CN107486226B - Catalyst, the preparation method and its usage of preparation of low carbon olefines by synthetic gas - Google Patents
Catalyst, the preparation method and its usage of preparation of low carbon olefines by synthetic gas Download PDFInfo
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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- 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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- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The present invention relates to the catalyst of preparation of low carbon olefines by synthetic gas, preparation method and its usage, catalyst has main active component and helps active component, wherein main active component is iron oxide and zinc oxide, helping active component is magnesium carbonate.The preparation method of catalyst is detailed in specification.The invention has the advantages that: low-carbon alkene is directly obtained by synthesis gas, does not need methanol intermediate products, the production cost of low-carbon alkene is low, and selectivity of light olefin is high, and separation process is simple, and the conversion per pass of CO is high, methane and CO2Output is few, and operation energy consumption is lower.The purposes of catalyst of the present invention is the direct synthesizing low-carbon alkene of synthesis gas.
Description
Technical field
The present invention relates to the catalyst of alkene preparation, preparation method, specifically, being to be related to synthesis gas (hydrogen and an oxygen
Change carbon) catalyst, the preparation method and its usage of direct synthesizing low-carbon alkene.
Background technique
Low-carbon alkene usually refers to the alkene that carbon atom number is less than or equal to 4, such as ethylene, propylene and fourth
Alkene etc. is Organic Chemicals most basic in petrochemical industry production, highly important status is occupied in national economy, uses
Way primarily can be used for producing the organic compound such as polyethylene, polypropylene, acrylonitrile, ethylene oxide or ethylene glycol etc.
Low-carbon alkene is mainly derived from petroleum cracking at present, wherein most low-carbon alkene by hydro carbons (ethane, propane,
Butane, naphtha, light diesel fuel and diesel oil hydrogenation tail oil etc.) steam cracking device production, small part propylene and butylene originate from oil refining
The dry-gas recovery of the catalytic cracking unit of factory.In China, naphtha is still most important ethylene cracking material at present.With the world
Expanding economy, market are continuously increased low-carbon alkene demand, in the world hydrocarbon vapours thermal cracking production ethylene and propylene dress
The production capacity set constantly is expanding, and particularly in China, the output of ethylene is increased with annual 5%~10% speed.But
It is as petroleum resources are increasingly in short supply, oil price is continuously improved, and the production cost of low-carbon alkene is continuously increased, this is seriously affected
The production and supply of low-carbon alkene.During hydrocarbon vapours producing ethylene by cracking, cost of material accounts for the 60% of production cost
~80%.Correct selection ethylene raw has a significant impact to petro chemical industry development, therefore selects economic raw material, to reduction
Cost has decisive meaning.
It is fairly limited in view of petroleum resources in the world, but coal and natural gas resource are abundant, therefore rationally using abundant
Coal and natural gas resource, converting natural gas to high value-added product and make full use of coal resources is by most attention
Project, efficiently using natural gas and coal has boundless prospect, huge economic benefit and social benefit.
Chemical products are produced using coal or natural gas, generally requires and coal or natural gas is reacted into generation with water and oxygen first
Hydrogen and CO gas as main component, then by CO transformation and acid gas removal, by sulphur therein, nitrogen oxides with
And the removing such as carbon dioxide, the ratio of hydrogen and CO is adjusted, synthesis gas (CO and hydrogen) is prepared.The production technology of synthesis gas at present
It is mature, and it is widely used in methanol production industrial process.By synthesis gas as raw material, selectively synthesizing low-carbon alkene,
Natural gas and coal are converted to high value added product, can not only ensure the supply of low-carbon alkene, reduce to petroleum resources according to
Rely, also rationally can efficiently develop and use coal and natural gas resource, alleviate the shortage of petroleum resources.
Gas renormalizing and coal gasification produce synthesis gas, and then synthesis gas is converted into the process of liquid product, referred to as GTL
(Gas-to-Liquids) and CTL (Coal-to-Liquids) technology.(natural gas prepares liquid production to GTL commercial technologies route
Product) Related product has methanol, dimethyl ether and synthetic oil.Although synthetic oil and dimethyl ether (DME) also have the device of comercial operation,
Methyl alcohol product installation is that GTL technology business application is most successful at present.
The method for the synthesis gas alkene that patent and document disclose at present has two classes: the side of synthesis gas Fiscber-Tropscb synthesis (F-T)
Method preparing low-carbon olefins；Synthesis gas is via methanol or the indirect preparing low-carbon olefins of dimethyl ether (MTO/MTP).
Preparing the traditional method of hydrocarbon by synthesis gas is F- T synthesis, early in the 1930s Germany just
There is the device production fuel of industrial application, however the discovery of the huge and cheap petroleum of Middle East reserves closes in the world greatly
Part F- T synthesis produces the commercial plant of fuel oil, has only in South Africa due to special politics and economic cause, F- T synthesis is raw
The industrial production for producing fuel oil is continued, and is developed well.The product of usual F- T synthesis is alkane, alkene and contains
The compound of oxygen, and the product publication of hydro carbons follows Schulz-Anderson-Florry distribution, i.e. Wn=(1- α)2nαn-1
(W is the mass fraction for the hydrocarbon that carbon atom number is n；N is carbon atom number, generally 1~30；α be chain growth constant, general 0.75
~0.95), so the hydrocarbon compound of F- T synthesis production has very wide carbon number distribution, it is difficult to have very high choosing to low-carbon alkene
Selecting property.Patent CN1083415A discloses method and supports Iron-Manganese Catalyst using MgO or silica-rich zeolite molecular sieve (phosphate aluminium molecular sieve),
Fischer-Tropsch catalyst is improved, the low-carbon alkene of higher yields can be obtained, but catalyst preparation is complicated, reaction
Temperature is higher, and in product methane selectivity it is high.Patent CN101265149 disclose a kind of method with two-stage catalytic agent by
Preparing low-carbon olefin prepares hydrocarbon mixture by synthesis gas with fischer-tropsch synthetic catalyst first, then carries out being disproportionated again anti-
Low-carbon alkene should be obtained, this obvious process route of method is long, and catalyst system is complicated.
Mobil company C.D.Chang et al. delivers patent US4025575 disclosure molecular sieve catalytic methanol and is converted into lower carbon number hydrocarbons
The method of compound, the eighties in last century, the scientist of UCC synthesize the molecular sieve of SAPO series, and SAPO-34 therein is to methanol
Generating ethylene and propylene has selectivity well, to generate the MTO with the methanol production alkene of good prospect
(methanol to olfin) technology.Patent US2007244000A1, US2007244348A1, US2008033218A1 and
It is method of the intermediate product by preparing low-carbon olefin that US2010294642A1 etc., which is by alcohol or ether,.The technology of MTO
Synthesizing methanol first is required, then, hydrocarbon is converted by methanol, thus process route is long.
Summary of the invention
It is an object of the invention to overcome the shortcomings of the prior art, and provide a kind of new carbon monoxide and
Catalyst, the preparation method and its usage of the direct synthesizing low-carbon alkene of hydrogen.
Object of the present invention is to be achieved by the following measures: the catalyst of preparation of low carbon olefines by synthetic gas, which has master
Active component and active component is helped, wherein main active component is iron oxide and zinc oxide, helping active component is magnesium carbonate；Main activity
Group is divided into the composite oxides of iron oxide and zinc oxide, and wherein the atomic molar of iron and zinc ratio is 1:3~3:1, helps active component
Weight is calculated as 1%~5% with oxide.
The preparation method of the catalyst of preparation of low carbon olefines by synthetic gas, this method are using co-precipitation method: weigh iron and
The atomic molar ratio of zinc is after 1:3~3:1 ferric nitrate is mixed with zinc nitrate, deionized water to be added to be configured to weight concentration about 20%
Mixed solution；Weighing sodium carbonate adds deionized water to be configured to 20% w solution；It is stirred in 25~90 DEG C of waters bath with thermostatic control, by Fe
(NO3)3-Zn(NO3)2Mixed liquor and Na2CO3Solution cocurrent instills, and adjusts the rate of addition of two solution, keeps pH value 5~10, room
Temperature is placed, and aging 0.5~8 hour, filters, filter cake is washed with deionized water, and it is dry that the filter cake after cleaning is placed on drying box, then
In Muffle furnace, 4h is calcined at 300~650 DEG C to get unformed Fe-Zn/O composite oxides are arrived；The composite oxygen that will be obtained
Then compound compression molding is crushed the solid particle that 0.5~1.5mm size is made；Help active ingredients weight fraction 20%
The aqueous solution of magnesium carbonate the addition of Fe-Zn/O composite oxide catalysts is helped in active group, Fe- is made using the method for dipping
Zn/O oxide is totally submerged among solution, is impregnated 2h, is dried at 120 DEG C, in air atmosphere, 350 DEG C of roastings, roasting
3h obtains catalyst of the present invention.
The purposes of the catalyst of preparation of low carbon olefines by synthetic gas is used for carbon monoxide and the direct synthesizing low-carbon alkene of hydrogen, instead
Answering temperature is 250~350 DEG C, and reaction pressure is 2.0~5.0MPa, and unstrpped gas air speed is 1500~6000h-1。
The invention has the following advantages over the prior art:
1) low-carbon alkene, is directly obtained by synthesis gas, does not need methanol intermediate products, therefore the production cost of low-carbon alkene
It is low；
2), one-step synthesis method gas directly prepares selectivity of light olefin height, and product distribution is not by Schulz-
The limitation of Anderson-Florry distribution, without long-chain olefin and alkane product, product selectivity is high, and separation process is simple；
3), the conversion per pass of CO is high, methane and CO2Output is few, and operation energy consumption is lower.
Catalyst is using preceding needing to activate, and by catalyst breakage obtained, screening takes 20~40 mesh particle 1g, in loading
Diameter is the tubular reactor of 8mm, under normal pressure with the nitrogen of the hydrogen containing 5% first, is warming up to by 150 DEG C/h of speed program
300 DEG C, the activation for carrying out catalyst in 3 hours is kept the temperature, room temperature is then down to.
Evaluating catalyst is formed using synthesis gas mole are as follows:
CO 24%, H265%, CO 28%, remaining is Ar.
It is as follows that reaction system condition is controlled during evaluating catalyst:
2.0~5.0MPa of reaction pressure, 1500~6000h of gas space velocity-1, reaction temperature is 250~350 DEG C, and product is used
Gas-chromatography carries out on-line analysis.
Specific embodiment
The following examples are a further detailed description of the invention, but the present invention is not restricted by the embodiments.
Embodiment 1
No. 01-06 main active component iron oxide and the preparation of zinc oxide composite oxide catalysts
Add deionized water 100ml, the mixed solution being configured to after weighing 12.1 grams of ferric nitrates and 9.45 grams of zinc nitrate mixing；
26.5 grams of sodium carbonate are weighed, deionized water 100ml is added to be configured to 20% w solution.Two kinds of solution in 70 DEG C condition and flow into
Material, and control pH=9 ± 0.2 or so, continues to stir 30min after charging, in 80 DEG C static aging 2 hours.Material is through water
It is 12 hours dry at 120 DEG C in an oven after cleaning, it is then roasted 4 hours at 300~650 DEG C, is then cooled to room
Temperature obtains calcining iron oxide and zinc oxide composite oxide catalysts.Six catalyst that different maturing temperatures obtain, number
It is 01~06.The quality composition of synthetic catalyst is: ZnO 43.9% and FeO 56.1%, wherein Fe and Zn atomic molar ratio
For 1:1.
By the careful ground and mixed of above-mentioned synthetic catalyst, then compression molding is crushed, sieves, obtains 40~60 mesh sizes
Catalyst.Catalyst is evaluated by method above-mentioned using fixed bed reactors, and on-line analysis obtains after reaction two hours
To the results are shown in Table 1.
The result of table 1, which can be seen that 350 DEG C of obtained catalyst of maturing temperature, higher CO conversion ratio, maturing temperature
It is low, C2~C4The selectivity of alkene is high.
The result of the catalyst preparing low-carbon olefin of the different maturing temperatures of table 1
Embodiment 2
03, No. 07-09 main active component iron oxide and the preparation of zinc oxide composite oxide catalysts
Catalyst is prepared using 1 same procedure of aqueous solution and embodiment of different weight ferric nitrate and zinc nitrate, is obtained
Sediment, it is 12 hours dry at 120 DEG C in an oven, it is then roasted 4 hours at 350 DEG C, is then cooled to room temperature, obtains
Iron oxide and zinc oxide composite oxide catalysts, Fe and Zn atomic molar ratio are 1:2,2:1 and 3:1, and catalyst number is
07~09.Above-mentioned catalyst and 03 catalyst are evaluated using fixed bed reactors, and on-line analysis obtains after reaction two hours
It the results are shown in Table 2.
The catalyst reaction result of 2 difference Fe/Zn ratio of table
Above-mentioned data can be seen that in the range of Fe/Zn=1:2~3:1, and CO conversion ratio can be more than 85%, Fe/
When Zn=1:2, selectivity of light olefin is lower, and product heavy constituent is more, when Fe/Zn ratio is greater than 2:1, selectivity of light olefin drop
It is low, when Fe/Zn=1:1, selectivity of light olefin highest.
Embodiment 3
No. 03 main active component iron oxide and zinc oxide composite oxide catalysts, in different temperatures, pressure and reactant
Under conditions of product air speed, the Evaluation results of catalyst are shown in Table 3~5.
Influence of the 3 differential responses temperature of table to catalyst performance
Table 3 statistics indicate that, reaction temperature be lower than 300 DEG C when, selectivity of light olefin is lower, temperature increase, CO2Yield increases
Greatly, 300 DEG C of reaction temperature when, No. 03 catalyst has preferable selectivity of light olefin and higher reactivity.
The evaluation result of catalyst under 4 different pressures of table
Reaction pressure increases, and CO conversion ratio slightly improves, and it is advantageous for illustrating that reaction pressure is improved to catalyst activity raising
, but reaction pressure increases the selectivity for reducing low-carbon alkene.
The reaction result of catalyst under 5 differential responses condition air speed of table
Lower reaction velocity is conducive to improve the selectivity of CO conversion ratio and low-carbon alkene.
Embodiment 4
10-12 catalyst of the present invention
Embodiment 1 is obtained 03 catalyst load potassium K element to be modified, obtains the catalyst for helping active component.Match
The potassium hydroxide solution of different weight score processed mixes it with 03 catalyst of catalyst, so that Fe-Zn/O oxide soaks completely
Not among solution, 2h is impregnated, then dries it at 120 DEG C, in air atmosphere, under 350 DEG C of certain maturing temperatures,
Roasting 3h obtains catalyst, obtains containing potassium catalyst, wherein the weight content of potassium is 1%~5% (K2O meter).Using implementation
The identical method catalyst performance of example 1 can be carried out evaluation, the results are shown in Table 6.
Table 6 contains the evaluation result for helping the catalyst of active component potassium K
The data of table 6 can be seen that after addition helps active component potassium K, and catalyst shows the selectivity of low-carbon alkene
It writes and improves.
Embodiment 5
13-15 catalyst of the present invention
Embodiment 1 is obtained 03 catalyst load magnesium Mg element to be modified, obtains the catalyst for helping active component.Match
The carbonic acid magnesium solution of different weight score processed mixes it with 03 catalyst of catalyst, so that Fe-Zn/O oxide is totally submerged
Among solution, 2h is impregnated, then dries it at 120 DEG C, in air atmosphere, under 350 DEG C of certain maturing temperatures, roasting
It burns 3h and obtains catalyst, obtain containing Mg catalyst, wherein the weight content of magnesium is 1%~5% (MgO meter).Using embodiment 1
Identical method catalyst performance can be carried out evaluation, the results are shown in Table 7.
Table 7 contains the evaluation result for helping the catalyst of active component magnesium Mg
The data of table 7 can be seen that after addition helps active component magnesium Mg, and catalyst obtains the selectivity of low-carbon alkene
It is significantly increased.
Claims (3)
1. the catalyst of preparation of low carbon olefines by synthetic gas, it is characterised in that: the catalyst contains main active component and helps active component,
Wherein main active component is iron oxide and zinc oxide, and helping active component is magnesium carbonate；Main active component is iron oxide and zinc oxide
Composite oxides, wherein the atomic molar of iron and zinc ratio is 1:3~3:1, help active component weight be calculated as 1% with oxide~
5%。
2. the preparation method of the catalyst of preparation of low carbon olefines by synthetic gas as described in claim 1, it is characterised in that: this method is
Use co-precipitation method: weigh iron and zinc atomic molar ratio mixed for 1:3~3:1 ferric nitrate with zinc nitrate after, add from
Sub- water is configured to the mixed solution that weight concentration is 20%；Weighing sodium carbonate adds deionized water to be configured to 20% w solution；25~
It is stirred in 90 DEG C of waters bath with thermostatic control, by Fe (NO3 )3 -Zn(NO3 )2 Mixed liquor and Na2 CO3 Solution cocurrent instills, and adjusts two solution
Rate of addition, keep pH value 5~10, be placed at room temperature for, aging 0.5~8 hour, filter, filter cake is washed with deionized water, clean
It is dry that filter cake afterwards is placed on drying box, then in Muffle furnace, calcines 4h at 300~650 DEG C to get unformed Fe- is arrived
Zn/O composite oxides；Then the composite oxides compression molding that will be obtained is crushed the solid that 0.5~1.5mm size is made
Grain；The magnesium carbonate aqueous solution for helping active ingredients weight fraction 20%, using the method for dipping, by Fe-Zn/O composite oxides
Catalyst addition helps in active component aqueous solution, is totally submerged Fe-Zn/O oxide among solution, 2h is impregnated, at 120 DEG C
Drying, in air atmosphere, 350 DEG C of roastings roast 3h, obtain the catalyst.
3. the purposes of the catalyst of application preparation of low carbon olefines by synthetic gas described in claim 1, it is characterised in that: the catalyst
For carbon monoxide and the direct synthesizing low-carbon alkene of hydrogen, reaction temperature is 250~350 DEG C, reaction pressure is 2.0~
5.0MPa, unstrpped gas air speed are 1500~6000h-1 。
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| CN104437511B (en) * | 2013-09-24 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for producing light olefins by fixed bed and preparation method for catalyst for producing light olefins by fixed bed |
| CN105854915B (en) * | 2016-04-14 | 2019-03-22 | 宁夏大学 | A kind of catalyst and preparation method thereof for preparing low-carbon olefin |
| CN107185542B (en) * | 2017-05-05 | 2020-05-22 | 北京石油化工学院 | Supported Fe-Zn/CNTs catalyst and preparation method thereof |
| CN109704900B (en) * | 2017-10-26 | 2021-11-30 | 中国石油化工股份有限公司 | Method for preparing olefin by synthesis gas one-step method |
| CN109701628A (en) | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Composite catalyst containing phosphate aluminium molecular sieve and its application in one-step method from syngas alkene |
| CN109569623B (en) * | 2018-12-06 | 2021-03-16 | 清华大学 | Catalyst for directly preparing olefin from synthesis gas, preparation method and use method |
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| CN1537674A (en) * | 2003-04-15 | 2004-10-20 | 北京化工大学 | Iron/active carbon catalyst used for preparing ethylene, propylene, butylene from synthetic gas |
| CN101391219A (en) * | 2008-11-10 | 2009-03-25 | 上海兖矿能源科技研发有限公司 | FT synthesis sintered iron catalyst and preparation method and use thereof |
| CN101396662A (en) * | 2007-09-28 | 2009-04-01 | 北京化工大学 | Nano catalyst for producing low carbon olefin hydrocarbon using synthesis gas and preparation method thereof |
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| EP1153660A3 (en) * | 1997-06-18 | 2002-01-09 | ExxonMobil Chemical Patents Inc. | Conversion of synthesis gas to lower olefins using modified molecular sieves |
| CN1199730C (en) * | 2002-06-12 | 2005-05-04 | 中国科学院山西煤炭化学研究所 | Ferromanganese catalyst for Fischer-Tropsch synthesis and method for preparing the same |
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| CN102698764A (en) | 2012-10-03 |
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