable cage Size is conducive to the generation of low-carbon alkene.
Between the weight ratio 0.1-20 range between active ingredient and B component in the catalyst component A, preferably 0.3-5。
The metal composite oxide is made of the crystal grain that size is 5-30nm, deep from grain surface to intra-die direction Degree is in the distance range of 0.3nm, there are a large amount of oxygen vacancies, i.e., the reasonable opinion stoichiometric ratio 60% of oxygen atom mole hereinafter, It is preferred that oxygen atom mole is reasonable to discuss stoichiometric ratio 60%-10%, more preferably 40-10%；Surface Lacking oxygen is defined as (oxygen Atomic mol is reasonable to discuss nonstoichiometric molar ratio content), corresponding Lacking oxygen molar ratio is preferably 40-90%, more preferably 60-90%.
It is can choose in the component A added with dispersing agent, dispersing agent Al2O3、SiO2、Cr2O3、ZrO2、TiO2、ZnO One of or two kinds, metal composite oxide is scattered in dispersing agent, and content of the dispersing agent in component A is in 0.05- 90wt.%, remaining is active metal composite oxide, and suitable dispersing agent is conducive to control oxide nano-particles size, And it is conducive to shaping of catalyst.
The backbone element composition of the molecular sieve of CHA, AEI topological structure can be Si-Al-O, Ga-Al-O, Ti-Si- O, one of Si-Al-P-O, Al-P-O, Ge-Al-O or two kinds or more；
Physics mode mixing can be used one of mechanical stirring, ball milling, shaking table mixing, mechanical lapping or two kinds with Upper progress is compound.
A kind of method that synthesis gas directly converts producing light olefins, using synthesis gas as unstripped gas, using above-mentioned catalyst, Conversion reaction is carried out in fixed bed or moving bed.
Synthesis gas is H2/ CO gaseous mixture, H2/ CO molar ratio is 0.2-3.5, preferably 0.3-2.5；The pressure of the synthesis gas Power is 0.5-10MPa, and reaction temperature is 300-600 DEG C, air speed 300-10000h-1；Synthesis gas H2/ CO molar ratio is 0.2- 3.5, preferably 0.3-2.5.
The preparation process of metal composite oxide is: using cerium, zirconates presoma, adds urea, ammonium hydroxide, carbon thereto Yu Shuizhong is mutually mixed sour ammonium at room temperature；Above-mentioned mixed liquor is aged, washing, filtering and drying are then taken out, it is resulting solid Body roasts in air atmosphere or sodium hydroxide solution is added in water using cerium, zirconates presoma using the method for hydrothermal synthesis Hot kettle high temperature high pressure crystallization is taken out afterwards be filtered for a period of time, washs, dry, and obtained solid roasts in air atmosphere, Obtain metal composite oxide CexZr (1-x) O2.
Using one of etching agents such as oleic acid, methenamine, ethylenediamine, ammonium hydroxide, hydrazine hydrate or two kinds or more, by metal Oxide is soaked in etchant solution；Above-mentioned suspended matter is heated 30-90 minutes at 100-150 DEG C, then takes out washing Filtering obtains the metal oxide under reaction atmosphere with exhibiting high surface oxygen vacancies；The dry reduction in atmosphere by filtrate Processing, atmosphere are inert gas or inert gas and reducibility gas gaseous mixture, inert gas N2, one of He and Ar Or two kinds or more, reducing atmosphere H2, CO one or two or more kinds, the body of inert gas and reducibility gas in gaseous mixture Product is handled 0.5-5 hours, treatment temperature is 20-350 DEG C than being 100/10-0/100.
The present invention compared with prior art the advantages of it is as follows:
(1) present invention is different from traditional preparing light olefins from methanol technology (referred to as MTO), realizes one-step method and directly will Synthesis gas is converted into low-carbon alkene.
(2) preparation process of the composite catalyst in the present invention is simple, mild condition；And reaction process has very high production Product yield and selectivity, especially with CexZr (1-x) O2 oxide, oxide microscopic appearance is bar-like or spherical, preferably stick Shape, stability is preferable, and the selectivity of low-carbon alkene still can maintain the choosing of C2-C4 low-carbon alkene after 650h can be maintained to react Selecting property can achieve 65-73%, while byproduct methane is selectively extremely low (< 15%), has a good application prospect.
Specific embodiment
The present invention is further elaborated below by embodiment, but scope of the presently claimed invention is not by these realities Apply the limitation of example.Meanwhile embodiment has been merely given as realizing the partial condition of this purpose, but is not meant to must satisfy these Condition just can achieve this purpose.
Embodiment 1
One, the preparation of catalyst component A
(1) preparation of metal composite oxide CexZr (1-x) O2
(1) number is metal oxide 3, metal oxide 4, metal oxide 5, metal oxide 8, metal oxide 9 Sample use cerous nitrate, zirconium nitrate for presoma, add urea, ammonium hydroxide, ammonium carbonate Yu Shuizhong phase at room temperature thereto Mutually mixing；Above-mentioned mixed liquor is aged, washing, filtering and drying are then taken out, resulting solid roasts in air atmosphere, i.e., Obtain metal oxide CexZr (1-x) O2.
(2) number is metal oxide 1, and the sample of metal oxide 2, metal oxide 6, metal oxide 7 uses water The method of thermal synthesis uses cerous nitrate, zirconium nitrate for presoma, and sodium hydroxide solution is added in water heating kettle high temperature high pressure crystallization It takes out and is filtered after a period of time, wash, dry, obtained solid roasts in air atmosphere, obtains metal oxide CexZr (1-x)O2。
By above-mentioned sample using the etching agents such as oleic acid, methenamine, ethylenediamine, ammonium hydroxide, hydrazine hydrate, at normal temperature with metal Oxide ultrasound mixes, and metal oxide is soaked in etchant solution, and etching agent and metal oxide form complexing or direct Reduction reaction occurs；
Above-mentioned suspended matter is heated, washing filtering is then taken out, obtains the nano metal oxygen with exhibiting high surface oxygen vacancies Compound material.
In table 1: the mass ratio of catalyst and etching agent is 1:3.The mass ratio of oleic acid and methenamine is 1:1, not molten The mass ratio of agent, oleic acid and 5wt.% hydrazine hydrate is 95:5, without solvent；Specific treatment conditions include etching agent, temperature, processing Time and atmosphere type are as shown in table 1.
Dry or dry reduction:
The product of above-mentioned acquisition is by centrifugation or filtering, after being cleaned with deionized water, be dried in atmosphere or Dry and reduction treatment, atmosphere are the gaseous mixture of inert gas or inert gas and reproducibility gas, inert gas N2, He and One of Ar or two kinds or more, reducing atmosphere H2, CO one or two or more kinds, indifferent gas in dry reduction gaseous mixture The volume ratio of body and reducibility gas is 100/10~0/100, and dry and reduction treatment temperature is 350 DEG C, time 4h.I.e. Obtain the metal oxide materials that surface is rich in Lacking oxygen.Specific sample and its preparation condition such as table 1.Wherein surface Lacking oxygen is fixed Justice is (oxygen atom mole is reasonable to discuss nonstoichiometric molar ratio content).
The preparation and its performance parameter of 1 metal oxide materials of table
Two, the preparation of catalyst B (molecular sieve of CHA, AEL topological structure)
According to n (Al2O3)/n(P2O5)=1, n (SiO2)/n(Al2O3)=0.5, n (TEA)/n (Al2O3)=2, nH2O/n (Al2O3)=75.
Boehmite is mixed with deionized water, phosphoric acid is added, stirring 1h obtains homogeneous phase, and triethylamine is then added and stirs It mixes uniformly, is eventually adding silica solution, obtain Primogel after being aged 2h, transfer it in Autoclaves for synthesis, 180 DEG C quiet After state crystallization is quenched afterwards for 24 hours, washs, is dry, then 550 degree of roasting 6h obtain CHA molecular sieve in Muffle furnace.Corresponding product Successively it is defined as CHA1-4.
According to n (Al2O3)/n(P2O5)=1, n (TEAOH)/n (Al2O3)=1.4, nH2O/n(Al2O3)=50.
Boehmite is mixed with deionized water, phosphoric acid is added, stirring 1h obtains homogeneous phase, tetraethyl hydrogen is then added Amine-oxides stir evenly, and obtain Primogel after being aged 2h, transfer it in Autoclaves for synthesis, 150 DEG C of static crystallizations After being quenched, wash after 72h, being dry, then 550 degree of roasting 6h obtain AEI molecular sieve in Muffle furnace.Corresponding product is successively fixed Justice is AEI1-3；
Table 5 has the preparation and its performance parameter of the molecular sieve of CHA or AEL topological structure
Three, the preparation of catalyst
The catalyst A of required ratio and catalyst B are added to the container, transported using the high speed of these materials and/or container Separation, broken, mixing are realized in the effect of one or more of the raw extruding force of movable property, impact force, cutting power, frictional force etc. The purpose of, the conversion of mechanical energy, thermal energy and chemical energy is realized by modulation temperature and carrier gas atmosphere, further adjusts different component Between interaction.
In physics mode mixed process, 20-100 DEG C of mixing temperature can be set, it can be in atmosphere or directly in sky Carried out in gas, atmosphere are as follows: a) nitrogen and/or inert gas, b) gaseous mixture of hydrogen and nitrogen and/or inert gas, wherein hydrogen Volume of the gas in gaseous mixture is the gaseous mixture of 5~50%, c) CO and nitrogen and/or inert gas, and wherein CO is in gaseous mixture Volume be 5~20%, d) O2With the gaseous mixture of nitrogen and/or inert gas, wherein O2Volume in gaseous mixture is 5- 20%, the inert gas is one or more of helium, argon gas, neon.
Mechanical stirring: in stirred tank, being mixed catalyst A and B using stirring rod, by controlling mixing time (5min-120min) and rate (30-300r/min), the mixability and relative distance of adjustable catalyst A and B.
Ball milling: being rolled at a high speed in grinding pot using abrasive material and catalyst, is generated intense impact to catalyst, is rolled, reaches To dispersion, the effect of mixed catalyst A and B.By control abrasive material, (material can be stainless steel, agate, quartz.Size range: 5mm-15mm), with the ratio of catalyst (quality is than range: 20-100:1), the granularity and relative distance of adjustable catalyst.
Shaking table mixing method: catalyst A and B are pre-mixed, and are fitted into container；By the reciprocating vibration or circle that control shaking table Week oscillation, realizes the mixing of catalyst A and B；By adjusting hunting speed (range: 1-70r/min) and time (range: 5min- 120min), it realizes and uniformly mixes and adjust its relative distance.
Mechanical milling method: catalyst A and B are pre-mixed, and are fitted into container.In certain pressure (range: 5kg- Under 20kg), for example, by the lap tools such as machinery/magnetic stirring apparatus, ball mill, shaking table, autogenous mill/mortar and mixed catalysis Agent carries out relative motion (speed range: 30-300r/min), reaches and adjusts catalyst grain size, relative distance and realize uniformly mixed The effect of conjunction.
Specific catalyst preparation and its parameter attribute are as shown in table 6.
The preparation of 6 catalyst of table and its parameter attribute
Catalysis reaction example
By taking fixed bed reaction as an example, but catalyst is also applied for moving-burden bed reactor.The device is equipped with gas mass flow (tail gas of reactor is directly connect with the proportional valve of chromatography, carries out period real-time sampling point for meter, online product analysis chromatography Analysis).
The catalyst 2g of aforementioned present invention is placed in fixed bed reactors, using the air in Ar metathesis reactor, so Afterwards again in H2200 DEG C are warming up in atmosphere, switching and merging gas (H2/ CO molar ratio=0.2-3.5), the pressure of synthesis gas is 0.5- 10MPa is warming up to 300-600 DEG C of reaction temperature, adjusts the air speed of reactor feed gas to 500-10000ml/g/h.Product by Line chromatography tests and analyzes.
Change temperature, pressure and air speed, thus it is possible to vary reactivity worth.Low-carbon alkene after 650h (ethylene, propylene, butylene It is one or two or more kinds of) selectivity in the product is up to 65~73%, feed stock conversion 15-50%；Since catalyst is compound Metal oxide surface hydrogenation activity is not high, can avoid a large amount of generations of methane, and methane selectively is lower than 15%.
The concrete application and its effect data of 7 catalyst of table, the result after reacting 650h
The prior art: catalyst is the same as J in 201610600945.6 patent Examples.
The prior art 2: catalyst is the same as Z1 in 201610600945.6 patent Examples.
It is compared by embodiment, it is found that oxide containing CeZr is in suitable compositing range and preferred pattern Show more preferably selectivity.
Excellent selectivity of product is still able to maintain after reacting using long-lasting catalytic of the invention.
Above embodiments are provided just for the sake of the description purpose of the present invention, and are not intended to limit the scope of the invention.This The range of invention is defined by the following claims.It does not depart from spirit and principles of the present invention and the various equivalent replacements made and repairs Change, should all cover within the scope of the present invention.

Claims (10)

1. a kind of catalyst of oxide containing CeZr, the catalyst are physically mixed by component A and B component, component A Active ingredient is metal composite oxide, it is characterised in that: the metal composite oxide is CexZr (1-x) O2, x value model It encloses for 0.6-0.98, preferably 0.8-0.98, B component is molecular sieve.
2. the catalyst of the oxide according to claim 1 containing CeZr, it is characterised in that: the metal oxide it is microcosmic Pattern is bar-like or spherical, preferably rodlike.
3. the catalyst of the oxide according to claim 1 containing CeZr, it is characterised in that: B component is with CHA or AEI The molecular sieve of topological structure.
4. the catalyst of the oxide according to claim 1 containing CeZr, it is characterised in that: active ingredient and B in component A Weight ratio range between component is 0.1-20, preferably 0.3-5.
5. the catalyst of the oxide containing CeZr described in any one according to claim 1, it is characterised in that: the composition metal Oxide is surface Lacking oxygen in the distance range of 0.3nm from grain surface to intra-die direction depth under reaction atmosphere It is 40% or more, preferably 40-90%, more preferably 60-90%.
6. the catalyst of the oxide containing CeZr described in -5 any one according to claim 1, it is characterised in that: the component A In it is also an option that be added with dispersing agent, dispersing agent Al2O3、SiO2、Cr2O3、ZrO2、TiO2, one of ZnO or two kinds, Metal composite oxide is scattered in dispersing agent, and for content of the dispersing agent in component A in 0.05-90wt.%, remaining is compound gold Belong to oxide.
7. the catalyst of the oxide containing CeZr described in -5 any one according to claim 1, it is characterised in that: the CHA, The molecular sieve of AEI topological structure backbone element composition be Si-Al-O, Ga-Al-O, Ti-Si-O, Si-Al-P-O, Al-P-O, One of Ge-Al-O or two kinds or more.
8. the catalyst of the oxide according to claim 1 containing CeZr, it is characterised in that: the physics mode mixing uses Mechanical stirring, ball milling, shaking table mixing, one of mechanical lapping or two kinds or more carry out compound.
9. a kind of method that co hydrogenation directly converts producing light olefins, it is characterised in that: it is with the conjunction containing CO and H2 It is unstripped gas at gas, conversion reaction is carried out in fixed bed or moving bed, used catalyst is that claim 1-7 is any The oxide catalyst containing CeZr.
10. according to the method described in claim 9, it is characterized by: the synthesis gas is H2/ CO gaseous mixture, H2/ CO molar ratio For 0.2-3.5, preferably 0.3-2.5；The pressure of the synthesis gas is 0.5-10MPa, and reaction temperature is 300-600 DEG C, air speed For 300-10000h-1；Synthesis gas H2/ CO molar ratio is 0.2-3.5, preferably 0.3-2.5.
CN201711089864.5A 2017-11-08 2017-11-08 Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation Active CN109745965B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711089864.5A CN109745965B (en) 2017-11-08 2017-11-08 Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711089864.5A CN109745965B (en) 2017-11-08 2017-11-08 Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation

Publications (2)

Publication Number Publication Date
CN109745965A true CN109745965A (en) 2019-05-14
CN109745965B CN109745965B (en) 2021-11-05

Family

ID=66401398

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711089864.5A Active CN109745965B (en) 2017-11-08 2017-11-08 Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation

Country Status (1)

Country Link
CN (1) CN109745965B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110479364A (en) * 2019-09-02 2019-11-22 太原理工大学 A kind of method that bifunctional catalyst and CO add hydrogen directly to convert producing light olefins
CN112108180A (en) * 2019-06-21 2020-12-22 中国科学院大连化学物理研究所 Catalyst for preparing low-carbon olefin by directly converting synthesis gas and preparation method thereof
CN112191278A (en) * 2020-10-27 2021-01-08 正大能源材料(大连)有限公司 Bifunctional catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof
CN112675904A (en) * 2019-10-18 2021-04-20 中国石油化工股份有限公司 Carbon-containing catalyst and application thereof in one-step synthesis gas production of low-carbon olefin
CN112844362A (en) * 2021-01-27 2021-05-28 陕西师范大学 Method for improving activity of metal oxide catalyst in oxidation and oxidative dehydrogenation reaction
CN114602452A (en) * 2022-03-15 2022-06-10 中国科学院赣江创新研究院 Self-template porous cerium-zirconium solid solution and preparation method thereof
CN114733565A (en) * 2021-01-07 2022-07-12 国家能源投资集团有限责任公司 Composite catalyst, preparation method and application thereof, and method for preparing low-carbon olefin by synthesis gas one-step method

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074490A (en) * 2007-06-15 2007-11-21 北京工业大学 Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes
CN101920207A (en) * 2010-05-10 2010-12-22 内蒙古大学 Synthetic gas-to-oil cobalt-based catalyst using cerium-zirconium solid solution as carrier
US20150158791A1 (en) * 2013-12-06 2015-06-11 Exxonmobil Chemical Patents Inc. Production of C2+ Olefins
CN106311317A (en) * 2015-07-02 2017-01-11 中国科学院大连化学物理研究所 Catalyst and method for directly preparing light olefins from synthesis gas by one-step process
CN106345514A (en) * 2016-07-29 2017-01-25 厦门大学 Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof
CN106540740A (en) * 2016-10-28 2017-03-29 厦门大学 Catalyst by synthesis gas high selectivity light aromatics and preparation method thereof
CN106540674A (en) * 2016-10-26 2017-03-29 中科合成油技术有限公司 A kind of metal-doped zirconia catalyst and preparation method thereof and the application in gas catalyzed conversion is catalyzed and synthesized

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101074490A (en) * 2007-06-15 2007-11-21 北京工业大学 Method for producing spherical, tie-shaped and octahedral polycrystalline Ce0.6Zr0.3Y0.1O2 particles of um sizes
CN101920207A (en) * 2010-05-10 2010-12-22 内蒙古大学 Synthetic gas-to-oil cobalt-based catalyst using cerium-zirconium solid solution as carrier
US20150158791A1 (en) * 2013-12-06 2015-06-11 Exxonmobil Chemical Patents Inc. Production of C2+ Olefins
CN106311317A (en) * 2015-07-02 2017-01-11 中国科学院大连化学物理研究所 Catalyst and method for directly preparing light olefins from synthesis gas by one-step process
CN106345514A (en) * 2016-07-29 2017-01-25 厦门大学 Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof
CN106540674A (en) * 2016-10-26 2017-03-29 中科合成油技术有限公司 A kind of metal-doped zirconia catalyst and preparation method thereof and the application in gas catalyzed conversion is catalyzed and synthesized
CN106540740A (en) * 2016-10-28 2017-03-29 厦门大学 Catalyst by synthesis gas high selectivity light aromatics and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PAN XIULIAN ET AL.: "Selective conversion of syngas to light olefins", 《SCIENCE》 *
QINGHONG ZHANG ET AL.: "Direct and Highly Selective Conversion of Synthesis Gas into Lower Olefins: Design of a Bifunctional Catalyst Combining Methanol Synthesis and Carbon–Carbon Coupling", 《ANGEWANDTE CHEMIE》 *
于飞: "合成气催化转化直接制备低碳烯烃研究进展", 《燃料化学学报》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112108180A (en) * 2019-06-21 2020-12-22 中国科学院大连化学物理研究所 Catalyst for preparing low-carbon olefin by directly converting synthesis gas and preparation method thereof
CN110479364A (en) * 2019-09-02 2019-11-22 太原理工大学 A kind of method that bifunctional catalyst and CO add hydrogen directly to convert producing light olefins
CN112675904A (en) * 2019-10-18 2021-04-20 中国石油化工股份有限公司 Carbon-containing catalyst and application thereof in one-step synthesis gas production of low-carbon olefin
CN112675904B (en) * 2019-10-18 2023-08-04 中国石油化工股份有限公司 Carbon-containing catalyst and application thereof in one-step method for producing low-carbon olefin by using synthesis gas
CN112191278A (en) * 2020-10-27 2021-01-08 正大能源材料(大连)有限公司 Bifunctional catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof
CN112191278B (en) * 2020-10-27 2023-04-07 正大能源材料(大连)有限公司 Bifunctional catalyst for directly preparing low-carbon olefin from synthesis gas and preparation method and application thereof
CN114733565A (en) * 2021-01-07 2022-07-12 国家能源投资集团有限责任公司 Composite catalyst, preparation method and application thereof, and method for preparing low-carbon olefin by synthesis gas one-step method
CN114733565B (en) * 2021-01-07 2024-04-02 国家能源投资集团有限责任公司 Composite catalyst, preparation method and application thereof, and method for preparing low-carbon olefin by one-step synthesis gas
CN112844362A (en) * 2021-01-27 2021-05-28 陕西师范大学 Method for improving activity of metal oxide catalyst in oxidation and oxidative dehydrogenation reaction
CN112844362B (en) * 2021-01-27 2023-07-21 陕西师范大学 Method for improving activity of metal oxide catalyst in oxidation and oxidative dehydrogenation reactions
CN114602452A (en) * 2022-03-15 2022-06-10 中国科学院赣江创新研究院 Self-template porous cerium-zirconium solid solution and preparation method thereof
CN114602452B (en) * 2022-03-15 2023-10-17 中国科学院赣江创新研究院 Self-template porous cerium-zirconium solid solution and preparation method thereof

Also Published As

Publication number Publication date
CN109745965B (en) 2021-11-05

Similar Documents

Publication Publication Date Title
CN108144643B (en) Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas
CN109745965A (en) A method of the catalyst and co hydrogenation of the oxide containing CeZr directly convert producing light olefins
CN109939667B (en) Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas
CN108568313B (en) Catalyst and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation
CN107661774B (en) Catalyst and method for preparing low-carbon olefin by directly converting synthesis gas
CN108970600A (en) A kind of method that catalyst and synthesis gas directly convert producing light olefins
CN109939728A (en) A kind of method that supported catalyst and synthesis gas directly convert producing light olefins
CN107774302B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN108970638B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN111346672B (en) Method for preparing low-carbon olefin by doping heteroatom molecular sieve to catalyze synthesis gas with high selectivity
EP3900829A1 (en) Method for the preparation of low-carbon olefin in high selectivity from synthesis gas catalyzed by heteroatom-doped molecular sieve
CN108940355A (en) A kind of method of base-modified catalyst and carbon monoxide hydrogenation ethylene
CN109939723A (en) A kind of method that catalyst and synthesis gas directly convert ethylene processed
CN108927132A (en) A kind of method of bifunctional catalyst and co hydrogenation ethylene
CN108970635B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN108970637B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN108568311B (en) Catalyst and method for preparing ethylene by directly converting synthesis gas
CN107661773B (en) Method for preparing liquid fuel and co-producing low-carbon olefin by directly converting catalyst and synthesis gas
CN109939722A (en) A kind of method of organic base-modified composite catalyst and co hydrogenation ethylene
CN111346669B (en) Method for preparing low-carbon olefin by catalyzing synthesis gas through heteroatom-doped molecular sieve
CN109939668A (en) A method of the B acid catalyst of type containing LF and synthesis gas directly convert ethylene processed
CN112973781B (en) Catalyst and direct conversion of synthesis gas to prepare C2And C3Process for the preparation of olefins
CN112973659B (en) Bifunctional catalyst containing SAPO-17 molecular sieve and application of bifunctional catalyst in reaction of preparing low-carbon olefin from synthesis gas
CN109939669A (en) A kind of method of base-modified composite catalyst and carbon monoxide hydrogenation ethylene
CN110152716A (en) A kind of method that selectivity sloughs the catalyst and carbon monoxide hydrogenation ethylene of MOR12 annulus Al

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant