CN105709768A - Preparation method for catalyst used in preparation of olefin from synthetic gas - Google Patents
Preparation method for catalyst used in preparation of olefin from synthetic gas Download PDFInfo
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method for a catalyst used in preparation of low-carbon olefin from synthetic gas. The preparation method comprises the following steps: (1) subjecting an alumina carrier to equivalent-volume saturated impregnation of a buffer solution containing an ammonium salt, then drying the alumina carrier until the adsorption quantity of the buffer solution containing the ammonium salt is 30 to 60% of the saturated solution absorption quantity of the alumina carrier and carrying out ageing, drying and roasting so as to obtain a modified alumina carrier; (2) impregnating the modified alumina carrier prepared in the step (1) in a zinc salt solution by using a nonsaturated impregnation method and then carrying out drying and roasting; (3) impregnating the roasted carrier in the step (2) with a wetting solution containing an adsorbent by using the nonsaturated impregnation method; and (4) impregnating the adsorbent-containing carrier obtained in the step (3) in a solution containing active metal iron and an auxiliary agent manganese and carrying out drying and roasting so as to obtain the catalyst used in preparation of low-carbon olefin from synthetic gas. The catalyst has the characteristics of long-cycle operation activity and high stability and is beneficial for industrial application and promotion.
Description
Technical field
The present invention relates to a kind of synthesis gas alkene catalyst and preparation method thereof, relate in particular to a kind of load-type iron-based preparation of low carbon olefines by synthetic gas Catalysts and its preparation method of high-activity stable.
Background technology
The low-carbon alkene such as ethylene, propylene is important basic organic chemical industry raw material, and along with the development of chemical industry, its demand is more and more big.Up to now, the approach of the low-carbon alkene such as preparing ethylene, propylene is mainly through light oil cracking process, and along with the exhaustion day by day of petroleum resources in global range, following energy resource structure certainly will shift.Compared with petroleum resources, coal and natural gas resource relative abundance, develop the low-carbon alkene production technology based on coal and natural gas and have great importance.From the exploitation of synthesis gas (can be converted to by natural gas and coal) directly preparing ethylene, propylene technology, the dependence to petroleum resources not only can be reduced, and to some rich gas oil starvation area chemistry industrial expansion important in inhibitings.
CN1065026A discloses a kind of preparation of ethylene by use of synthetic gas method, the preparation method relating to catalyst is chemical precipitation method, mechanical mixing, have employed noble metal or rare metal, for instance niobium, gallium, praseodymium, scandium, indium, cerium, lanthanum, ytterbium etc. more than ten plant chemical element, and ethylene selectivity is 65%-94%, but CO conversion ratio is very low, only 10%, 12% and about 15%, CO recycles the consumption that certainly will bring the energy, and catalyst cost is high.CN01144691.9 discloses nanocatalyst of a kind of preparation of ethylene by use of synthetic gas, propylene and preparation method thereof, adopts laser pyrolysis processes to be prepared in conjunction with the combination technique of solid state reaction with Fe3C is main Fe base nano-catalyst application and preparing low-carbon olefin, and achieves certain effect, but due to the practical laser technology of needs, makes preparation technology comparatively laborious, and raw material adopts Fe (CO)5, the cost of catalyst is higher, industrialization difficulty.CN03109585.2 disclose a kind of for preparation of ethylene by use of synthetic gas, propylene, butene reaction ferrum/activated-carbon catalyst, adopt activated carbon as carrier, Fe is as active center, adopt vacuum impregnation technology successfully by Fe load on the activated carbon, Fe and auxiliary agent is made to be able to high degree of dispersion on the activated carbon, thus improving catalytic effect, and greatly reduce the cost of catalyst.And catalyst without feedstock circulation when, CO conversion ratio is up to 96-99%, in gas-phase product, CH compound selective reaches 69.5%, and wherein ethylene, propylene, butylene selectivity in CH compound reach more than 68%.But activated carbon is as catalyst carrier not only bad mechanical strength but also shaping of catalyst is difficult, affects service life and the stability of catalyst, be unfavorable for commercial Application.
CN102441383A, CN101940958A, CN102441400A, CN102441384A be respectively adopted organic compounds containing nitrogen solution, acid solution, the buffer solution of ammonium salt-containing, the mode such as hydrothermal treatment consists silica-gel carrier is carried out impregnation process, prepare Fe base silica gel supported synthesis gas and directly prepare light olefins catalyst, reduce Fe and SiO2Strong interaction between carrier.But the activity stability that above-mentioned Fe base silica gel supported synthesis gas directly prepares the long-term operation of light olefins catalyst still needs to be improved further.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of iron-based support type preparation of low carbon olefines by synthetic gas Catalysts and its preparation method being carrier with aluminium oxide, and this catalyst has the advantages that long-term operation activity stability is high, is conducive to commercial Application and popularization.
The preparation method of a kind of preparation of low carbon olefines by synthetic gas catalyst, comprises the steps:
(1) aqueous buffer solution of the saturated dipping ammonium salt-containing of alumina support equal-volume, at 95-110 DEG C, 0.5-1h is dried immediately after dipping, it is dried to the 30-60% that adsorbance is alumina support saturated absorption amount of solution of the buffer solution of ammonium salt-containing, after aging, dry, roasting, then prepares modified aluminium oxide supports；
(2) modified aluminium oxide supports that prepared by step (1) adopts unsaturated impregnation zinc solution, after drying roasting 1h-10h at 700 DEG C ~ 1000 DEG C, it is preferable that roasting 2h-8h at 800 DEG C ~ 900 DEG C；
(3) unsaturated infusion process carrier after fountain solution impregnation steps (2) roasting containing adsorbent is adopted, wherein said adsorbent is carbon number is the organic amine of 2～15, and the addition of described adsorbent accounts for 1% ~ 10% of the vehicle weight after step (2) roasting；
(4) step (3) carrier impregnation containing adsorbent contains active metal ferrum and the solution of auxiliary agent manganese, or else saturated spray impregnating metal auxiliary agent after drying, roasting, prepares preparation of low carbon olefines by synthetic gas catalyst then through after dry, roasting.
In the inventive method step (1), the aqueous buffer solution ammonium salt of ammonium salt-containing can be chosen from one or more in ammonium acetate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate etc..In buffer solution, the weight concentration of ammonium salt is 1%-35%, it is preferred to 5%-20%.Aging temperature is 50-95 DEG C, it is preferred to 60 ~ 80 DEG C, and ageing time is 0.5-10h, it is preferable that 2-5h.Aging rear baking temperature is 90-150 DEG C, and drying time is 0.5-36h, it is preferable that dry 8-24h at 100-120 DEG C.Roasting is roasting 2-15 hour at 280-500 DEG C, it is preferable that roasting 3-5 hour at 300-450 DEG C.
The inventive method, in step (2), zinc salt includes one or more in zinc chloride, zinc nitrate or zinc sulfate.Zinc solution is the aqueous solution of zinc salt, and in zinc solution, the mass fraction of zinc salt is 5-10%.
The inventive method, the 5-60% that pickup is alumina support saturated absorption amount of solution of zinc solution in step (2), it is preferable that 20-50%.Dip time is 1-5h, and dipping temperature is 40-60 DEG C.After dipping, baking temperature is 80-150 DEG C, and drying time is 2-15h.
The inventive method, in step (2), alumina support can adopt existing commercial goods, it is also possible to prepares by existing method.Support shapes can be spherical, bar shaped, flap-type.With spherical and bar shaped for best.
The inventive method, in step (3), organic amine includes one or more in fatty amine, hydramine, amide, aliphatic cyclic amine or aromatic amine.Specifically include one or more in monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylformamide, propionic acid amide., butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine, it is preferable that one or more in diethylamine, triethylamine, morphine.
In step of the present invention (3), dipping, containing the fountain solution of adsorbent, adopts unsaturated dipping, it is desirable to adopt unsaturated spraying, and wherein the volume ratio of dip amount used by unsaturated dipping and carrier saturated absorption amount of solution is 0.05 ~ 0.4.Dipping, containing after the fountain solution of adsorbent, can dry, it is also possible to direct impregnation contains the solution of active metal ferrum under the decomposition temperature less than selected adsorbent, wherein baking temperature is generally 60 DEG C～150 DEG C, 80 DEG C～120 DEG C are preferably, drying time 0.5h～20h, it is preferred to 1h～6h.When spraying the fountain solution containing adsorbent, the shower nozzle that atomizing effect is good should be selected, make solution evenly spread on alumina support.The dipping fountain solution dipping containing adsorbent can be made directly next step, it is possible to carry out next step again through health preserving after terminating, and conditioned time is 0.5～8h.
The inventive method, the 50-90% that amount is carrier saturated absorption amount of solution of unsaturated spray impregnating metal auxiliary agent potassium solution in step (4).The mass ratio respectively (65 ~ 75) of Fe and auxiliary agent K and Mn in the preparation of low carbon olefines by synthetic gas catalyst of preparation: (0.5 ~ 5): (23 ~ 34).Active metal solution or compounding agent solution preparation method known to the skilled person which, its solution concentration can be regulated by the consumption of each compound, thus preparing specified activity component and the catalyst of auxiliary agent content.The raw material of required active component and auxiliary agent is generally the compound of the types such as salt, oxide or acid, as source of iron is generally from one or more in ferric nitrate, iron chloride, iron sulfate, potassium source is from one or more in potassium nitrate, potassium carbonate, potassium chloride, and manganese source is generally from manganese nitrate or manganese chloride.
The inventive method, adds 2-15% in the solution containing active metal ferrum and auxiliary agent manganese, it is preferable that 5-10% ammonium citrate in mass in step (4).Adopting the iron salt solutions added containing ammonium citrate can improve the dispersion of active component, preparing the active component iron catalyst of little crystal grain, thus significantly improving the selectivity of low-carbon alkene.
The inventive method, through super-dry and calcination steps after dipping in step (4), described dry and roasting condition is all conventional, for instance, drying steps dries 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 350-700 DEG C.
A kind of preparation of low carbon olefines by synthetic gas catalyst adopting above method to prepare, with Fe for active component, with K and Mn for auxiliary agent, in catalyst, the weight percentage of Fe is 0.5%-20%, in catalyst, auxiliary agent is the mass ratio respectively (65 ~ 75) of K and Mn, Fe and auxiliary agent K and Mn: (0.5 ~ 5): (23 ~ 34).
The method of reducing of above-mentioned preparation of low carbon olefines by synthetic gas catalyst, adopts the gaseous mixture of chlorine and hydrogen to reduce, and chlorine volume content in gaseous mixture is 0.5-10%, preferred 1-5%, reduction temperature is 300-450 DEG C, and the recovery time is 3-10 hour, and pressure is 0.5-2MPa.Adopt above-mentioned method of reducing can improve the selectivity of butylene.
The inventive method, initially with the saturated oxide impregnation alumina supporter of buffer solution of ammonium salt-containing, concentrates in the internal gutter of carrier through the buffer solution of the dried ammonium salt of quick fraction, and carrier inside is mainly carried out partially modified by the buffer solution of ammonium salt.Then unsaturated impregnated zinc saline solution is adopted mainly the outer surface of alumina support and outside channel surfaces mainly to be modifiied.It is significantly different that the above-mentioned inside and outside duct to alumina support carries out the uneven modified inside and outside duct physico-chemical property making alumina support, the carbochain carrying the highly active low-carbon alkene simultaneously inhibiting generation to greatest extent increases and is hydrogenated with saturated, improves the conversion ratio of carbon monoxide.The inventive method by the mode of adsorbent occupy-place make active component iron and auxiliary agent Fe content by outer from be gradually increased, auxiliary agent potassium be that eggshell type is distributed, and significantly improves selectivity of catalyst.The physical and chemical performance of this catalyst, catalysis stability active, long-term operation are obtained for raising, and the combination property of catalyst highlights.
Detailed description of the invention
Further illustrate process and the effect of the present invention below in conjunction with embodiment, but following example do not constitute the restriction to the inventive method.
Example 1
(pore volume is 0.96ml/g, and specific surface area is 286.81m to weigh commercial alumina2/ g, saturated water adsorptive value is 145ml/g, thered is provided by Fushun branch company of Sinopec catalyst company limited, following example and comparative example all use this aluminium oxide), by the saturated spray oxide impregnation aluminum of ammonium carbonate solution that mass concentration is 5%, at 95 DEG C, after terminating, dry 1h immediately, adsorbance is alumina support saturated absorption amount of solution the 60% of dry ammonium carbonate solution processed, aging 7h at 60 DEG C, dries 24 hours, then at 5 hours prepared modified aluminium oxide supports of 300 DEG C of roastings in 100 DEG C.Above-mentioned modified aluminium oxide supports adopts unsaturated spray impregnation mass fraction to be the zinc nitrate aqueous solution of 5%, dipping temperature is 50 DEG C, dip time 3h, and pickup is the 20% of alumina support saturated absorption amount of solution, dry 5h, roasting 6h under 850 DEG C of roastings at 120 DEG C.The unsaturated spray dipping triethylamine aqueous solution of carrier after roasting, triethylamine aqueous solution spray volume is the 35% of the total saturated water adsorptive value of used carrier, and in triethylamine aqueous solution, the mass content of triethylamine is the 8% of carrier quality, at 100 DEG C of dry 5h after spray dipping.By final catalyst Fe content 9wt%, the carrier of absorption triethylamine adopts equi-volume impregnating dipping iron nitrate aqueous solution, and 100 DEG C dry 16 hours, roasting 4 hours in 550 DEG C.By Fe content in catalyst be 3.6wt%, Fe, K and Mn mass ratio be that 70:3:28 counts incipient impregnation manganese nitrate and potassium nitrate mixed liquor, 100 DEG C dry 16 hours, roasting 4 hours in 550 DEG C, gained catalyst is designated as C-1.The reaction result that C-1 catalyst synthesis gas directly prepares low-carbon alkene is as shown in table 1.
Catalyst Evaluation Test carries out in the continuous fixed bed reactors of high pressure, and to reduce 5 hours at pure hydrogen 350 DEG C, pressure is 1.0MPa.Switch synthesis gas after cooling to react.Reaction effluent is collected by hot trap, cold-trap respectively.Reaction condition is 280 DEG C, 1200h-1, 2.0MPa, H2/ CO=1(mol ratio).The 300h reaction result that C-1 catalyst synthesis gas directly prepares low-carbon alkene is as shown in table 1.
Example 2
Weigh commercial alumina, it is the 20% saturated spray oxide impregnation aluminum of ammonium acetate aqueous solution by mass concentration, at 110 DEG C, 0.5h is dried immediately after end, it is dried to adsorbance is alumina support saturated absorption amount of solution the 40% of ammonium acetate aqueous solution, at 80 DEG C aging 4 hours, drying 8 hours in 120 DEG C, then in 400 DEG C, roasting obtains modified aluminium oxide supports in 3 hours.Above-mentioned modified aluminium oxide supports adopts unsaturated impregnation mass fraction to be the zinc sulfate solution of 10%, and dipping temperature is 60 DEG C, dip time 2h, and pickup is the 40% of alumina support saturated absorption amount of solution, dry 10h, 900 DEG C of roasting 4h at 90 DEG C.The unsaturated spray dipping aqueous morphine solution of carrier after roasting, aqueous morphine solution spray volume is the 10% of the total saturated water adsorptive value of used carrier, and in aqueous morphine solution, the mass content of morphine is the 2% of carrier quality, and health preserving 5h after spray dipping, at 90 DEG C of dry 8h.Being 3.6wt% by final catalyst Fe content 9wt%, Fe content, the carrier of absorption morphine adopts equi-volume impregnating dipping ferric nitrate and manganese nitrate aqueous solution, and 100 DEG C dry 16 hours, roasting 4 hours in 550 DEG C.It is 70:3:28 by the mass ratio of Fe in catalyst, K and Mn, unsaturated spray dipping potassium nitrate solution, pickup is the 80% of carrier saturated absorption amount of solution, 100 DEG C dry 16 hours, roasting 4 hours in 550 DEG C, gained catalyst is designated as C-2,300h evaluation result in Table 1.
Example 3
Except adding, in the iron nitrate aqueous solution of dipping, the ammonium citrate that mass fraction is 5%, all the other are with embodiment 1, and prepared catalyst is designated as C-3,300h evaluation result in Table 1.
Example 4
Except adding, in the iron nitrate aqueous solution of dipping, the ammonium citrate that mass fraction is 10%, all the other are with embodiment 1, and prepared catalysis is designated as C-4, and 300 evaluation results are in Table 1.
Example 5
With embodiment 1, being different in that catalyst is reduced by the gaseous mixture adopting chlorine and hydrogen, chlorine volume content in gaseous mixture is 5%, and prepared catalyst is designated as C-5,300h evaluation result in Table 1.
Implement 6
With embodiment 1, being different in that catalyst adopts the gaseous mixture of chlorine and hydrogen to reduce, chlorine volume content in gaseous mixture is 1%, and all the other are with embodiment 1, and prepared catalyst is designated as C-6,300h evaluation result in Table 1.
Comparative example 1
Except the zinc nitrate aqueous solution adopting saturated spray impregnating effect mark to be 5%, all the other are with embodiment 1, and prepared catalyst is designated as B-1,300h evaluation result in Table 1.
Comparative example 2
Except not spraying dipping triethylamine aqueous solution, all the other are with embodiment 1, and prepared catalyst is designated as B-2,300h evaluation result in Table 1.
The reactivity worth of table 1 catalyst
Claims (25)
1. the preparation method of a preparation of low carbon olefines by synthetic gas catalyst, it is characterised in that: comprise the steps:
(1) aqueous buffer solution of the saturated dipping ammonium salt-containing of alumina support equal-volume, at 95-110 DEG C, 0.5-1h is dried immediately after dipping, it is dried to the 30-60% that adsorbance is alumina support saturated absorption amount of solution of the buffer solution of ammonium salt-containing, after aging, dry, roasting, then prepares modified aluminium oxide supports；
(2) modified aluminium oxide supports that prepared by step (1) adopts unsaturated impregnation zinc solution, after drying roasting 1h-10h at 700 DEG C ~ 1000 DEG C；
(3) unsaturated infusion process carrier after fountain solution impregnation steps (2) roasting containing adsorbent is adopted, wherein said adsorbent is carbon number is the organic amine of 2～15, and the addition of described adsorbent accounts for 1% ~ 10% of the vehicle weight after step (2) roasting；
(4) step (3) carrier impregnation containing adsorbent contains active metal ferrum and the solution of auxiliary agent manganese, or else saturated spray impregnating metal auxiliary agent after drying, roasting, prepares preparation of low carbon olefines by synthetic gas catalyst then through after dry, roasting.
2. method according to claim 1, it is characterised in that: in step (1), the aqueous buffer solution ammonium salt of ammonium salt-containing is one or more in ammonium acetate, ammonium formate, ammonium carbonate, ammonium hydrogen carbonate.
3. method according to claim 1, it is characterised in that: in buffer solution, the weight concentration of ammonium salt is 1%-35%.
4. method according to claim 1, it is characterised in that: step (1) aging temperature is 50-95 DEG C, and ageing time is 0.5-10h, and aging rear baking temperature is 90-150 DEG C, and drying time is 0.5-36h, and roasting is roasting 2-15 hour at 280-500 DEG C.
5. method according to claim 1, it is characterised in that: the dried roasting 2h-8h at 800 DEG C ~ 900 DEG C of step (2).
6. method according to claim 1, it is characterised in that: in step (2), zinc salt includes one or more in zinc chloride, zinc nitrate or zinc sulfate.
7. method according to claim 1, it is characterised in that: in step (2), zinc solution is the aqueous solution of zinc salt, and in zinc solution, the mass fraction of zinc salt is 5-10%.
8. method according to claim 1, it is characterized in that: the 5-60% that pickup is alumina support saturated absorption amount of solution of zinc solution in step (2), dip time is 1-5h, and dipping temperature is 40-60 DEG C, after dipping, baking temperature is 80-150 DEG C, and drying time is 2-15h.
9. method according to claim 1, it is characterised in that: the 20-50% that pickup is alumina support saturated absorption amount of solution of zinc solution in step (2).
10. method according to claim 1, it is characterised in that: in step (3), organic amine includes one or more in fatty amine, hydramine, amide, aliphatic cyclic amine or aromatic amine.
11. the method according to claim 1 or 7, it is characterised in that: in step (3), organic amine includes one or more in monoethyl amine, diethylamine, triethylamine, ethylenediamine, hexamethylene diamine, tert-butylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylformamide, propionic acid amide., butyramide, pyridine, morphine, aniline, diphenylamines, naphthalidine, dinaphthylamine.
12. method according to claim 11, it is characterised in that: in step (3), organic amine is one or more in diethylamine, triethylamine, morphine.
13. method according to claim 1, it is characterised in that: the dipping fountain solution containing adsorbent in step (3), adopt unsaturated spraying, wherein the volume ratio of dip amount used by unsaturated dipping and carrier saturated absorption amount of solution is 0.05 ~ 0.4.
14. method according to claim 1, it is characterized in that: in step (3), dipping is containing after the fountain solution of adsorbent, dry under the decomposition temperature less than selected adsorbent, or direct impregnation contains the solution of active metal ferrum, baking temperature is 60 DEG C～150 DEG C, drying time 0.5h～20h.
15. method according to claim 14, it is characterised in that: baking temperature is 80 DEG C～120 DEG C, and drying time is 1h～6h.
16. method according to claim 1, it is characterised in that: after the dipping fountain solution dipping containing adsorbent terminates in step (3), being made directly next step, or carry out next step again through health preserving, conditioned time is 0.5～8h.
17. method according to claim 1, it is characterised in that: the mass ratio respectively (65 ~ 75) of Fe and auxiliary agent K and Mn in preparation of low carbon olefines by synthetic gas catalyst prepared by step (4): (0.5 ~ 5): (23 ~ 34).
18. method according to claim 1, it is characterised in that: the 50-90% that amount is carrier saturated absorption amount of solution of unsaturated spray impregnating metal auxiliary agent potassium solution in step (4).
19. method according to claim 1, it is characterised in that: source of iron is one or more in ferric nitrate, iron chloride, iron sulfate, and potassium source is one or more in potassium nitrate, potassium carbonate, potassium chloride, and manganese source is manganese nitrate or manganese chloride.
20. method according to claim 1, it is characterised in that: step (4) adds 2-15% ammonium citrate in mass in the solution containing active metal ferrum and auxiliary agent manganese.
21. method according to claim 20, it is characterised in that: step (4) adds 5-10% ammonium citrate in mass in the solution containing active metal ferrum and auxiliary agent manganese.
22. method according to claim 1, it is characterised in that: through super-dry and calcination steps after step (3) dipping, drying steps dries 8-24 hour at 50-150 DEG C, and calcination steps is roasting 2-10 hour at 350-700 DEG C.
23. the preparation of low carbon olefines by synthetic gas catalyst adopting claim 1-22 either method to prepare, it is characterized in that: this catalyst is with Fe for active component, with K and Mn for auxiliary agent, in catalyst, the weight percentage of Fe is the mass ratio respectively (65 ~ 75) of 0.5%-20%, Fe and auxiliary agent K and Mn: (0.5 ~ 5): (23 ~ 34).
24. the method for reducing of catalyst described in claim 23, it is characterized in that: adopting the gaseous mixture of chlorine and hydrogen to reduce, chlorine volume content in gaseous mixture is 0.5-10%, and reduction temperature is 300-450 DEG C, recovery time is 3-10 hour, and pressure is 0.5-2MPa.
25. method of reducing according to claim 24, it is characterised in that: chlorine volume content in gaseous mixture is 1-5%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107827691A (en) * | 2017-11-06 | 2018-03-23 | 中石化炼化工程（集团）股份有限公司 | A kind of method of synthesis gas preparing low-carbon olefins |
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| CN102441400A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas |
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| US4001144A (en) * | 1975-12-19 | 1977-01-04 | Kaiser Aluminum & Chemical Corporation | Process for modifying the pore volume distribution of alumina base catalyst supports |
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| CN107827691A (en) * | 2017-11-06 | 2018-03-23 | 中石化炼化工程（集团）股份有限公司 | A kind of method of synthesis gas preparing low-carbon olefins |
| CN107827691B (en) * | 2017-11-06 | 2020-09-01 | 中石化炼化工程（集团）股份有限公司 | Method for preparing low-carbon olefin from synthesis gas |
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