CN103071528A - Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method - Google Patents
Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method Download PDFInfo
- Publication number
- CN103071528A CN103071528A CN2013100196934A CN201310019693A CN103071528A CN 103071528 A CN103071528 A CN 103071528A CN 2013100196934 A CN2013100196934 A CN 2013100196934A CN 201310019693 A CN201310019693 A CN 201310019693A CN 103071528 A CN103071528 A CN 103071528A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- core
- oxide
- reaction
- shell
- 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
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 239000011258 core-shell material Substances 0.000 title abstract 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 25
- 239000013078 crystal Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000975 co-precipitation Methods 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004458 analytical method Methods 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 238000004817 gas chromatography Methods 0.000 claims description 8
- 239000008246 gaseous mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 241000269350 Anura Species 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- 238000007873 sieving Methods 0.000 abstract description 2
- 239000012495 reaction gas Substances 0.000 abstract 1
- 239000002808 molecular sieve Substances 0.000 description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- -1 copper Zinc-aluminium Chemical compound 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- DBQFKMXHMSMNRU-UHFFFAOYSA-N [Zn].[Co].[Cu] Chemical compound [Zn].[Co].[Cu] DBQFKMXHMSMNRU-UHFFFAOYSA-N 0.000 description 4
- HEWIALZDOKKCSI-UHFFFAOYSA-N [Ni].[Zn].[Mn].[Cu] Chemical compound [Ni].[Zn].[Mn].[Cu] HEWIALZDOKKCSI-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- LREHXGIFWKYNGI-UHFFFAOYSA-N copper zinc cerium(3+) oxygen(2-) Chemical compound [O-2].[Ce+3].[Zn+2].[Cu+2] LREHXGIFWKYNGI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FGDHWCKEYPFXGZ-UHFFFAOYSA-N copper zinc oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[Zn+2].[Cu+2].[O-2].[O-2].[O-2] FGDHWCKEYPFXGZ-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- WHROWQPBDAJSKH-UHFFFAOYSA-N [Mn].[Ni].[Cr] Chemical compound [Mn].[Ni].[Cr] WHROWQPBDAJSKH-UHFFFAOYSA-N 0.000 description 1
- GZSJSGZGZXGFOW-UHFFFAOYSA-N [Zn].[Ce].[Cu] Chemical compound [Zn].[Ce].[Cu] GZSJSGZGZXGFOW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种核壳结构催化剂及由合成气一步法制取低碳烯烃的方法。核壳结构催化剂将甲醇合成反应与MTO反应耦合在一起，使合成气一步转化为低碳烯烃。核壳催化剂以甲醇合成催化剂为核，MTO反应催化剂为壳，在该核壳结构催化剂上由合成气一步制取低碳烯烃的过程为：反应气首先透过壳层催化剂孔道进入核催化剂进行反应生成甲醇，生成的甲醇在扩散出壳层催化剂的过程中接触壳层催化剂的活性中心并反应生成低碳烯烃。本发明简化了工艺路线，打破了甲醇合成反应的反应平衡，提高CO的转化率；壳层同时抑制了生成的烯烃与核催化剂的接触，避免了生成的烯烃被核催化剂催化成烷烃；壳层独有的孔道结构还具有分子筛分作用，降低了高碳产物生成。
The invention discloses a catalyst with a core-shell structure and a method for preparing low-carbon olefins from synthesis gas in one step. The core-shell structure catalyst couples the methanol synthesis reaction and the MTO reaction, so that the synthesis gas can be converted into light olefins in one step. The core-shell catalyst uses the methanol synthesis catalyst as the core and the MTO reaction catalyst as the shell. The process of producing low-carbon olefins from synthesis gas on the core-shell structure catalyst in one step is as follows: the reaction gas first passes through the pores of the shell catalyst and enters the core catalyst for reaction. Methanol is generated, and the generated methanol contacts the active center of the shell catalyst and reacts to generate low-carbon olefins during the process of diffusing out of the shell catalyst. The invention simplifies the process route, breaks the reaction balance of methanol synthesis reaction, and improves the conversion rate of CO; at the same time, the shell layer inhibits the contact between the generated olefins and the core catalyst, and prevents the generated olefins from being catalyzed into alkanes by the core catalyst; the shell layer The unique pore structure also has the effect of molecular sieving, which reduces the generation of high-carbon products.
Description
Technical field
The invention provides a kind of catalyst with core-casing structure and by the method for one-step method from syngas preparing low-carbon olefins, belong to the synthetic catalyst research field of low-carbon alkene.
Technical background
Low-carbon alkene is important Organic Chemicals, and China's consumption demand is large, but the degree of self-sufficiency is low.The method of preparing low-carbon olefins is divided by raw material and can be divided into generally 3 large classes at present: petroleum path, natural gas route and coal route.For the present situation of rich coal, oil starvation, weak breath, take coal as the raw material preparing synthetic gas, again by the synthesis gas preparing low-carbon olefins, this provides a desirable approach for be converted into the basic organic chemical industry raw material from non-oil resource.
Present industrial production low-carbon alkene adopts the method for fractional steps to carry out, and namely first produces methyl alcohol by synthesis gas, prepares low-carbon alkene by methanol dehydration again.For the methyl alcohol synthetic reaction, Britain ICI company has researched and developed the catalyst that consists of the copper Zinc-aluminium in 1966, catalyst for methanol obtains large development in recent years, by improving active component in degree of scatter and the specific area of carrier surface, improved reactivity, life-span and the mechanical strength of catalyst; For MTO(Methanol to Olefins, methanol-to-olefins) reaction, the most ripe with the research of ZSM-5 molecular sieve, its aperture is relatively large, and the primary product that obtains is propylene and C4+ hydro carbons.The synthetic SAPO-34 molecular sieve of U.S.'s union carbide corporation had the active high and high characteristics of selectivity of light olefin in 1984, was used widely.Take SAPO-34 as catalyst MTO process, methanol conversion reaches 100%, and ethylene selectivity is higher than 50%, and low-carbon alkene C2～C4 total recovery is higher than 85%, almost without the product more than the C5.
Catalyst with core-casing structure is a kind of novel reaction catalyst that two consecutive reactions better are coupled, its cardinal principle is that product is carried out first step reaction at catalyst nucleus, the process that first step product diffuses out by shell catalyst is carried out the second step reaction, the product of having guaranteed the first step all can be carried out the second step reaction, improved the selective of purpose product, simultaneously so that chemical balance constantly move to the product direction.(J.Am.Chem.Soc., 2010,132 such as Yang, p8129) having prepared cupric oxide zinc oxide aluminium oxide is that nuclear and HZSM-5 are the catalyst with core-casing structure of shell, and use it for by the direct preparation of dimethyl ether by using synthesis gas reaction, dimethyl ether selectively reaches 96%, apparently higher than the catalyst of physical mixed.The present invention proposes to adopt catalyst with core-casing structure that methyl alcohol synthetic reaction and MTO reaction is coupling in the reactor to carry out, by synthesis gas one-step synthesis low-carbon alkene.This one-step method has been simplified technical process, has improved selectivity of product.
Summary of the invention
In order to overcome the deficiencies in the prior art, the purpose of this invention is to provide a kind of catalyst with core-casing structure and by the method for one-step method from syngas preparing low-carbon olefins.
A kind of catalyst with core-casing structure by the one-step method from syngas preparing low-carbon olefins, the nuclear of this catalyst with core-casing structure are methanol synthesis catalyst; The shell of this catalyst with core-casing structure is the MTO catalysts of outer molecular screen membrane structure; The shell thickness is the 1-15 micron.
Described shell film adopts the crystal seed method preparation, and described nuclear adopts the coprecipitation preparation.
Described methanol synthesis catalyst is cupric oxide and zinc oxide, and adds in the following auxiliary agent one or more: zirconia, aluminium oxide, nickel oxide, cobalt oxide, cerium oxide, iron oxide, manganese oxide, silica, magnesia, calcium oxide, titanium oxide, vanadium oxide, chromium oxide, niobium oxide, molybdenum oxide, tin oxide.
Described MTO catalysts is modified ZSM-5 Series Molecules sieve membrane or SAPO Series Molecules sieve membrane.
A kind ofly utilize described catalyst with core-casing structure by the method for one-step method from syngas preparing low-carbon olefins, its step is as follows:
1) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
2) reduction makes reaction tube be down to room temperature after finishing, and, is warming up to reaction temperature again and reacts to predetermined reaction pressure with synthesis gas booster reaction system; Predetermined reaction pressure is 1-10MPa; Synthesis gas composition: by volume, H
2: CO is 1-6:1; Reaction temperature is 200-500 ℃; Feed volume air speed 1000-10000h
-1
Regulate the mass ratio of core catalyst and lamella catalyst by changing described shell thickness, thus the conditioned reaction process.
Described step 2) utilizes gas-chromatography on-line analysis product composition in.
Beneficial effect of the present invention: adopt catalyst with core-casing structure, synthetic being coupling in the reactor with two reactions of MTO reaction of methyl alcohol reacted, simplified process route, the product of previous step reaction is as the reactant of next step reaction, can impel by the chemical reaction equilibrium of constantly breaking the methyl alcohol synthetic reaction reaction to carry out to the direction of product always, improve the selective of the conversion ratio of CO and ethene, propylene.The thickness of shell homogeneous makes the methyl alcohol that generates at catalyst nucleus all have equal chance to see through lamella catalyst and carries out the MTO reaction, has improved the purpose products collection efficiency; Shell has suppressed the alkene of generation and contacting of catalyst nucleus simultaneously, and the alkene of having avoided generating is catalyzed into alkane by catalyst nucleus; The exclusive pore passage structure of shell also has the molecule sieving actoion, reduces high carbon product and generates, thereby suppress the catalyst coking and deactivation, prolongs the service life of composite catalyst.
Description of drawings
Fig. 1 catalyst with core-casing structure structural representation.
Fig. 2 catalyst with core-casing structure Electronic Speculum picture.
Fig. 3 catalyst with core-casing structure cross section Electronic Speculum picture.
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated.
A kind of catalyst with core-casing structure by the one-step method from syngas preparing low-carbon olefins, the nuclear of this catalyst with core-casing structure are methanol synthesis catalyst; The shell of this catalyst with core-casing structure is the MTO catalysts of outer molecular screen membrane structure; The shell thickness is the 1-15 micron, and the aperture of shell film is 0.3-0.6nm.Its schematic diagram is seen Fig. 1, only represent in the drawings entering and diffusion process of a direction, in fact synthesis gas can enter the core catalyst through all directions of shell film, and the methyl alcohol of generation also can in the process that diffuse out the MTO reaction occur from all directions of shell film.
Described shell film adopts the crystal seed method preparation, and described nuclear adopts the coprecipitation preparation.
Described methanol synthesis catalyst is cupric oxide and zinc oxide, and adds in the following auxiliary agent one or more: zirconia, aluminium oxide, nickel oxide, cobalt oxide, cerium oxide, iron oxide, manganese oxide, silica, magnesia, calcium oxide, titanium oxide, vanadium oxide, chromium oxide, niobium oxide, molybdenum oxide, tin oxide.
Described MTO catalysts is modified ZSM-5 Series Molecules sieve membrane or SAPO Series Molecules sieve membrane.
Embodiment 1
1) with salpeter solution and the Na of copper zinc-aluminium
2CO
3The solution co-precipitation, suction filtration, oven dry and roasting get the copper Zinc-aluminium;
2) press Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is the synthetic liquid of 0.3:1:0.2:2:100 configuration, at 150 ℃ of hydro-thermal reaction 20h, gets the molecular sieve crystal seed.Crystal seed is coated on copper Zinc-aluminium carrier surface, the carrier that applies crystal seed is put into synthetic liquid at 170 ℃ of crystallization 100h, make the catalyst with core-casing structure of SAPO-17 molecular screen membrane coated copper Zinc-aluminium, the gained catalyst with core-casing structure is seen Fig. 2, its sectional view is seen Fig. 3,6 microns of molecular sieve thickness, the aperture of shell film are 0.4nm;
3) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
4) make reaction tube be down to room temperature after reduction finishes,, be warming up to again reaction temperature and react to predetermined pressure with synthesis gas booster reaction system, and with gas-chromatography on-line analysis product composition.Reaction pressure 1MPa; Synthesis gas composition: by volume, H
2: CO is 1:1; Reaction temperature is 200 ℃; Charging air speed 1000h
-1The CO conversion ratio is 20%, and ethene and Propylene Selectivity are 96%.
1) with salpeter solution and the Na of copper zinc cobalt
2CO
3The solution co-precipitation, suction filtration, oven dry and roasting get copper zinc cobalt/cobalt oxide;
2) press Al
2O
3: SiO
2: TPAOH:EtOH:H
2The mol ratio of O is the synthetic liquid of 2:1:0.01:5:300 configuration, at 180 ℃ of hydro-thermal reaction 10h, gets the molecular sieve crystal seed.Crystal seed is coated on copper zinc cobalt/cobalt oxide carrier surface, the carrier that applies crystal seed is put into synthetic liquid at 190 ℃ of crystallization 50h, make the catalyst with core-casing structure of modified zsm-5 zeolite film coated copper zinc cobalt/cobalt oxide, 15 microns of molecular sieve thickness, the aperture of shell film is 0.5nm;
3) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
4) make reaction tube be down to room temperature after reduction finishes,, be warming up to again reaction temperature and react to predetermined pressure with synthesis gas booster reaction system, and with gas-chromatography on-line analysis product composition.Reaction pressure 1MPa; Synthesis gas composition, by volume, H
2/ CO is 6; Reaction temperature is 500 ℃; Feed volume air speed 10000h
-1The CO conversion ratio is 15%, and ethene and Propylene Selectivity are 97%.
Embodiment 3
1) with the salpeter solution of copper zinc, hydrochloric acid solution and the Na of nickel manganese chromium
2CO
3The solution co-precipitation, suction filtration, oven dry and roasting get copper zinc-nickel manganese chromated oxide;
2) press Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is the synthetic liquid of 3:2:1.5:0.1:500 configuration, at 160 ℃ of hydro-thermal reaction 40h, gets the molecular sieve crystal seed.Crystal seed is coated on copper zinc-nickel manganese chromated oxide carrier surface, the carrier that applies crystal seed is put into synthetic liquid at 165 ℃ of crystallization 70h, make the catalyst with core-casing structure of SAPO-34 molecular screen membrane coated copper zinc-nickel manganese chromated oxide, 1 micron of molecular sieve thickness;
3) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
4) make reaction tube be down to room temperature after reduction finishes,, be warming up to again reaction temperature and react to predetermined pressure with synthesis gas booster reaction system, and with gas-chromatography on-line analysis product composition.Reaction pressure 5MPa; Synthesis gas composition: H
2/ CO is 4; Reaction temperature is 400 ℃; Charging air speed 4000h
-1The CO conversion ratio is 25%, and ethene and Propylene Selectivity are 99%.
Embodiment 4
1) with the salpeter solution of copper zinc, sulfuric acid solution and the Na of titanium
2CO
3The solution co-precipitation, suction filtration, oven dry and roasting get copper zinc titanium oxide;
2) press Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is the synthetic liquid of 1.2:0.8:2.5:1.5:70 configuration, at 175 ℃ of hydro-thermal reaction 50h, gets the molecular sieve crystal seed.Crystal seed is coated on copper Zinc-aluminium carrier surface, the carrier that applies crystal seed is put into synthetic liquid at 190 ℃ of crystallization 30h, make the catalyst with core-casing structure of SAPO-26 molecular screen membrane coated copper zinc titanium oxide, 6 microns of molecular sieve thickness;
3) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
4) make reaction tube be down to room temperature after reduction finishes,, be warming up to again reaction temperature and react to predetermined pressure with synthesis gas booster reaction system, and with gas-chromatography on-line analysis product composition.Reaction pressure 7MPa; Synthesis gas composition: H
2/ CO is 3; Reaction temperature is 300 ℃; Charging air speed 7000h
-1The CO conversion ratio is 20%, and ethene and Propylene Selectivity are 96%.
Embodiment 5
1) with salpeter solution and the Na of copper zinc cerium
2CO
3The solution co-precipitation, suction filtration, oven dry and roasting get copper zinc cerium oxide;
2) press Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is the synthetic liquid of 2.3:1.9:1:3.2:420 configuration, at 185 ℃ of hydro-thermal reaction 20h, gets the molecular sieve crystal seed.Crystal seed is coated on copper zinc cerium oxide carrier surface, the carrier that applies crystal seed is put into synthetic liquid at 195 ℃ of crystallization 50h, make the catalyst with core-casing structure of SAPO-26 molecular screen membrane coated copper zinc cerium oxide, 3 microns of molecular sieve thickness;
3) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
4) make reaction tube be down to room temperature after reduction finishes,, be warming up to again reaction temperature and react to predetermined pressure with synthesis gas booster reaction system, and with gas-chromatography on-line analysis product composition.Reaction pressure 7MPa; Synthesis gas composition: H
2/ CO is 3; Reaction temperature is 300 ℃; Charging air speed 7000h
-1The CO conversion ratio is 22%, and ethene and Propylene Selectivity are 97%.
Embodiment 6
1) with salpeter solution, Ludox and the Na of copper zinc
2CO
3The solution co-precipitation, suction filtration, oven dry and roasting get copper zinc Si oxide;
2) press Al
2O
3: P
2O
5: SiO
2: TEAOH:H
2The mol ratio of O is the synthetic liquid of 2.3:1.9:1:3.2:420 configuration, at 185 ℃ of hydro-thermal reaction 20h, gets the molecular sieve crystal seed.Crystal seed is coated on copper zinc Si oxide carrier surface, the carrier that applies crystal seed is put into synthetic liquid at 195 ℃ of crystallization 50h, make the catalyst with core-casing structure of SAPO-26 molecular screen membrane coated copper zinc Si oxide, 5 microns of molecular sieve thickness;
3) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
4) make reaction tube be down to room temperature after reduction finishes,, be warming up to again reaction temperature and react to predetermined pressure with synthesis gas booster reaction system, and with gas-chromatography on-line analysis product composition.Reaction pressure 3MPa; Synthesis gas composition: H
2/ CO is 5; Reaction temperature is 400 ℃; Charging air speed 4000h
-1The CO conversion ratio is 24%, and ethene and Propylene Selectivity are 96%.
Claims (7)
1. the catalyst with core-casing structure by the one-step method from syngas preparing low-carbon olefins is characterized in that, the nuclear of this catalyst with core-casing structure is methanol synthesis catalyst; The shell of this catalyst with core-casing structure is the MTO catalysts of outer molecular screen membrane structure; The shell thickness is the 1-15 micron.
2. such as the catalyst with core-casing structure of claim 1 by the one-step method from syngas preparing low-carbon olefins, it is characterized in that described shell film adopts the crystal seed method preparation, described nuclear adopts the coprecipitation preparation.
3. such as the catalyst with core-casing structure of claim 1 by the one-step method from syngas preparing low-carbon olefins, it is characterized in that, described methanol synthesis catalyst is cupric oxide and zinc oxide, and adds in the following auxiliary agent one or more: zirconia, aluminium oxide, nickel oxide, cobalt oxide, cerium oxide, iron oxide, manganese oxide, silica, magnesia, calcium oxide, titanium oxide, vanadium oxide, chromium oxide, niobium oxide, molybdenum oxide, tin oxide.
4. such as the catalyst with core-casing structure of claim 1 by the one-step method from syngas preparing low-carbon olefins, it is characterized in that described MTO catalysts is modified ZSM-5 Series Molecules sieve membrane or SAPO Series Molecules sieve membrane.
5. one kind is utilized each described catalyst with core-casing structure of claim 1-4 by the method for one-step method from syngas preparing low-carbon olefins, it is characterized in that its step is as follows:
1) catalyst with core-casing structure for preparing is added in the reaction tube, with the hydrogen reducing of nitrogen dilution, wherein to account for the volume percent content of gaseous mixture be 5% to hydrogen;
2) reduction makes reaction tube be down to room temperature after finishing, and, is warming up to reaction temperature again and reacts to predetermined reaction pressure with synthesis gas booster reaction system; Predetermined reaction pressure is 1-10MPa; Synthesis gas composition: by volume, H
2: CO is 1-6:1; Reaction temperature is 200-500 ℃; Feed volume air speed 1000-10000h
-1
6. method as claimed in claim 5 is characterized in that, regulates the mass ratio of core catalyst and lamella catalyst by changing described shell thickness, thus the conditioned reaction process.
7. method as claimed in claim 5 is characterized in that, described step 2) in utilize gas-chromatography on-line analysis product composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100196934A CN103071528A (en) | 2013-01-21 | 2013-01-21 | Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013100196934A CN103071528A (en) | 2013-01-21 | 2013-01-21 | Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103071528A true CN103071528A (en) | 2013-05-01 |
Family
ID=48148345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013100196934A Pending CN103071528A (en) | 2013-01-21 | 2013-01-21 | Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103071528A (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301868A (en) * | 2013-07-10 | 2013-09-18 | 河北大学 | Core-shell structural nano catalyst as well as preparation method and application thereof |
| CN103349997A (en) * | 2013-07-14 | 2013-10-16 | 中建安装工程有限公司 | Composite membrane core-shell structure catalyst and its CO2 hydrogenation method to prepare low-carbon hydrocarbons |
| CN104152172A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Process for converting methanol into diesel |
| CN104148119A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Roll forming catalyst |
| CN104178203A (en) * | 2014-09-09 | 2014-12-03 | 安徽工程大学 | Method for converting methanol into diesel oil |
| CN104801337A (en) * | 2015-03-19 | 2015-07-29 | 沈阳化工大学 | Ethanol catalyst prepared from synthesis gas and dimethyl ether with one-step method as well as preparation method of ethanol catalyst |
| CN105473224A (en) * | 2013-07-31 | 2016-04-06 | 沙特基础工业公司 | Catalyst and process for the production of olefins from syngas |
| CN107282102A (en) * | 2017-06-22 | 2017-10-24 | 中国天辰工程有限公司 | A kind of preparation method of metal load type molecular sieve catalyst |
| CN107349954A (en) * | 2017-07-05 | 2017-11-17 | 江南大学 | A kind of synthesis gas directly prepares multi-stage nano reactor catalyst and its preparation and application of aromatic compound |
| US9919981B2 (en) | 2014-07-11 | 2018-03-20 | Dow Global Technologies Llc | Conversion of carbon monoxide, carbon dioxide, or a combination thereof over hybrid catalyst |
| CN108137431A (en) * | 2015-10-30 | 2018-06-08 | 陶氏环球技术有限责任公司 | Synthetic gas is converted into the method for alkene using bifunctional chromium oxide/zinc oxide-SAPO-34 catalyst |
| CN109261199A (en) * | 2018-09-27 | 2019-01-25 | 太原理工大学 | A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications |
| CN109465014A (en) * | 2018-12-19 | 2019-03-15 | 中大立信（北京）技术发展有限公司 | A kind of dual purpose catalyst, the preparation method and the usage of controllable ozone and decomposing hydrogen dioxide solution speed |
| CN109704899A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method that synthesis gas prepares alkene |
| CN110563592A (en) * | 2019-09-18 | 2019-12-13 | 宁夏大学 | method for preparing dimethylamine from carbon dioxide, hydrogen and ammonia in one step |
| WO2020005703A1 (en) * | 2018-06-29 | 2020-01-02 | Dow Global Technologies Llc | Hybrid catalysts comprising a mixed metal oxide component for production of c2 and c3 hydrocarbons |
| CN111001431A (en) * | 2019-12-06 | 2020-04-14 | 西南化工研究设计院有限公司 | Core-shell catalyst for preparing ethanol from dimethyl ether and synthesis gas by one-step method and preparation method and application thereof |
| CN111266131A (en) * | 2020-03-02 | 2020-06-12 | 正大能源材料(大连)有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and use method thereof |
| US10787611B2 (en) | 2016-12-22 | 2020-09-29 | Dow Global Technologies Llc | Process to convert synthesis gas to olefins using a bifunctional chromium/zinc oxide-SAPO-34 catalyst |
| CN113351215A (en) * | 2020-03-05 | 2021-09-07 | 石河子市中易连疆新能源有限责任公司 | Core-shell structure catalyst, preparation method and application thereof |
| CN117138783A (en) * | 2023-08-30 | 2023-12-01 | 安徽大学 | A catalyst with a double yolk egg-shaped structure wrapped with beta molecular sieve and its preparation method and application |
| US11884605B2 (en) | 2018-06-29 | 2024-01-30 | Dow Global Technologies Llc | Hybrid catalysts comprising a zeolite and a mixed metal oxide component for converting syngas into C2 and C3 olefins |
| US11986799B2 (en) | 2018-12-28 | 2024-05-21 | Dow Global Technologies Lllc | Catalysts comprising a zirconia and gallium oxide component for production of C2 to C4 olefins |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849575A (en) * | 1987-11-25 | 1989-07-18 | Uop | Production of olefins |
| CN101265149A (en) * | 2008-04-25 | 2008-09-17 | 北京化工大学 | A kind of method that takes syngas as raw material two-stage method to prepare light olefins |
| WO2009074801A1 (en) * | 2007-12-12 | 2009-06-18 | Bp P.I.C. | A process for the conversion of n-butanol to di-isobutene and prqpene |
| CN101947467A (en) * | 2010-09-14 | 2011-01-19 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
| CN102245541A (en) * | 2008-12-10 | 2011-11-16 | 雪佛龙美国公司 | Improved process for conversion of synthesis gas to hydrocarbons using a zeolite-methanol catalyst system |
| CN102448609A (en) * | 2009-05-29 | 2012-05-09 | 国际壳牌研究有限公司 | Method for preparing gas separation molecular sieve membrane |
-
2013
- 2013-01-21 CN CN2013100196934A patent/CN103071528A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4849575A (en) * | 1987-11-25 | 1989-07-18 | Uop | Production of olefins |
| WO2009074801A1 (en) * | 2007-12-12 | 2009-06-18 | Bp P.I.C. | A process for the conversion of n-butanol to di-isobutene and prqpene |
| CN101265149A (en) * | 2008-04-25 | 2008-09-17 | 北京化工大学 | A kind of method that takes syngas as raw material two-stage method to prepare light olefins |
| CN102245541A (en) * | 2008-12-10 | 2011-11-16 | 雪佛龙美国公司 | Improved process for conversion of synthesis gas to hydrocarbons using a zeolite-methanol catalyst system |
| CN102448609A (en) * | 2009-05-29 | 2012-05-09 | 国际壳牌研究有限公司 | Method for preparing gas separation molecular sieve membrane |
| CN101947467A (en) * | 2010-09-14 | 2011-01-19 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
Non-Patent Citations (2)
| Title |
|---|
| RENFENG NIE ETAL.: "Core-shell structured CuO-ZnO@H-ZSM-5 catalysts for CO hydrogenation to dimethyl ether", 《FUEL》, vol. 96, 29 February 2012 (2012-02-29), pages 419 - 425 * |
| 金炜阳等: ""分子筛包覆型催化剂的制备和应用"", 《化学进展》, vol. 23, no. 10, 31 October 2011 (2011-10-31) * |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301868B (en) * | 2013-07-10 | 2015-04-01 | 河北大学 | Core-shell structural nano catalyst as well as preparation method and application thereof |
| CN103301868A (en) * | 2013-07-10 | 2013-09-18 | 河北大学 | Core-shell structural nano catalyst as well as preparation method and application thereof |
| CN103349997A (en) * | 2013-07-14 | 2013-10-16 | 中建安装工程有限公司 | Composite membrane core-shell structure catalyst and its CO2 hydrogenation method to prepare low-carbon hydrocarbons |
| CN103349997B (en) * | 2013-07-14 | 2015-05-06 | 中建安装工程有限公司 | Composite membrane core-shell structure catalyst and its CO2 hydrogenation method to prepare low-carbon hydrocarbons |
| CN105473224A (en) * | 2013-07-31 | 2016-04-06 | 沙特基础工业公司 | Catalyst and process for the production of olefins from syngas |
| US9919981B2 (en) | 2014-07-11 | 2018-03-20 | Dow Global Technologies Llc | Conversion of carbon monoxide, carbon dioxide, or a combination thereof over hybrid catalyst |
| CN104152172A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Process for converting methanol into diesel |
| CN104148119A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Roll forming catalyst |
| CN104152172B (en) * | 2014-09-08 | 2016-01-06 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of is the technique of diesel oil by methanol conversion |
| CN104148119B (en) * | 2014-09-08 | 2016-09-28 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of catalyst rolling molding |
| CN104178203A (en) * | 2014-09-09 | 2014-12-03 | 安徽工程大学 | Method for converting methanol into diesel oil |
| CN104178203B (en) * | 2014-09-09 | 2015-12-02 | 安徽工程大学 | A kind of is the method for diesel oil by methanol conversion |
| CN104801337A (en) * | 2015-03-19 | 2015-07-29 | 沈阳化工大学 | Ethanol catalyst prepared from synthesis gas and dimethyl ether with one-step method as well as preparation method of ethanol catalyst |
| CN108137431A (en) * | 2015-10-30 | 2018-06-08 | 陶氏环球技术有限责任公司 | Synthetic gas is converted into the method for alkene using bifunctional chromium oxide/zinc oxide-SAPO-34 catalyst |
| CN108137431B (en) * | 2015-10-30 | 2021-04-23 | 陶氏环球技术有限责任公司 | Method for converting synthesis gas to olefins using bifunctional chromia/zinc oxide-SAPO-34 catalysts |
| US10329209B2 (en) | 2015-10-30 | 2019-06-25 | Dow Global Technologies, Llc | Process to convert synthesis gas to olefins over a bifunctional chromium oxide/zinc oxide-SAPO-34 catalyst |
| US10787611B2 (en) | 2016-12-22 | 2020-09-29 | Dow Global Technologies Llc | Process to convert synthesis gas to olefins using a bifunctional chromium/zinc oxide-SAPO-34 catalyst |
| CN107282102A (en) * | 2017-06-22 | 2017-10-24 | 中国天辰工程有限公司 | A kind of preparation method of metal load type molecular sieve catalyst |
| CN107282102B (en) * | 2017-06-22 | 2020-02-28 | 中国天辰工程有限公司 | Preparation method of metal-loaded molecular sieve catalyst |
| CN107349954A (en) * | 2017-07-05 | 2017-11-17 | 江南大学 | A kind of synthesis gas directly prepares multi-stage nano reactor catalyst and its preparation and application of aromatic compound |
| CN107349954B (en) * | 2017-07-05 | 2020-10-09 | 江南大学 | Multistage nano reactor catalyst for directly preparing aromatic compound from synthesis gas and preparation and application thereof |
| CN109704899B (en) * | 2017-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Method for preparing olefin from synthesis gas |
| CN109704899A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | The method that synthesis gas prepares alkene |
| US11884605B2 (en) | 2018-06-29 | 2024-01-30 | Dow Global Technologies Llc | Hybrid catalysts comprising a zeolite and a mixed metal oxide component for converting syngas into C2 and C3 olefins |
| US11446642B2 (en) | 2018-06-29 | 2022-09-20 | Dow Global Technologies Llc | Hybrid catalysts comprising a mixed metal oxide component for production of C2 and C3 hydrocarbons |
| WO2020005703A1 (en) * | 2018-06-29 | 2020-01-02 | Dow Global Technologies Llc | Hybrid catalysts comprising a mixed metal oxide component for production of c2 and c3 hydrocarbons |
| CN112218712B (en) * | 2018-06-29 | 2023-12-22 | 陶氏环球技术有限责任公司 | For the production of C 2 And C 3 Hybrid catalyst for hydrocarbons comprising mixed metal oxide components |
| CN112218712A (en) * | 2018-06-29 | 2021-01-12 | 陶氏环球技术有限责任公司 | For production of C2And C3Hybrid catalyst comprising mixed metal oxide components for hydrocarbons |
| CN109261199B (en) * | 2018-09-27 | 2021-03-19 | 太原理工大学 | Catalyst, preparation method and application of high-stability synthesis gas for directly producing low-carbon olefins |
| CN109261199A (en) * | 2018-09-27 | 2019-01-25 | 太原理工大学 | A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications |
| CN109465014B (en) * | 2018-12-19 | 2021-08-03 | 中大立信（北京）技术发展有限公司 | Double-effect catalyst capable of regulating and controlling decomposition rate of ozone and hydrogen peroxide, preparation method and application thereof |
| CN109465014A (en) * | 2018-12-19 | 2019-03-15 | 中大立信（北京）技术发展有限公司 | A kind of dual purpose catalyst, the preparation method and the usage of controllable ozone and decomposing hydrogen dioxide solution speed |
| US11986799B2 (en) | 2018-12-28 | 2024-05-21 | Dow Global Technologies Lllc | Catalysts comprising a zirconia and gallium oxide component for production of C2 to C4 olefins |
| CN110563592B (en) * | 2019-09-18 | 2022-08-12 | 宁夏大学 | A kind of method for preparing dimethylamine from carbon dioxide, hydrogen and ammonia in one step |
| CN110563592A (en) * | 2019-09-18 | 2019-12-13 | 宁夏大学 | method for preparing dimethylamine from carbon dioxide, hydrogen and ammonia in one step |
| CN111001431A (en) * | 2019-12-06 | 2020-04-14 | 西南化工研究设计院有限公司 | Core-shell catalyst for preparing ethanol from dimethyl ether and synthesis gas by one-step method and preparation method and application thereof |
| CN111266131A (en) * | 2020-03-02 | 2020-06-12 | 正大能源材料(大连)有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and use method thereof |
| CN111266131B (en) * | 2020-03-02 | 2023-04-07 | 正大能源材料(大连)有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and preparation method and use method thereof |
| CN113351215A (en) * | 2020-03-05 | 2021-09-07 | 石河子市中易连疆新能源有限责任公司 | Core-shell structure catalyst, preparation method and application thereof |
| CN113351215B (en) * | 2020-03-05 | 2022-12-20 | 石河子市中易连疆新能源有限责任公司 | A kind of core shell structure catalyst, its preparation method and application |
| CN117138783A (en) * | 2023-08-30 | 2023-12-01 | 安徽大学 | A catalyst with a double yolk egg-shaped structure wrapped with beta molecular sieve and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103071528A (en) | Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method | |
| CN103349997B (en) | Composite membrane core-shell structure catalyst and its CO2 hydrogenation method to prepare low-carbon hydrocarbons | |
| CN101157593B (en) | Method for producing light olefins from methanol or/and dimethyl ether | |
| CN103664447B (en) | The method of synthesis gas alkene processed | |
| CN101381271B (en) | Method for preparing ethylene and propylene by means of copyrolysis | |
| CN104056653B (en) | A kind of catalyst for producing propylene with methanol | |
| CN104056654B (en) | A kind of ZSM-5 molecular sieve compositions, preparation method and application thereof | |
| CN104148106A (en) | Catalyst for producing low-carbon olefin by using synthesis gas and preparation method of catalyst | |
| CN104250186B (en) | A kind of preparation method of low-carbon alkene | |
| CN102365252A (en) | Method for reacting natural gas to aromatics while electrochemically removing hydrogen and electrochemically reacting the hydrogen to water | |
| CN103193580B (en) | Method for preparing low-carbon olefin by using supported catalyst through synthesis gas one-step process | |
| CN103521253A (en) | Catalyst for preparation of low-carbon olefine from synthesis gas through one-step method and preparation method thereof | |
| CN105254462B (en) | A kind of technique of methanol-to-olefins co-production gasoline and aromatic hydrocarbons | |
| CN105983440A (en) | Composite nanometer thin layer molecular sieve and preparation method and application | |
| CN101381272B (en) | Method for preparing ethylene and propylene by two-step method | |
| CN109701604B (en) | Multifunctional catalyst system with core-shell structure and application thereof | |
| CN103664436A (en) | Method for directly transforming synthesis gas into low-carbon olefin | |
| CN109433257B (en) | A kind of catalyst for producing ethylene by oxidative ethane dehydrogenation of carbon dioxide and preparation method thereof | |
| CN110015939B (en) | Method and device for producing hydrogen and co-producing methane by coal | |
| CN105435801A (en) | A supported iron catalyst, a preparing method thereof and applications of the catalyst | |
| US11192791B2 (en) | Light hydrocarbon partial oxidation catalyst and carbon monoxide production method using same | |
| CN117258828A (en) | Method for preparing aromatic hydrocarbon by carbon dioxide hydrogenation on zinc oxide-zirconium dioxide@C/multi-level pore nano ZSM-5 molecular sieve dual-function catalyst | |
| CN107824214B (en) | Method for preparing low-carbon olefin from synthesis gas | |
| JP6678450B2 (en) | Partial oxidation catalyst and method for producing carbon monoxide using the same | |
| CN105439788B (en) | A kind of method that olefine selective in product is improved in methanol-to-olefins reaction process |
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: 20130501 |