CN104888838B - A kind of catalyst of direct producing light olefins of hud typed synthesis gas and preparation method and application - Google Patents
A kind of catalyst of direct producing light olefins of hud typed synthesis gas and preparation method and application Download PDFInfo
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Abstract
A kind of catalyst of the direct producing light olefins of hud typed synthesis gas is made up of active component, auxiliary agent and carrier, and its percentage by weight composition is：Cobalt oxide：2.0~20%, manganese oxide 2.5~20%, metal promoter oxide content 0.05~2.0%, carrier is 58~95%.The present invention has high selectivity, while CO can be substantially reduced2The advantage of selectivity.
Description
Technical field
It is direct more particularly to a kind of hud typed synthesis gas the invention belongs to a kind of catalyst and preparation method and application
The catalyst and preparation method of producing light olefins and the application in low-carbon alkene synthesis.
Technical background
Low-carbon alkene (ethene, propylene and butylene) is as important petrochemical industry basic material, and application is extremely extensive, mainly
Purposes has following aspect：Ethene is mainly used in synthetic rubber, synthetic resin (such as polystyrene, polyvinyl chloride), synthetic fibers, ring
The organic synthesis product such as oxidative ethane, explosive, ethanol, acetaldehyde, acetic acid, it is possible to instead of acetylene to cut and welding metal, also
Fruit ripener can be made, synthetic resin and plastics is currently used primarily in.Propylene is mainly for the production of polypropylene (PP), acrylonitrile
(AN), expoxy propane (PO), acetone, butanol, octanol, acrylic acid and isopropanol etc., other purposes also include alkylate oil, urged
Change overlapping and dimerization, for high-octane gasoline blending stock etc..Butylene is mainly for the production of MEK, high-knock rating gasoline group
Point, and for producing anhydride maleique, sec-butyl alcohol, polybutene and acetic anhydride etc..
In recent years, the international well-known chemical company such as BASF, Dow/S ü d-Chemie proposes the coal base synthesis of exploitation a new generation
The process route of gas alkene directly processed.Compared with coal based synthetic gas through methanol-to-olefins route, being mainly characterized by of technique passes through
The principle of F- T synthesis (Fischer-Tropsch Synthesis, FTs), by synthesis gas alkene directly processed, it is to avoid middle production
The synthesis of thing methanol and purification procedures, the process route are shorter, and Installed capital cost and operating cost are relative to coal-based methanol system
Olefin process route is relatively low, is expected to reduce the cost of unit olefin product.
The domestic and international progress of the petrochemical material such as low-carbon alkene technology of ethene, propylene and butylene is directly produced from synthesis gas
Differ.It is effective control product distribution while olefine selective is improved to need the key problem solved at present.Classical
F-T catalyst is general to produce based on heavy hydrocarbon, and the yield of light hydrocarbon especially low-carbon alkene is relatively low.VIII cycle metals：Fe、
Co, Ni and Ru etc. study more in F-T synthesis, and for selectivity synthesis alkene, Fe, Co catalyst are due to possessing economy
Research is more deep, and some catalyst system and catalyzings have been achieved for preferable result.For Fe, Co bases catalyst generally by with
In the synthesis of long-chain hydro carbons, such as paraffin and diesel oil, the research of low-carbon alkene is rarely used in.In the last few years, grinding with people
Study carefully discovery, Co base catalyst can also be used for the preparation of light hydrocarbon, petrochemical material such as ethene, third are directly particularly produced from synthesis gas
Alkene, butylene etc..Co bases catalyst is studied in F-T reactions by Many researchers, is as a result shown：Bar is prepared in similar
Under part, the performance of Co base catalyst is more excellent than Fe base, particularly in terms of the life-span of catalyst.Although Fe bases
Catalyst research obtains more deep, but the subject matter showed when being reacted for low-carbon alkene is that water gas shift reaction is higher,
So as to cause CO2Selectivity it is higher, and resulting C utilization rates are very low, limit its application.Chen etc. studies Co-Mo
Bimetallic catalyst, catalyst composition 6Co:lMo:4K:100SiO2, in reaction temperature 553K, pressure 101Kpa, CO/H2=1:
19~19:Modified through Mo when 1, chain growth probability and olefin(e) centent increase, and ethene and methane content ratio are up to 70% in product
~100%.Mo addition inhibits the generation of methane simultaneously.And the generation activation energy of light hydrocarbon is compared with Co base catalyst degradations
10-15%.Therefore, by developing New Co base catalyst, it is expected to improve the selectivity of low-carbon alkene in specific manner, and this is new
Type catalyst has low CO2The characteristics of.
Molecular sieve has special pore passage structure feature, therefore is widely used in preparing low-carbon olefin reaction
In, and have made some progress.Because different molecular sieve carriers has different surface acidic-basic properties and pore passage structure, therefore system
Standby catalyst has very big difference in terms of the direct producing light olefins of synthesis gas.The more commonly used molecular sieve has ZSM-5, ZSM-
12nd, Silicalite-1, Silicalite-2 etc..Domestic Chinese Academy of Sciences Dalian Chemistry and Physics Institute Xu Long child is using high silica alumina ratio ZSM-5 as load
Body, the Fe-Mn-K/ZSM-5 catalyst of high selectivity and high activity is prepared for by infusion process, is 320 DEG C in reaction temperature, pressure
Power is 2.0MPa, air speed 1000h-1, H2Under/CO=2, CO conversion ratio is up to 70%~90%, and the selectivity of low-carbon alkene is
71%~74%.Therefore, selection ZSM-5 is as carrier, by the regulation of effect of acidity and basicity and pore passage structure, is expected to improve low
The selectivity of carbon olefin.
Thus prepare and synthesis gas is converted into low-carbon alkene by the catalyst of application tool core shell structure, can high selectivity
Ground synthesizing low-carbon alkene, the CO of reduction2Selectivity, with Important Academic value and realistic meaning.
The content of the invention
It is an object of the invention to provide a kind of high selectivity, while CO can be substantially reduced2The core shell structure catalysis of selectivity
Agent and preparation method and the application in low-carbon alkene synthesis.
Catalyst of the present invention is made up of active component, auxiliary agent and carrier, and its percentage by weight composition is：Cobalt oxide：2.0~
20%, manganese oxide 2.5~20%, metal promoter oxide content 0.05~2.0%, carrier is 58~95%.Carrier boils for silicon
Stone.
Catalyst with core-casing structure physico-chemical property as described above：Kernel diameter be 5~50nm, shell thickness be 10~
100nm, 400~1400m of specific surface area of catalyst2/ g, 0.5~2.5cm of pore volume3/ g, catalyst particle diameter size be 60~
200nm。
Metal promoter as described above is one or both of ruthenium, rhodium, palladium, platinum, lanthanum, cerium, rhenium, magnesium, zirconium, caesium etc..
The preparation method of catalyst of the present invention is as follows：
(1), constituted by catalyst, by Co (NO3)3·6H2O and Mn (NO3)2It is 10~50wt%'s to be configured to concentration respectively
Solution, then adds soluble metal auxiliary compound, and it is 0.05~2wt% to make its concentration, and it is dense in equal volume with the solution
25~28wt%NH of degree3·H2O solution co-precipitations, sediment obtains Co, Mn mixture and sunk through aging, washing, filtering
Form sediment；
(2) it is tetraethyl orthosilicate by colloidal sol mol ratio using TPAOH TPAOH as structure directing agent
(TEOS):TPAOH:Aluminium isopropoxide (CH3)2CHO)3Al:5H2O:Ethanol (EtOH)=1.0~3:0.25~0.5:0.025~
0.06:50~80:2~5, this several material will be added in the stainless steel cauldron containing polytetrafluoroethyllining lining successively,
2~4h is stirred under 60~80 10~20rpm of DEG C ﹑ until forming the uniform colloidal sol of glassy yellow, obtains colloidal sol；
(3) Co, Mn mixture precipitation is added in colloidal sol again stir evenly it is uniform, 120~180 DEG C and rotating speed be 10~
After 10~20h of crystallization under 30rpm, natural cooling, floccule is obtained, and filtrate pH value is washed till repeatedly less than 8 with deionized water, 60
12~24h is dried at~80 DEG C, is calcined 5~10h at 450~550 DEG C to remove organic lead in 1~3K/min heating rate
To agent, required catalyst is obtained.
Soluble metal auxiliary compound as described above is the metals such as ruthenium, rhodium, palladium, platinum, lanthanum, cerium, rhenium, magnesium, zirconium, caesium
Nitrate or chlorate.
Catalyst obtained by the present invention can be used for fixed bed Fischer-Tropsch synthesis device, and reaction condition is：Reaction pressure 1.5
~3Mpa, 150~300 DEG C of reaction temperature, GHSV=1000~2000h-1, H2/ CO=1.5~3 (mol ratio).
The present invention has the following advantages that compared with prior art：
1st, the catalyst crystal time is short, substantially reduces process cycle.
2nd, obtaining catalyst using the inventive method has that core metal particle size is small, and shell thickness is adjustable, and
Specific surface area is larger, the characteristics of pore volume is big.
3rd, catalyst of the present invention carries out low-carbon alkene synthetic quantity, and CO conversion ratios are up to 50~90%, and product quality content is constituted：
CH4<5%, C2=C4>=70%, C5-C12≤ 20%, C12+<5%, CO2<0.5%.
Embodiment
Embodiment 1
By 300ml 10wt%Co (NO3)3·6H2O and 200ml 10wt%Mn (NO3)2Solution is mixed, and adds chlorination
Ruthenium, it is 0.05wt% to make its content, then by its 500ml NH isometric with the solution3·H2O (25-28wt%) solution is simultaneously
Stream co-precipitation, sediment obtains Co, Mn mixture precipitation through aging, washing, filtering.
Using TPAOH TPAOH as structure directing agent, colloidal sol mol ratio is 1.0TEOS:0.25TPAOH:
0.025((CH3)2CHO)3Al:50H2O:2EtOH.This several material will be added to containing polytetrafluoroethyllining lining not successively
Become rusty in steel reactor, stir 2h until forming the uniform colloidal sol of glassy yellow under 60 DEG C ﹑ 10rpm, obtain 150ml colloidal sols.Again by Co, Mn
Mixture precipitation is added in colloidal sol and stirred, the crystallization 10h in the case where 120 DEG C and rotating speed are 10rpm.After natural cooling, spend from
Sub- water is washed till filtrate pH value for 7.9 repeatedly, and 12h is dried at 60 DEG C, 1K/min heating rate be calcined at 450 DEG C 5h with
Organic directing agent is removed, catalyst C-1 needed for obtaining.Its catalyst composition is shown in Table 1.
Obtained catalyst is used for fixed bed Fischer-Tropsch synthesis device, reaction condition is：Reaction pressure 1.5Mpa, reaction
150 DEG C of temperature, GHSV=1000h-1, H2/ CO=1.5 (mol ratio).Products therefrom distribution is shown in Table 2.
Embodiment 2
By 500ml 10wt%Co (NO3)3·6H2O and 300ml 50wt%Mn (NO3)2Solution is mixed, and is added a certain amount of
Lanthanum nitrate, make its content be 2wt%, then by its NH isometric with the mixed solution3·H2O (25-28wt%) solution is simultaneously
Stream co-precipitation, sediment obtains Co, Mn mixture precipitation through aging, washing, filtering.
Using TPAOH TPAOH as structure directing agent, colloidal sol mol ratio is 3TEOS:0.5TPAOH:0.06
((CH3)2CHO)3Al:80H2O:5EtOH.This several material be will be added into the stainless steel containing polytetrafluoroethyllining lining successively
In reactor, 4h is stirred until forming the uniform colloidal sol of glassy yellow under 80 DEG C ﹑ 20rpm, 200ml colloidal sols are obtained.Co, Mn are mixed again
Thing precipitation, which is added in colloidal sol, to be stirred evenly, the crystallization 20h in the case where 180 DEG C and rotating speed are 30rpm.After natural cooling, with deionized water repeatedly
It is 7.9 to be washed till filtrate pH value, and 24h is dried at 80 DEG C, is calcined 10h at 550 DEG C to have removed in 3K/min heating rate
Machine directed agents, catalyst C-2 needed for obtaining.Its catalyst composition is shown in Table 1.
Obtained catalyst is used for fixed bed Fischer-Tropsch synthesis device, reaction condition is：Reaction pressure 3Mpa, reaction temperature
300 DEG C of degree, GHSV=2000h-1, H2/ CO=3 (mol ratio).Products therefrom distribution is shown in Table 2.
Embodiment 3
By 350ml 15wt%Co (NO3)3·6H2O and 300ml 50wt%Mn (NO3)2Solution is mixed, and is added a certain amount of
Chloroplatinic acid, make its content be 0.5wt%, then by its NH isometric with the mixed solution3·H2O (25-28wt%) solution
Co-precipitation, sediment obtains Co, Mn mixture precipitation through aging, washing, filtering.
Using TPAOH TPAOH as structure directing agent, colloidal sol mol ratio is 1.5TEOS:0.3TPAOH:0.03
((CH3)2CHO)3Al:50H2O:2EtOH.This several material be will be added into the stainless steel containing polytetrafluoroethyllining lining successively
In reactor, 2h is stirred until forming the uniform colloidal sol of glassy yellow under 60 DEG C ﹑ 15rpm, 150ml colloidal sols are obtained.Co, Mn are mixed again
Thing precipitation, which is added in colloidal sol, to be stirred evenly, the crystallization 12h in the case where 120 DEG C and rotating speed are 15rpm.After natural cooling, with deionized water repeatedly
It is 7.9 to be washed till filtrate pH value, and 12h is dried at 60 DEG C, 6h is calcined at 450 DEG C in 1K/min heating rate organic to remove
Directed agents, catalyst C-3 needed for obtaining.Its catalyst composition is shown in Table 1.
Obtained catalyst is used for fixed bed Fischer-Tropsch synthesis device, reaction condition is：Reaction pressure 2Mpa, reaction temperature
250 DEG C of degree, GHSV=1200h-1, H2/ CO=2 (mol ratio).Products therefrom distribution is shown in Table 2.
Embodiment 4
By 400ml 20wt%Co (NO3)3·6H2O and 300ml 15wt%Mn (NO3)2Solution is mixed, and is added a certain amount of
Zirconium oxychloride, make its content be 1wt%, then by its NH isometric with the mixed solution3·H2O (25-28wt%) solution
Co-precipitation, sediment obtains Co, Mn mixture precipitation through aging, washing, filtering.
Using TPAOH TPAOH as structure directing agent, colloidal sol mol ratio is 2TEOS:0.3TPAOH:0.04
((CH3)2CHO)3Al:60H2O:3EtOH.This several material be will be added into the stainless steel containing polytetrafluoroethyllining lining successively
In reactor, 2h is stirred until forming the uniform colloidal sol of glassy yellow under 70 DEG C ﹑ 10rpm, 180ml colloidal sols are obtained.Co, Mn are mixed again
Thing precipitation, which is added in colloidal sol, to be stirred evenly, the crystallization 15h in the case where 150 DEG C and rotating speed are 10rpm.After natural cooling, with deionized water repeatedly
It is 7.9 to be washed till filtrate pH value, and 12h is dried at 70 DEG C, 6h is calcined at 450 DEG C in 1K/min heating rate organic to remove
Directed agents, catalyst C-4 needed for obtaining.Its catalyst composition is shown in Table 1.
Obtained catalyst is used for fixed bed Fischer-Tropsch synthesis device, reaction condition is：Reaction pressure 2.5Mpa, reaction
230 DEG C of temperature, GHSV=1500h-1, H2/ CO=1.8 (mol ratio).Products therefrom distribution is shown in Table 2.
Embodiment 5
By 450ml 30wt%Co (NO3)3·6H2O and 250ml 10wt%Mn (NO3)2Solution is mixed, and is added a certain amount of
Magnesium nitrate, make its content be 1.5wt%, then by its NH isometric with the mixed solution3·H2O (25-28wt%) solution
Co-precipitation, sediment obtains Co, Mn mixture precipitation through aging, washing, filtering.
Using TPAOH TPAOH as structure directing agent, colloidal sol mol ratio is 3TEOS:0.4TPAOH:0.04
((CH3)2CHO)3Al:60H2O:3EtOH.This several material be will be added into the stainless steel containing polytetrafluoroethyllining lining successively
In reactor, 3h is stirred until forming the uniform colloidal sol of glassy yellow under 70 DEG C ﹑ 10rpm, 200ml colloidal sols are obtained.Co, Mn are mixed again
Thing precipitation, which is added in colloidal sol, to be stirred evenly, the crystallization 16h in the case where 150 DEG C and rotating speed are 20rpm.After natural cooling, with deionized water repeatedly
It is 7.9 to be washed till filtrate pH value, and 16h is dried at 65 DEG C, 5h is calcined at 500 DEG C in 2K/min heating rate organic to remove
Directed agents, catalyst C-5 needed for obtaining.Its catalyst composition is shown in Table 1.
Obtained catalyst is used for fixed bed Fischer-Tropsch synthesis device, reaction condition is：Reaction pressure 2Mpa, reaction temperature
200 DEG C of degree, GHSV=1000h-1, H2/ CO=2 (mol ratio).Products therefrom distribution is shown in Table 2.
Embodiment 6
By 400ml 40wt%Co (NO3)3·6H2O and 250ml 20wt%Mn (NO3)2Solution is mixed, and is added a certain amount of
Palladium bichloride, make its content be 1wt%, then by its NH isometric with the mixed solution3·H2O (25-28wt%) solution is simultaneously
Stream co-precipitation, sediment obtains Co, Mn mixture precipitation through aging, washing, filtering.
Using TPAOH TPAOH as structure directing agent, colloidal sol mol ratio is 2TEOS:0.3TPAOH:0.05
((CH3)2CHO)3Al:70H2O:3EtOH.This several material be will be added into the stainless steel containing polytetrafluoroethyllining lining successively
In reactor, 2h is stirred until forming the uniform colloidal sol of glassy yellow under 70 DEG C ﹑ 15rpm, 200ml colloidal sols are obtained.Co, Mn are mixed again
Thing precipitation, which is added in colloidal sol, to be stirred evenly, the crystallization 20h in the case where 160 DEG C and rotating speed are 15rpm.After natural cooling, with deionized water repeatedly
It is 7.9 to be washed till filtrate pH value, and 20h is dried at 70 DEG C, 8h is calcined at 500 DEG C in 2K/min heating rate organic to remove
Directed agents, catalyst C-6 needed for obtaining.Its catalyst composition is shown in Table 1.
Obtained catalyst is used for fixed bed Fischer-Tropsch synthesis device, reaction condition is：Reaction pressure 2.3Mpa, reaction
230 DEG C of temperature, GHSV=1500h-1, H2/ CO=2.5 (mol ratio).Products therefrom distribution is shown in Table 2.
The architectural feature of the catalyst of table 1
The Fischer-Tropsch synthesis result of the catalyst of table 2
| Catalyst | Reaction condition | CO conversion ratios % | C1% | C2-4 =% | C5-12% | C12+ |
| C-1 | 150 DEG C, 1000h-1, | 55 | 4.8 | 73 | 18 | 4 |
| C-2 | 300 DEG C, 2000h-1, | 80 | 4.5 | 72 | 20 | 3 |
| C-3 | 250 DEG C, 1200h-1, | 60 | 4.5 | 73 | 18 | 4.2 |
| C-4 | 230 DEG C, 1500h-1, | 60 | 4.3 | 76 | 15 | 4.5 |
| C-5 | 200 DEG C, 1000h-1, | 55 | 4.3 | 75 | 18 | 2.3 |
| C-6 | 230 DEG C, 1500h-1, | 70 | 4.6 | 72 | 19 | 4.1 |
Claims (5)
1. a kind of catalyst of the direct producing light olefins of hud typed synthesis gas, it is characterised in that catalyst is by active component, auxiliary agent
With carrier composition, its percentage by weight composition is：
Active component：Cobalt oxide 2.0~20%, manganese oxide 2.5~20%；Metal promoter oxide 0.05~2.0%；Carrier silicon boils
Stone 58~95%；Active component constitutes kernel with auxiliary agent, and silicone zeolite is shell；
Catalyst physico-chemical property：Kernel diameter is 5~50 nm, and shell thickness is 10~100 nm, specific surface area of catalyst
400~1400 m2/ g, the cm of pore volume 0.5~2.53/ g, catalyst particle diameter size is 60~200 nm.
2. a kind of catalyst of the hud typed direct producing light olefins of synthesis gas as claimed in claim 1, it is characterised in that described
Metal promoter one or both of for ruthenium, rhodium, palladium, platinum, lanthanum, cerium, rhenium, magnesium, zirconium, caesium.
3. a kind of preparation side of the catalyst of hud typed direct producing light olefins of synthesis gas as described in claim any one of 1-2
Method, it is characterised in that comprise the following steps：
(1), constituted by catalyst, by Co (NO3)3•6H2O and Mn (NO3)2The solution that concentration is 10~50wt% is configured to respectively,
Mixing, then adds soluble metal auxiliary compound, and it is 0.05~2wt% to make its concentration, obtains mixed solution, will be with mixing
Isometric 25~28wt% the NH of solution3•H2O solution co-precipitations, sediment obtains Co, Mn and mixed through aging, washing, filtering
Compound is precipitated；
(2) it is tetraethyl orthosilicate by mol ratio, using TPAOH as structure directing agent:TPAOH:
Aluminium isopropoxide: H2O:Ethanol=1.0~3:0.25~0.5:0.025~0.06:50~80:2~5, by this several material successively
Be added in the stainless steel cauldron containing polytetrafluoroethyllining lining, under the rpm of 60~80 DEG C ﹑ 10~20 stir 2~4h until
The uniform colloidal sol of glassy yellow is formed, colloidal sol is obtained；
(3), Co, Mn mixture precipitation are added in colloidal sol again and stirred evenly, it is brilliant in the case where 120~180 DEG C and rotating speed are 10~30 rpm
Change after 10~20h, natural cooling, be washed till filtrate pH value repeatedly with deionized water less than 8,12~24h is dried at 60~80 DEG C,
With 1~3K/min heating rate, it is warming up to 450~550 DEG C of h of roasting temperature 5~10 to remove organic directing agent, obtains institute
Need catalyst.
4. a kind of preparation method of the catalyst of the hud typed direct producing light olefins of synthesis gas as claimed in claim 3, it is special
Levy be described soluble metal auxiliary compound for ruthenium, rhodium, palladium, platinum, lanthanum, cerium, rhenium, magnesium, zirconium, the nitrate of caesium metal or
Chlorate.
5. a kind of application of the catalyst of hud typed direct producing light olefins of synthesis gas as described in claim any one of 1-2,
It is characterized in that catalyst is used for fixed bed Fischer-Tropsch synthesis device, reaction condition is：The MPa of reaction pressure 1.5~3, reaction
Temperature 150~300oThe h of C, GHSV=1000~2000-1, H2/ CO mol ratio=1.5~3.
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| CN106607048B (en) * | 2015-10-21 | 2019-06-11 | 中国石油化工股份有限公司 | The method of fixed bed production low-carbon alkene |
| CN109939668B (en) * | 2018-01-26 | 2020-05-22 | 中国科学院大连化学物理研究所 | Method for preparing ethylene by directly converting synthesis gas and catalyst containing LF type B acid |
| CN111111666B (en) * | 2020-01-06 | 2022-07-05 | 江南大学 | Cobalt-based Fischer-Tropsch catalyst and preparation method and application thereof |
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| CN103664436A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for directly transforming synthesis gas into low-carbon olefin |
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| JPS63294950A (en) * | 1987-05-27 | 1988-12-01 | Cataler Kogyo Kk | Catalyst for reducing nitrogen oxide |
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| CN101804351B (en) * | 2010-04-01 | 2012-05-30 | 中国科学院山西煤炭化学研究所 | Preparation method and application of core-shell structure cobalt-base catalyst of middle distillate for synthesis gas preparation |
| CN103521259B (en) * | 2012-07-03 | 2016-02-10 | 中国石油化工股份有限公司 | Synthesis gas alkene catalyst and preparation method thereof |
| CN103664447B (en) * | 2012-09-05 | 2016-05-18 | 中国石油化工股份有限公司 | The method of synthesis gas alkene processed |
| CN104549447B (en) * | 2013-10-28 | 2017-07-14 | 中国石油化工股份有限公司 | Synthesis gas alkene catalyst and preparation method thereof |
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| US4217240A (en) * | 1976-09-02 | 1980-08-12 | E. I. Du Pont De Nemours And Company | Stable aluminosilicate aquasols having uniform size particles and their preparation |
| CN101185899A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application |
| CN103664436A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for directly transforming synthesis gas into low-carbon olefin |
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