CN109261199A - A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications - Google Patents
A kind of catalyst of the direct producing light olefins of high stability synthesis gas, preparation method and applications Download PDFInfo
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- CN109261199A CN109261199A CN201811128470.0A CN201811128470A CN109261199A CN 109261199 A CN109261199 A CN 109261199A CN 201811128470 A CN201811128470 A CN 201811128470A CN 109261199 A CN109261199 A CN 109261199A
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- catalyst
- molecular sieve
- synthesis gas
- light olefins
- producing light
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 30
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 86
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 230000009467 reduction Effects 0.000 claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000012495 reaction gas Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 239000002905 metal composite material Substances 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 10
- 150000004706 metal oxides Chemical class 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 229910052799 carbon Inorganic materials 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- -1 ethylene, propylene, butadiene Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007039 two-step reaction Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- 229910014574 C—SiO2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7065—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of catalyst, preparation method and applications that producing light olefins are directly converted for synthesis gas.Catalyst of the invention is made of with cladded type molecular sieve catalyst 0.4:1~2:1 in mass ratio through physical mixed grinding metal oxide catalyst, and wherein metal oxide catalyst is the ZrO that Zr/Zn molar ratio is 2:12ZnO catalyst, cladded type molecular sieve catalyst are that pure silicon Silicalite-1 molecular sieve coats cladded type M@Silicalite-1 molecular sieve catalyst made of SAPO-34 or SSZ-13 molecular sieve.The cladded type molecular sieve catalyst acidity is adjustable, pore structure is abundant, large specific surface area, is applied to synthesis gas simultaneously with metal oxide catalyst and directly convert selectivity of light olefin, reduction by-product CO can be improved in reaction for preparing light olefins2Selectivity, and catalyst life can be extended.
Description
Technical field
The present invention relates to a kind of bifunctional catalyst and preparations that producing light olefins are directly converted for one-step method from syngas
Method more particularly to a kind of preparation method of cladded type composite molecular sieve catalyst.
Background technique
Low-carbon alkene (ethylene, propylene, butadiene) is important basic chemical industry raw material, is widely used in synthetic rubber, modeling
In the organic chemicals such as material, organic solvent.Very important effect is played in industrial production and national economy.
Preparation of low carbon olefines by synthetic gas mainly has FTO (by preparation of low carbon olefines by synthetic gas) and MTO (using methanol as intermediate product two
Footwork producing light olefins) two approach.Wherein the path FTO is that synthesis gas is turned at high temperature via iron-based, cobalt-base catalyst
Change, reaction product is mostly C5+Hydrocarbon, the selectivity of low-carbon alkene is difficult to break through the Anderson- in F- T synthesis in product
Schulz-Flory is distributed (58%), and this method is not the optimal selection of highly selective preparing low-carbon olefins.The path MTO is by two steps
Then methanol is introduced second that is, first in first reactor at a lower temperature by CO synthesizing methanol by hydrogenating by tandem reaction
It is converted into low-carbon alkene through molecular sieve catalytic at high temperature in a reactor, but two-step reaction temperature is inconsistent, reaction process
Energy consumption is high, equipment investment is costly.Based on factors above, catalyst needed for the two-step reaction of the path MTO is combined together, is designed
A kind of bifunctional catalyst carries out two-step reaction in the same reactor, and target product selectivity can be significantly higher than FTO
Path, at the same compared to the path MTO can it is energy saving, reduce cost.
Chinese patent CN106994366A reports a kind of Fe3C-SiO2The catalyst of@SAPO-34 coreshell type structure, this is urged
Agent be applied to Fischer-Tropsch synthesis in when, synthesis gas pass through molecular sieve shell enter catalyst nucleus and with its surface Fe base activity
Position interaction generates a series of hydrocarbon products by Fischer-Tropsch synthesis, under the confinement effect of shell molecular sieve pore passage, produces
Long-chain hydro carbons is restricted to external diffusion in object, only generates C1-C6Short-chain hydrocarbons effectively increase the selectivity of lower carbon number hydrocarbons.
Chinese patent CN108273548A discloses a kind of ZnO-Al2O3The preparation side of@SAPO-34 catalyst with core-casing structure
Method, this catalyst are with meso-porous ZnO-Al2O3For nuclear phase, micropore SAPO-34 is the catalyst with core-casing structure of shell phase, nuclear phase ZnO-
Al2O3Suitable L-B acid concerted catalysis center is formed with shell phase SAPO-34, improves the conversion ratio of methanol.The catalyst is used for
CO2Add hydrogen through CO can be improved simultaneously in preparing light olefins from methanol two-step process2Conversion ratio and low-carbon alkene selectivity.
Summary of the invention
The purpose of the present invention is to provide a kind of highly selective, high stability synthesis gas directly to convert urging for low-carbon alkene processed
The preparation method and application of agent and the catalyst.
The purpose of the present invention is what is realized by following technical concept.
A kind of catalyst of the direct producing light olefins of high stability synthesis gas, which is characterized in that the catalyst is by A, B two
Kind of component according to mass ratio 0.4:1~2:1 through physical mixed, grind；Wherein, it is 2 that the component A, which is Zr/Zn molar ratio:
1 ZrO2- ZnO metal composite oxide, the B component are the micropore that pure silicon Silicalite-1 molecular sieve coats CHA structure
The M@Silicalite-1 molecular sieve of cladded type structure made of sial system molecular sieve M, the micropore of CHA structure in the B component
The quality of sial system molecular sieve M and Silicalite-1 are 5~1:1 than range.
The component A Zr/Zn molar ratio is the ZrO of 2:12- ZnO metal composite oxide can use well known existing
Technology, such as the preparation of co-precipitation method；The microporous silicon of the B component pure silicon Silicalite-1 molecular sieve cladding CHA structure
Hydrothermal synthesis method preparation, specific skill can be used in the M@Silicalite-1 molecular sieve of cladded type structure made of aluminium system molecular sieve M
Art scheme is as follows.
(1) SAPO-34 or SSZ-13 molecular sieve is synthesized using hydro-thermal method first, the molecular sieve of synthesis is washed into
Property, drying and spare after 500 DEG C of roasting 6h.Gained SAPO-34 molecular sieve SiO2/Al2O3Molar ratio be 0.05~0.5,
SSZ-13 molecular sieve SiO2/Al2O3Molar ratio is 15~40, and the two specific surface area is in 400m2/ g or more, crystallite dimension 0.5
~2.0 μm.
(2) 4-propyl bromide (TPABr) for 1.0mol/L being added in SAPO-34 the or SSZ-13 molecular sieve after roasting is molten
3h is stirred in liquid at room temperature and carries out function dough.Simultaneously prepare at room temperature a certain proportion of tetraethyl ammonium hydroxide (TEAOH),
Ethyl orthosilicate (TEOS), deionized water, 0.5~6h of stirring are allowed to form vitreosol, by the SAPO-34 of function dough or
Stirring and 1~8h of aging in vitreosol is added in SSZ-13 molecular sieve, is then transferred in hydrothermal crystallizing kettle at 170~210 DEG C
24~72h of lower crystallization, the product after crystallization are washed to neutral, dry and obtain cladded type in 500~550 DEG C of 3~10h of roasting
Molecular sieve.
(3) quality of SAPO-34 or SSZ-13 molecular sieve and Silicalite-1 are 5~1:1 than range.
It is well known that SAPO-34 and SSZ-13 molecular sieve is the micropore sial system molecular sieve of common CHA structure, have
Higher selectivity of light olefin is widely used in preparing light olefins from methanol (MTO) technique.But SAPO-34 and SSZ-13
Be easy to produce carbon distribution and inactivate, for example, SAPO-34 molecular sieve outer surface occur carbon distribution be its inactivation a main cause.
Silicalite-1 molecular sieve has bigger aperture compared with both the above molecular sieve, is conducive to reactants and products and is being catalyzed
It is spread in agent.It is covered on the outer surface SAPO-34 (or SSZ-13) using Silicalite-1 as shell, prepares cladded type structure
SAPO-34@Silicalite-1 or SSZ-13@Silicalite-1 molecular sieve, using pure silicon Silicalite-1 molecular sieve
It prevents ethylene, propylene in the enterprising single step reaction of acidic site of catalyst external surface, reduces the generation of carbon distribution, improve low-carbon alkene
Selectivity.In addition, directly converted by synthesis gas there are a large amount of water gas shift reaction in preparing low carbon olefin hydrocarbon, it is available
The good hydrophobicity of Silicalite-1 molecular sieve, weakens the generation of water gas shift reaction, and reaching reduces by-product CO2Selection
The purpose of property.
The invention further relates to a kind of application of the catalyst of the direct producing light olefins of synthesis gas in fixed bed reactors, urge
The reducing condition of agent are as follows: 360~440 DEG C of reduction temperature, reducing atmosphere H2/N2(molar ratio is 0.4~2.0), recovery time
For 1~10h；Catalyst reaction condition is 380~430 DEG C, 5~30bar of reaction pressure, reaction gas H2/ CO molar ratio 1.0~
2.5,3000~5000mL/ of gas space velocity (gh).
Cladded type molecular sieve catalyst of the present invention has compared to SAPO-34 molecular sieve or SSZ-13 molecular sieve
Following substantive distinguishing features and progress:
(1) preparation method of catalyst of the present invention, overall flow is simple, metal oxide catalyst and cladded type molecular sieve
It is applied in syngas catalytic conversion reaction after catalyst mixing, it can be achieved that synthesis gas directly converts producing light olefins, reduction energy
Consumption reduces equipment investment.
(2) cladded type molecular sieve catalyst of the invention is coated on SAPO-34 using pure silicon Silicalite-1 molecular sieve
Or SSZ-13 molecular sieve surface, the highly acid position of molecular sieve surface is covered, thus reaction product can be prevented in catalyst strong acid
Property generates carbon distribution on position, extends the service life of catalyst.
(3) in cladded type molecular sieve catalyst of the invention, Silicalite-1 molecular sieve is a kind of good hydrophobicity
Substance is covered on SAPO-34 or SSZ-13 molecular sieve surface, can reduce the generation of water gas shift reaction in reaction, effectively drop
Low by-product CO2Selectivity.
Specific embodiment
Preparation method disclosed in this patent is further described below by specific embodiment, but the present invention is not by following
The limitation of embodiment.
Embodiment 1
ZrO is prepared using co-precipitation method2: ZnO molar ratio is the metal composite oxide of 2:1.Specific method is to press
The zirconium nitrate and zinc nitrate that Zr/Zn molar ratio is 2 are configured to the aqueous solution of 1.0mol/L, while preparing the sodium carbonate of 1.0mol/L
Solution is as precipitating reagent.Then by above two solution cocurrent be added dropwise in 100mL beaker precipitating and under 70 DEG C of water-baths it is strong
Stirring controls rate of addition and pH in precipitation process is made to remain 7.0.Obtained sediment aging 2h at 70 DEG C, then mistake
Filter, washing remove Na+, finally at 100 DEG C dry 12h, roasting 5h obtains ZrO at 500 DEG C2- ZnO oxide catalyst.
By SiO2/Al2O3Molar ratio is 0.25, specific surface area 485m2The SAPO-34 molecular sieve of/g and 1.0mol/L's
4h progress is stirred at room temperature in TPABr solution, is then centrifuged for being dried to obtain TPA+Functionalized SAPO-34 molecular sieve.By quality
Than 15.6 parts of ethyl orthosilicates to be slowly dropped to 10.0 part 20% of tetraethyl ammonium hydroxide, shape in 135.0 parts of deionized waters
At clear solution and continue to stir 2h, weighs 10.0 parts of above-mentioned functionalized SAPO-34 molecular sieves and be added in clear solution, and
It is vigorously stirred 2h at room temperature, then the crystallization 72h at 170 DEG C in crystallizing kettle.Product is after centrifugation, washing, drying after crystallization
Solid 500 DEG C of roasting 6h in Muffle furnace obtain the cladded type molecular sieve that SAPO-34@Silicalite-1 mass ratio is 2.15 and urge
Agent.1 part and 2 parts of cladded type molecular sieve catalyst of above-mentioned metal oxide catalyst is taken, simultaneously tabletting is screened to for grinding after mixing
20~40 mesh are spare.
The reduction of catalyst, activity rating condition and specific step is as follows: the catalyst of a certain amount of 20~40 mesh is taken first
It is placed in fixed bed reactors, is 400 DEG C, also Primordial Qi H in reduction temperature2:N2Volume ratio is 1:1, recovery time 4h.Reduction
Reduction autogenous cutting is changed to raw material reaction gas, raw material reaction gas H afterwards2: the volume ratio of CO is 1:1, and reaction temperature is 400 DEG C, reacts
Pressure 10bar, gas space velocity are 3600mL/ (gh).Sampling analysis after stable reaction, activity rating reaction result see attached list 1.
Embodiment 2
Prepare ZrO2: ZnO molar ratio is the metal composite oxide of 2:1, and specific preparation method and process are the same as embodiment 1.
By SiO2/Al2O3Molar ratio is 0.15, specific surface area 460m2The SAPO-34 molecular sieve of/g and 1.0mol/L's
4h progress is stirred at room temperature in TPABr solution, is then centrifuged for being dried to obtain TPA+Functionalized SAPO-34 molecular sieve.By quality
Than 15.6 parts of ethyl orthosilicates to be slowly dropped to 6.4 part 35% of tetraethyl ammonium hydroxide, are formed in 100.0 parts of deionized waters
Clear solution simultaneously continues to stir 1h, weighs 15.0 parts of above-mentioned functionalized SAPO-34 molecular sieves and is added in clear solution, and in room
3h is vigorously stirred under temperature, then the crystallization 48h at 180 DEG C in crystallizing kettle.Product consolidating after centrifugation, washing, drying after crystallization
Body 550 DEG C of roasting 8h in Muffle furnace obtain the cladded type molecular sieve catalytic that SAPO-34@Silicalite-1 mass ratio is 3.01
Agent.2 parts and 5 parts of cladded type molecular sieve catalyst of above-mentioned metal oxide catalyst are taken, simultaneously tabletting is screened to 20 for grinding after mixing
~40 mesh are spare.
The reduction of catalyst, activity rating condition and specific step is as follows: the catalyst of a certain amount of 20~40 mesh is taken first
It is placed in fixed bed reactors, is 380 DEG C, also Primordial Qi H in reduction temperature2:N2Volume ratio is 1.2:1, recovery time 6h.Also
Reduction autogenous cutting is changed to raw material reaction gas, raw material reaction gas H after original2: the volume ratio of CO is 2:1, and reaction temperature is 410 DEG C, instead
Answering pressure 20bar, gas space velocity is 4800mL/ (gh).Sampling analysis after stable reaction, activity rating reaction result are seen attached list
1。
Embodiment 3
Prepare ZrO2: ZnO molar ratio is the metal composite oxide of 2:1, and specific preparation method and process are the same as embodiment 1.
By SiO2/Al2O3Molar ratio is 0.25, specific surface area 485m2The SAPO-34 molecular sieve of/g and 1.0mol/L's
4h progress is stirred at room temperature in TPABr solution, is then centrifuged for being dried to obtain TPA+Functionalized SAPO-34 molecular sieve.By quality
Than 15.6 parts of ethyl orthosilicates to be slowly dropped to 15.0 part 25% of tetraethyl ammonium hydroxide, are formed in 50.0 parts of deionized waters
Clear solution simultaneously continues to stir 5h, weighs 20.0 parts of above-mentioned functionalized SAPO-34 molecular sieves and is added in clear solution, and in room
3h is vigorously stirred under temperature, then the crystallization 36h at 180 DEG C in crystallizing kettle.Product consolidating after centrifugation, washing, drying after crystallization
Body 500 DEG C of roasting 4h in Muffle furnace obtain the cladded type molecular sieve catalytic that SAPO-34@Silicalite-1 mass ratio is 4.26
Agent.1 part and 1 part of cladded type molecular sieve catalyst of above-mentioned metal oxide catalyst is taken, simultaneously tabletting is screened to 20 for grinding after mixing
~40 mesh are spare.
The reduction of catalyst, activity rating condition and specific step is as follows: the catalyst of a certain amount of 20~40 mesh is taken first
It is placed in fixed bed reactors, is 370 DEG C, also Primordial Qi H in reduction temperature2:N2Volume ratio is 0.8:1, recovery time 5h.Also
Reduction autogenous cutting is changed to raw material reaction gas, raw material reaction gas H after original2: the volume ratio of CO is 1:1, and reaction temperature is 420 DEG C, instead
Answering pressure 15bar, gas space velocity is 3600mL/ (gh).Sampling analysis after stable reaction, activity rating reaction result are seen attached list
1。
Embodiment 4
Prepare ZrO2: ZnO molar ratio is the metal composite oxide of 2:1, and specific preparation method and process are the same as embodiment 1.
By SiO2/Al2O3Molar ratio is 20, specific surface area 610m2The SSZ-13 molecular sieve of/g and 1.0mol/L's
4h progress is stirred at room temperature in TPABr solution, is then centrifuged for being dried to obtain TPA+Functionalized SSZ-13 molecular sieve.In mass ratio
By 15.6 parts of ethyl orthosilicates be slowly dropped to 8.2 part 35% of tetraethyl ammonium hydroxide, formed in 80.0 parts of deionized waters it is saturating
Bright solution simultaneously continues to stir 3h, weighs 20.0 parts of above-mentioned functionalized SSZ-13 molecular sieves and is added in clear solution, and in room temperature
Under be vigorously stirred 6h, then crystallization is for 24 hours at 200 DEG C in crystallizing kettle.Solid of the product after centrifugation, washing, drying after crystallization
520 DEG C of roasting 6h obtain the cladded type molecular sieve catalyst that SSZ-13@Silicalite-1 mass ratio is 4.09 in Muffle furnace.
1 part and 1 part of cladded type molecular sieve catalyst of above-mentioned metal oxide catalyst is taken, simultaneously tabletting is screened to 20~40 for grinding after mixing
Mesh is spare.
The reduction of catalyst, activity rating condition and specific step is as follows: the catalyst of a certain amount of 20~40 mesh is taken first
It is placed in fixed bed reactors, is 410 DEG C, also Primordial Qi H in reduction temperature2:N2Volume ratio is 0.6:1, recovery time 3h.Also
Reduction autogenous cutting is changed to raw material reaction gas, raw material reaction gas H after original2: the volume ratio of CO be 1.5:1, reaction temperature be 390 DEG C,
Reaction pressure 25bar, gas space velocity are 3200mL/ (gh).Sampling analysis after stable reaction, activity rating reaction result are shown in attached
Table 1.
Comparative example 1
ZrO is prepared using co-precipitation method2: ZnO molar ratio is the metal oxide of 2:1.
1 part and 2 parts of SAPO-34 molecular sieve catalyst of above-mentioned metal oxide catalyst is taken, grinding and tabletting after mixing
It is spare to be sieved to 20~40 mesh.
The reduction of catalyst, activity rating condition and specific step is as follows: the catalyst of a certain amount of 20~40 mesh is taken first
It is placed in fixed bed reactors, is 400 DEG C, also Primordial Qi H in reduction temperature2:N2Volume ratio is 1:1, recovery time 3h.Reduction
Reduction autogenous cutting is changed to raw material reaction gas, raw material reaction gas H afterwards2: the volume ratio of CO is 1:1, and reaction temperature is 400 DEG C, reacts
Pressure 10bar, gas space velocity are 3600mL/ (gh).Sampling analysis after stable reaction, activity rating reaction result see attached list 1.
Evaluation results are shown in Table 1 for catalyst activity in embodiment 1 to 4 and comparative example 1.
1 catalyst activity evaluation response result of table
Note: the selective calculation method of all hydro carbons removes CO2It obtains.
By table 1, it is apparent that the catalyst of the direct producing light olefins of the claimed synthesis gas of the application is answered
For carrying out the reaction of high―temperature nuclei low-carbon alkene, in addition to embodiment 4, CO in synthesis gas in the remaining embodiments in fixed bed reactors
Conversion ratio significantly improves, and CH in all embodiments4Selectivity can be down to 12% or so, C2 =-C4 =Olefine selective can be improved to
72% or more, and ethylenic alkoxy rate can reach 9.0 in product, show that catalyst of the present invention is applied in syngas catalytic conversion reaction,
The high efficiency conversion that preparing low-carbon olefin can be achieved, reduces energy consumption of reaction.
It should be noted that catalyst of the present invention is applied to carry out the reaction of high―temperature nuclei low-carbon alkene in fixed bed reactors
When, the service life of four embodiments is respectively 30h, 29h, 22h, 28h, and comparative example 1 is only 22h, shows cladded type of the present invention point
Sub- sieve catalyst has better stability compared to SAPO-34 molecular sieve, and catalytic life is longer.
Claims (10)
1. the catalyst that a kind of high stability synthesis gas directly converts producing light olefins, which is characterized in that the catalyst is by A, B
Two kinds of components according to mass ratio 0.4:1~2:1 through physical mixed, grind；Wherein, the component A is that Zr/Zn molar ratio is
The ZrO of 2:12- ZnO metal composite oxide, the B component are that pure silicon Silicalite-1 molecular sieve coats the micro- of CHA structure
The M@Silicalite-1 molecular sieve of cladded type structure made of hole sial system molecular sieve M, CHA structure is micro- in the B component
The quality of hole sial system molecular sieve M and Silicalite-1 are 5~1:1 than range.
2. the catalyst of the direct producing light olefins of high stability synthesis gas as described in claim 1, which is characterized in that described
The specific surface area of the micropore sial system molecular sieve M of CHA structure is 400m2/ g or more, crystallite dimension are 0.5~2.0 μm.
3. the catalyst of the direct producing light olefins of high stability synthesis gas as claimed in claim 1 or 2, which is characterized in that institute
The micropore sial system molecular sieve M for stating CHA structure is SAPO-34 molecular sieve or SSZ-13 molecular sieve.
4. the catalyst of the direct producing light olefins of high stability synthesis gas as claimed in claim 3, which is characterized in that described
SiO in SAPO-34 molecular sieve2/Al2O3Molar ratio is 0.05~0.5.
5. the catalyst of the direct producing light olefins of high stability synthesis gas as claimed in claim 3, which is characterized in that described
SiO in SSZ-13 molecular sieve2/Al2O3Molar ratio is 15~40.
6. a kind of preparation method of the catalyst of the direct producing light olefins of high stability synthesis gas, includes the following steps:
1) ZrO that Zr/Zn molar ratio is 2:1 is prepared2- ZnO metal composite oxide；
2) the M@Silicalite-1 molecular sieve of cladded type structure is prepared, wherein M is SAPO-34 molecular sieve or SSZ-13 molecule
Sieve；
3) by ZrO2The M@Silicalite-1 molecular sieve of-ZnO metal composite oxide and cladded type structure, according to mass ratio
0.4:1~2:1, physical mixed, grinding, tabletting sieving, obtains the catalyst of the direct producing light olefins of high stability synthesis gas.
7. the preparation method of the catalyst of the direct producing light olefins of high stability synthesis gas according to claim 6, special
Sign is, the detailed process that the M@Silicalite-1 system with molecular sieve for preparing of cladded type structure is standby is,
1) first synthesize M molecular sieve, it is then that the molecular sieve of synthesis is washed to neutral, dry and in 500 DEG C of roasting 6h；
2) the M molecular sieve after roasting is added in the 4-propyl bromide of 1.0mol/L and stirs 3h progress function dough at room temperature,
Obtain the M molecular sieve of function dough；
3) a certain proportion of tetraethyl ammonium hydroxide, ethyl orthosilicate, deionized water solution are prepared at room temperature, stirring 0.5~
6h is allowed to form vitreosol；
4) will the resulting function dough of step 2) M molecular sieve be added the resulting vitreosol of step 3) in, stir and aging 1~
8h is then transferred in hydrothermal crystallizing kettle 24~72h of crystallization at 170~210 DEG C；
5) product after crystallization obtained by step 4) is washed to neutral, drying, then in 500~550 DEG C of 3~10h of roasting, is obtained
Cladded type M@Silicalite-1 molecular sieve.
8. the preparation method of the catalyst of the direct producing light olefins of high stability synthesis gas according to claim 7, special
Sign is, tetraethyl ammonium hydroxide in step 3), ethyl orthosilicate, deionized water mass parts ratio be (6~15): 15.6:
(50~140).
9. the catalyst of the direct producing light olefins of high stability synthesis gas described in a kind of any one of claims 1 to 5 is solid
Application in fixed bed reactor, which is characterized in that the catalyst is restored first, then again by the catalyst after reduction
Applied to the direct producing light olefins catalysis reaction of synthesis gas, it is catalyzed the condition of reaction are as follows: 380~430 DEG C of reaction temperature, reaction pressure
5~30bar of power, reaction gas H2/ CO molar ratio 1.0~2.5,3000~5000mL/ of gas space velocity (gh).
10. the catalyst of the direct producing light olefins of high stability synthesis gas as claimed in claim 9 is in fixed bed reactors
Application, which is characterized in that the condition that the catalyst is restored are as follows: 360~440 DEG C of reduction temperature, reducing atmosphere is
H2/N2=0.4~2.0, the recovery time is 1~10h.
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