CN107486226A - 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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- CN107486226A CN107486226A CN201710694728.2A CN201710694728A CN107486226A CN 107486226 A CN107486226 A CN 107486226A CN 201710694728 A CN201710694728 A CN 201710694728A CN 107486226 A CN107486226 A CN 107486226A
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- 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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- 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
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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, it is magnesium carbonate to help active component.The preparation method of catalyst refers to specification.The method have the advantages that：Low-carbon alkene is directly obtained by synthesis gas, it is not necessary to which 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 CO conversion per pass 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
It is to be related to synthesis gas (hydrogen and an oxygen specifically the present invention relates to the catalyst of alkene preparation, preparation method
Change carbon) catalyst, the preparation method and its usage of direct synthesizing low-carbon alkene.
Background technology
Low-carbon alkene, as a rule refer to the alkene that carbon number is less than or equal to 4, such as ethene, propylene and fourth
Alkene etc., it is Organic Chemicals most basic in petrochemical industry production, highly important status is occupied in national economy, it is used
Way primarily can be used for producing such as the organic compound of polyethylene, polypropylene, acrylonitrile, oxirane or ethylene glycol etc.
Low-carbon alkene is mainly derived from petroleum cracking at present, wherein most low-carbon alkenes 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 to low-carbon alkene demand, in the world hydrocarbon vapours thermal cracking production ethene and propylene dress
The production capacity put constantly is expanding, and particularly in China, the output of ethene is with annual 5%~10% speed increase.But
It is as petroleum resources are increasingly in short supply, oil price is improved constantly, and the production cost of low-carbon alkene is continuously increased, and this has a strong impact on
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 reducing
Cost has decisive meaning.
In view of petroleum resources are fairly limited in the world, but coal and natural gas resource enrich, therefore rationally utilize what is enriched
Coal and natural gas resource, it is by most attention to be converted into high value-added product and make full use of coal resources natural gas
Problem, effectively there is boundless prospect, huge economic benefit and social benefit using natural gas and coal.
Using coal or natural gas production chemical products, generally require and first generate coal or natural gas with water and oxygen reaction
Hydrogen and CO are the gas of main component, then by CO conversion and acid gas removal, by sulphur therein, nitrogen oxides with
And the removing such as carbon dioxide, hydrogen and CO ratio are adjusted, prepares synthesis gas (CO and hydrogen).The production technology of synthesis gas at present
It is ripe, and it is widely used in methanol production industrial process.By synthesis gas as raw material, optionally synthesizing low-carbon alkene,
Natural gas and coal are changed into 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 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 fluid product, is referred to as GTL
And CTL (Coal-to-Liquids) technology (Gas-to-Liquids).(natural gas prepares liquid production to GTL commercial technologies route
Product) Related product has methanol, dimethyl ether and artificial oil.Although artificial oil and dimethyl ether (DME) also have the device of comercial operation,
Methyl alcohol product installation is that GTL technology business applications are most successful at present.
The method for the synthesis gas alkene that patent and document disclose has two classes at present：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).
It is F- T synthesis to prepare the traditional method of hydrocarbon by synthesis gas, early in the 1930s Germany just
There is the device production fuel of commercial Application, but the discovery of the huge and cheap oil of Middle East reserves closes big in the world
The commercial plant of part F- T synthesis production fuel oil, has only in South Africa due to special politics and economic cause, F- T synthesis life
The industrial production of production fuel oil is continued, and is developed well.The product of usual F- T synthesis for alkane, alkene and contains
The compound of oxygen, and the product issue of hydro carbons follows Schulz-Anderson-Florry distributions, i.e. Wn=(1- α)2nαn-1
(W is the mass fraction for the hydrocarbon that carbon number is n；N is carbon number, generally 1~30；α is 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 there is 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, hydrocarbon mixture is prepared by synthesis gas with fischer-tropsch synthetic catalyst first, then carry out being disproportionated instead again
Low-carbon alkene, this obvious process route length of method, catalyst system and catalyzing complexity should be obtained.
Mobil companies 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, UCC scientist synthesize the molecular sieve of SAPO series, and SAPO-34 therein is to methanol
Generating ethene and propylene has selectivity well, so as to produce the MTO of the methanol production alkene with good prospect
(methanol to olfin) technology.Patent US2007244000A1, US2007244348A1, US2008033218A1 and
US2010294642A1 etc. is the method for intermediate product by preparing low-carbon olefin by alcohol or ether.MTO technology
Synthesizing methanol first is required for, then, hydrocarbon is converted into by methanol, thus process route is long.
The content 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.
The present invention seeks to be achieved by the following measures：The catalyst of preparation of low carbon olefines by synthetic gas, the catalyst have master
Active component and active component is helped, wherein main active component is iron oxide and zinc oxide, it is magnesium carbonate to help active component；Main activity
Component is the composite oxides of iron oxide and zinc oxide, and wherein the atomic molar ratio of iron and zinc is 1：3~3：1, help 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 to use co-precipitation method：Weigh iron and
The atomic molar ratio of zinc is 1：3~3：After 1 ferric nitrate mixes with zinc nitrate, deionized water is added to be configured to weight concentration about 20%
Mixed solution；Weighing sodium carbonate adds deionized water to be configured to 20% w solution；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, aging 0.5~8 hour, filters, filter cake is washed with deionized water, and the filter cake after cleaning, which is placed on drying box, to be dried, then
In Muffle furnace, 4h is calcined at 300~650 DEG C, that is, obtains unformed Fe-Zn/O composite oxides；The composite oxygen that will be obtained
Compound compression molding, then crush the solid particle that 0.5~1.5mm sizes are made；Help active ingredients weight fraction 20%
Magnesium carbonate the aqueous solution, using the methods of dipping, Fe-Zn/O composite oxide catalysts are added and helped in activearm, make Fe-
Zn/O oxides are totally submerged among solution, are impregnated 2h, are dried at 120 DEG C, in air atmosphere, 350 DEG C of roastings, roasting
3h, obtain catalyst of the present invention.
The purposes of the catalyst of preparation of low carbon olefines by synthetic gas, for carbon monoxide and the direct synthesizing low-carbon alkene of hydrogen, instead
It is 250~350 DEG C to answer temperature, and reaction pressure is 2.0~5.0MPa, and unstrpped gas air speed is 1500~6000h-1。
The present invention has the following advantages that compared with prior art：
1) low-carbon alkene, is directly obtained by synthesis gas, it is not necessary to 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 its product is distributed not by Schulz-
The limitation of Anderson-Florry distributions, without long-chain olefin and alkane product, product selectivity is high, and separation process is simple；
3), CO conversion per pass is high, methane and CO2Output is few, and operation energy consumption is lower.
Catalyst is using preceding needing to activate, and by obtained catalyst breakage, screening takes 20~40 mesh particle 1g, in loading
Footpath is 8mm tubular reactor, with the nitrogen containing 5% hydrogen at ambient pressure 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 incubated, is then down to room temperature.
Evaluating catalyst use synthesis gas mole composition for：
CO 24%, H265%, CO 28%, remaining is Ar.
Control reaction system condition as follows 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.
Embodiment
The following examples are that the present invention is described in further detail, but the present invention is not restricted by the embodiments.
Embodiment 1
It is prepared by No. 01-06 main active component iron oxide and 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, add deionized water 100ml to be configured to 20% w solution.Two kinds of solution in 70 DEG C condition and flow into
Material, and controlled pH=9 ± 0.2 or so, continues to stir 30min after charging, in 80 DEG C of static agings 2 hours.Material is through water
After cleaning, dried 12 hours at 120 DEG C in an oven, be then calcined 4 hours at 300~650 DEG C, be then cooled to room
Temperature, obtain calcining iron oxide and zinc oxide composite oxide catalysts.Six catalyst that different sintering temperatures obtain, it is numbered
For 01~06.The quality of synthetic catalyst forms：ZnO 43.9% and FeO 56.1%, wherein Fe and Zn atomic molars ratio
For 1：1.
By the careful ground and mixed of above-mentioned synthetic catalyst, compression molding, then crush, sieve, obtain 40~60 mesh sizes
Catalyst.Catalyst is evaluated by foregoing method using fixed bed reactors, reaction two hours after on-line analysis obtain
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 sintering temperature, higher CO conversion ratios, sintering temperature
It is low, C2~C4The selectivity of alkene is high.
The result of the catalyst preparing low-carbon olefin of 1 different sintering temperatures of table
Embodiment 2
03rd, prepared by No. 07-09 main active component iron oxide and zinc oxide composite oxide catalysts
Catalyst is prepared using the same procedure of the aqueous solution and embodiment 1 of different weight ferric nitrate and zinc nitrate, obtained
Sediment, dried 12 hours at 120 DEG C in an oven, be then calcined 4 hours at 350 DEG C, be then cooled to room temperature, obtain
Iron oxide and zinc oxide composite oxide catalysts, itself Fe and Zn atomic molars ratio are 1：2,2：1 and 3：1, catalyst, which is numbered, is
07~09.Above-mentioned catalyst and 03 catalyst are evaluated using fixed bed reactors, reaction two hours after on-line analysis obtain
It the results are shown in Table 2.
2 different Fe/Zn of table than catalyst reaction result
Above-mentioned data can be seen that in Fe/Zn=1：2~3：In the range of 1, CO conversion ratios can be more than 85%, Fe/
Zn=1：When 2, selectivity of light olefin is relatively low, and product heavy constituent is more, and Fe/Zn ratios are more than 2：When 1, selectivity of light olefin drop
It is low, Fe/Zn=1：When 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 differential responses temperature of table 3 to catalyst performance
The as shown by data of table 3, when reaction temperature is less than 300 DEG C, selectivity of light olefin is relatively low, temperature rise, CO2Yield increases
Greatly, during 300 DEG C of reaction temperature, No. 03 catalyst has preferable selectivity of light olefin and higher reactivity.
The evaluation result of catalyst under the different pressures of table 4
Reaction pressure raises, and CO conversion ratios slightly improve, and it is favourable to illustrate that reaction pressure is improved to catalyst activity raising
, but reaction pressure rise reduces the selectivity of low-carbon alkene.
The reaction result of catalyst under the differential responses condition air speed of table 5
Relatively low reaction velocity is advantageous to improve the selectivity of CO conversion ratios and low-carbon alkene.
Embodiment 4
10-12 catalyst of the present invention
Embodiment 1 is obtained into 03 catalyst load potassium K element to be modified, obtains helping the catalyst of active component.Match somebody with somebody
The potassium hydroxide solution of different weight fraction processed, it is mixed with the catalyst of catalyst 03 so that Fe-Zn/O oxides soak completely
Not among solution, 2h is impregnated, then dries it at 120 DEG C, in air atmosphere, under 350 DEG C of certain sintering temperatures,
Roasting 3h obtains catalyst, obtains containing potassium catalyst, the wherein weight content of potassium is 1%~5% (K2O is counted).Using implementation
The identical method catalyst performance of example 1 is evaluated, and the results are shown in Table 6.
Table 6 contains the evaluation result for the catalyst for helping active component potassium K
The data of table 6 be can be seen that after addition helps active component potassium K, and catalyst is shown to the selectivity of low-carbon alkene
Write and improve.
Embodiment 5
13-15 catalyst of the present invention
Embodiment 1 is obtained into 03 catalyst load magnesium Mg elements to be modified, obtains helping the catalyst of active component.Match somebody with somebody
The carbonic acid magnesium solution of different weight fraction processed, it is mixed with the catalyst of catalyst 03 so that Fe-Zn/O oxides are totally submerged
Among solution, 2h is impregnated, then dries it at 120 DEG C, in air atmosphere, under 350 DEG C of certain sintering temperatures, roasting
Burn 3h and obtain catalyst, obtain containing Mg catalyst, the wherein weight content of magnesium is 1%~5% (MgO meter).Using embodiment 1
Identical method catalyst performance is evaluated, and the results are shown in Table 7.
Table 7 contains the evaluation result for the catalyst for helping active component magnesium Mg
The data of table 7 can be seen that after addition helps active component magnesium Mg, and catalyst obtains to the selectivity of low-carbon alkene
It is significantly increased.
Claims (4)
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 it is magnesium carbonate to help active component；Main active component is iron oxide and zinc oxide
Composite oxides, wherein the atomic molar ratio of iron and zinc be 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 claimed in claim 1, it is characterised in that：This method is
Using co-precipitation method：The atomic molar ratio for weighing iron and zinc is 1：3~3：After 1 ferric nitrate mixes with zinc nitrate, 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
Stirred in~90 DEG C of waters bath with thermostatic control, by Fe (NO3)3-Zn(NO3)2Mixed liquor and Na2CO3Solution cocurrent instills, two solution of regulation
Rate of addition, pH value 5~10 is kept, room temperature is placed, and aging 0.5~8 hour, filters, filter cake is washed with deionized water, after cleaning
Filter cake be placed on drying box drying, then in Muffle furnace, 4h is calcined at 300~650 DEG C, that is, obtains unformed Fe-Zn/O
Composite oxides；The composite oxides compression molding that will be obtained, then crush the solid particle that 0.5~1.5mm sizes are made；Help
The magnesium carbonate aqueous solution of active ingredients weight fraction 20%, using the method for dipping, by Fe-Zn/O composite oxide catalytics
Agent is added and helped in the active component aqueous solution, Fe-Zn/O oxides is totally submerged among solution, is impregnated 2h, is dried at 120 DEG C
It is dry, in air atmosphere, 350 DEG C of roastings, 3h is calcined, obtains the catalyst.
3. 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 it is magnesium carbonate to help active component；Main active component is iron oxide and zinc oxide
Composite oxides, wherein the atomic molar ratio of iron and zinc be 1：3~3：1, help active component weight be calculated as 1% with oxide~
5%；The catalyst is prepared using co-precipitation method：The atomic molar ratio for weighing iron and zinc is 1：3~3：1 ferric nitrate and nitric acid
After zinc mixing, deionized water is added to be configured to the mixed solution that weight concentration is 20%；Weighing sodium carbonate adds deionized water to be configured to
20% w solution；Stirred in 25~90 DEG C of waters bath with thermostatic control, by Fe (NO3)3-Zn(NO3)2Mixed liquor and Na2CO3Solution and drip
Enter, adjust the rate of addition of two solution, keep pH value 5~10, room temperature is placed, and aging 0.5~8 hour, is filtered, is used deionized water
Filter wash cake, the filter cake after cleaning is placed on drying box and dried, then in Muffle furnace, 4h calcined at 300~650 DEG C, that is, is obtained
Unformed Fe-Zn/O composite oxides；The composite oxides compression molding that will be obtained, then crushes that 0.5~1.5mm is made is big
Small solid particle；The magnesium carbonate aqueous solution of active ingredients weight fraction 20% is helped, using the method for dipping, by Fe-Zn/
O composite oxide catalysts are added and helped in the active component aqueous solution, Fe-Zn/O oxides is totally submerged among solution, are soaked
Stain 2h, dry at 120 DEG C, in air atmosphere, 350 DEG C of roastings, be calcined 3h, obtain the catalyst.
4. the purposes of the catalyst of the preparation of low carbon olefines by synthetic gas described in application claim 1 or 3, it is characterised in that：It is described to urge
Agent is used for carbon monoxide and the direct synthesizing low-carbon alkene of hydrogen, and reaction temperature is 250~350 DEG C, and 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 |
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| CN102698764B (en) | 2017-10-13 |
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