CN109651030A - The method that synthesis gas directly prepares low-carbon alkene - Google Patents

The method that synthesis gas directly prepares low-carbon alkene Download PDF

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CN109651030A
CN109651030A CN201710934565.0A CN201710934565A CN109651030A CN 109651030 A CN109651030 A CN 109651030A CN 201710934565 A CN201710934565 A CN 201710934565A CN 109651030 A CN109651030 A CN 109651030A
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parts
synthesis gas
catalyst
low
carbon alkene
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CN109651030B (en
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李剑锋
陶跃武
宋卫林
庞颖聪
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0333—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
    • 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

Abstract

The present invention relates to the methods that synthesis gas directly prepares low-carbon alkene, mainly solve the problems, such as that CO conversion ratio is low low with selectivity of light olefin in preparation of low carbon olefines by synthetic gas reaction existing in the prior art.The method that the present invention uses synthesis gas directly to prepare low-carbon alkene, including using synthesis gas as raw material, raw material and catalyst haptoreaction generate and contain C2~C4Alkene, the catalyst includes following components based on parts by weight: a) 5~40 parts of iron series elements or its oxide；B) 1~20 part includes at least one of Group IIB element or its oxide；C) 1~20 part includes at least one of Group IVB element or its oxide；D) 10~40 parts of silica；E) technical solution of 10~50 parts of SBA-15 type molecular sieves, preferably solves the problems, such as this, can be used for the industrial production of preparation of low carbon olefines by synthetic gas.

Description

The method that synthesis gas directly prepares low-carbon alkene
Technical field
The present invention relates to the methods that synthesis gas directly prepares low-carbon alkene.
Background technique
Low-carbon alkene refers to the alkene that carbon atom number is less than or equal to 4.Using ethylene, propylene as the low-carbon alkene right and wrong of representative Often important basic organic chemical industry raw material, with the rapid growth of China's economy, for a long time, low-carbon alkene market is not for answering It asks.Currently, the petrochemical industry route that the production of low-carbon alkene mainly uses lighter hydrocarbons (ethane, naphtha, light diesel fuel) to crack, due to The long-term run at high level of growing lack and crude oil price of Global Oil resource develops low-carbon alkene industry and relies solely on petroleum light hydrocarbon Increasing raw material problem can be encountered for the tube cracking furnace technique of raw material, low-carbon alkene production technology and raw material must be polynary Change.The direct preparing low-carbon olefins of one-step method from syngas be exactly carbon monoxide and hydrogen under the action of catalyst, it is anti-by F- T synthesis The process of low-carbon alkene of the carbon atom number less than or equal to 4 should directly be made, which is not necessarily to as indirect method technique from conjunction At gas through methanol or dimethyl ether, alkene is further prepared, simplification of flowsheet greatly reduces investment.Petroleum resources are short at home It lacks, it is current that external dependence degree is higher and higher, international oil price constantly rises violently, selects synthesis gas producing olefinic hydrocarbons technique that can widen former material Expect source, synthesis gas will be produced by raw material of crude oil, natural gas, coal and recyclable materials, it can be for based on high cost feedstocks As naphtha steam cracking technology in terms of provide alternative solution.The coal price of China coal resources and relative moderate abundant It is refined oil for Development of Coal and provides the good market opportunity using preparation of low carbon olefines by synthetic gas technique.And it is abundant in Natural Gas In China Oil gas field near, if Gas Prices are cheap, and application preparation of low carbon olefines by synthetic gas technique fabulous opportunity.If energy Using China's coal abundant and natural gas resource, pass through gas making producing synthesis gas (gaseous mixture of carbon monoxide and hydrogen), hair The substitute energy source for petroleum technology of preparation of low carbon olefines by synthetic gas is opened up, will be of great significance to energy problem, China is solved.
One-step method from syngas producing light olefins technique functions are derived from traditional Fischer-Tropsch synthesis, traditional Fischer-Tropsch synthetic Carbon number distribution defer to ASF distribution, each hydro carbons all has that theoretical maximum is selective, such as C2-C4The selectivity of fraction is up to 57%, gasoline fraction (C5-C11) selectivity be up to 48%.Chain growth probability α value is bigger, and the selectivity of product heavy hydrocarbon is got over Greatly.Once α value has determined, the selectivity of entire synthetic product is determined that, chain growth probability α value depend on catalyst composition, Granularity and reaction condition etc..In recent years, it has been found that due to alkene secondary counter caused by alhpa olefin adsorbing again on a catalyst It answers, product distribution is distributed away from ideal ASF.F- T synthesis is a kind of strong exothermal reaction, and a large amount of reaction heat will promote catalyst Carbon deposit reaction is easier to generate methane and low-carbon alkanes, leads to selectivity of light olefin sharp fall；Secondly, complicated power It is unfavorable that factor is also caused to selectivity synthesis low-carbon alkene；The ASF distribution of Fischer-Tropsch synthetic limits synthesizing low-carbon alkene Selectivity.The catalyst of F- T synthesis gas producing light olefins is mainly iron catalyst series, is directly made to improve synthesis gas The selectivity of low-carbon alkene is taken, physics and chemical modification can be carried out to fischer-tropsch synthetic catalyst, as being suitable for using molecular sieve Cellular structure is conducive to low-carbon alkene and diffuses out metal active centres in time, inhibits the secondary response of low-carbon alkene；Improve gold Belong to ion dispersibility, also there is preferable olefine selective；Support-metal strong interaction change can also be improved low-carbon alkene choosing Selecting property；The suitable transition metal of addition, can be enhanced the bond energy of active component and carbon, and methane is inhibited to generate, and improve low-carbon alkene Selectivity；Electronics accelerating auxiliaries are added, CO chemisorption heat is promoted to increase, adsorbance also increases, and hydrogen adsorptive capacity reduces, as a result Selectivity of light olefin increases；Catalyst acid center is eliminated, the secondary response of low-carbon alkene can be inhibited, improve its selectivity. By the Support effect and the certain transition metal promoters of addition and alkali metal promoter of catalyst carrier, catalyst performance can obviously improve Can, develop the fischer-tropsch synthetic catalyst of the highly selective producing light olefins of novel high-activity with the non-ASF distribution of product.
One-step method from syngas produces low-carbon alkene, it has also become one of the research hotspot of fischer-tropsch synthetic catalyst exploitation.Middle section In patent CN1083415A disclosed in Dalian Chemical Physics Research Institute, institute, with the Group IIAs such as MgO alkali metal oxide or silica-rich zeolite Iron-Mn catalyst system that molecular sieve (or phosphorus aluminium zeolite) supports, makees auxiliary agent with highly basic K or Cs ion, in synthesis of gas produced low-carbon Olefine reaction pressure is 1.0~5.0MPa, at 300~400 DEG C of reaction temperature, can get higher active (CO conversion ratio 90%) With selectivity (selectivity of light olefin 66%).But the catalyst preparation process is complicated, especially the system of carrier zeolite molecular sieve Standby forming process higher cost, is unfavorable for industrialized production.The number of patent application 01144691.9 that Beijing University of Chemical Technology is declared In, use laser pyrolysis processes combination solid phase reaction combination technique to be prepared for Fe3Fe base nano-catalyst based on C is applied to close At gas producing light olefins, and good catalytic effect is achieved, due to needing using laser pyrolysis technology, preparation process is more numerous Trivial, raw material uses Fe (CO)5, catalyst cost is very high, and industrialization is difficult.The patent that Beijing University of Chemical Technology is declared In ZL03109585.2, using vacuum impregnation technology to prepare manganese, copper, zinc silicon, potassium etc. is the Fe/ activated-carbon catalyst of auxiliary agent for closing At gas reaction for preparing light olefins, under conditions of no unstripped gas recycles, CO conversion ratio 96%, low-carbon alkene is in hydrocarbon Selectivity 68%.The molysite and auxiliary agent manganese salt that the catalyst preparation uses are more expensive and less soluble ferric oxalate and acetic acid Manganese, while with ethanol as solvent, just unavoidably increase the cost of material and operating cost of catalyst preparation process.It is further The cost for reducing catalyst, in its number of patent application 200710063301.9, catalyst uses common drug and reagent system It is standby, the molysite used be ferric nitrate, manganese salt is manganese nitrate, and sylvite is potassium carbonate, and active carbon is coconut husk charcoal, can catalyst must flow High-temperature roasting and Passivation Treatment are carried out under dynamic nitrogen protection, needs special installation, preparation process is complicated, higher cost.And it is above-mentioned CO conversion ratio and selectivity of light olefin of the catalyst in preparation of low carbon olefines by synthetic gas reaction are lower.
Summary of the invention
The technical problem to be solved by the present invention is to CO conversion ratio in preparation of low carbon olefines by synthetic gas technology in the prior art is low The problem low with selectivity of light olefin in product provides the method that synthesis gas directly prepares low-carbon alkene, and this method is for closing When at gas reaction for preparing light olefins, have the advantages that selectivity of light olefin is high in CO high conversion rate and product.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
The method that synthesis gas directly prepares low-carbon alkene, including using synthesis gas as raw material, raw material and catalyst haptoreaction It generates and contains C2~C4Alkene, the catalyst includes following components based on parts by weight:
A) 5~40 parts of iron series elements or its oxide；
B) 1~20 part includes at least one of Group IIB element or its oxide；
C) 1~20 part includes at least one of Group IVB element or its oxide；
D) 10~40 parts of silica；
E) 10~50 parts of SBA-15 type molecular sieves.
In above-mentioned technical proposal, H in synthesis gas2Molar ratio with CO is preferably 1~3.
In above-mentioned technical proposal, reaction temperature is preferably 250~400 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 1.0~3.0MPa.
In above-mentioned technical proposal, feed gas volume air speed is preferably 500~5000h-1。
In above-mentioned technical proposal, the iron series element is selected from least one of iron, cobalt and nickel.The oxide of iron is preferred For di-iron trioxide, the oxide of cobalt is preferably cobaltosic oxide.
In above-mentioned technical proposal, component a) content is preferably 10~35 parts.
In above-mentioned technical proposal, component b) content is preferably 5~15 parts.
In above-mentioned technical proposal, component c) content is preferably 5~15 parts.
In above-mentioned technical proposal, component d) content is preferably 15~35 parts.
In above-mentioned technical proposal, component e) content is preferably 15~45 parts.
In above-mentioned technical proposal, it is also preferable to include Group IIA element or its oxides by component b).
In above-mentioned technical proposal, Group IIB element preferably includes Zn or its oxide.
In above-mentioned technical proposal, IIA element preferably includes Mg or its oxide, at this time Zn (or its oxide) and Mg (or Its oxide) between there is in terms of selectivity of light olefin synergistic effect in improving CO high conversion rate and product.
Zn (or its oxide) and the ratio of Mg are not particularly limited, and Zn or its oxide are in terms of ZnO and Mg or its oxidation Object is in terms of MgO, and Zn (or its oxide) and Mg (or its oxide) weight ratio can be but not limited to 0.5~5, more specifically Non-limiting weight ratio can be 0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.5,1.6,1.7,1.8,2.0,2.1,2.2, 2.5,3.0,3.5,4.0,4.5 etc..
In above-mentioned technical proposal, it is also preferable to include VB race element or its oxides by component c).
In above-mentioned technical proposal, Group IVB element preferably includes Zr or its oxide.
In above-mentioned technical proposal, VB element preferably includes V or its oxide, at this time Zr (or its oxide) and V (or its oxygen Compound) between there is in terms of selectivity of light olefin synergistic effect in improving CO high conversion rate and product.
Zr (or its oxide) and the ratio of V are not particularly limited, and Zr or its oxide are with ZrO2Meter and V or its oxidation Object is with V2O5Meter, Zr (or its oxide) and V (or its oxide) weight ratio can be but not limited to 0.1~5, more specifically non- Restricted weight ratio can be 0.1,0.2,0.3,0.4,0.5,0.6,0.8,1.0,1.2,1.4,1.6,1.8,2.0,2.2, 2.5,3.0,3.5,4.0,4.5 etc..
In above-mentioned technical proposal, SBA-15 type molecular sieve preferably using include at least one of rare earth element element or its Oxide is the SBA-15 molecular sieve of modifier modification.
In above-mentioned technical proposal, SBA-15 type molecular sieve preferably using further include at least one of IA element element or its Oxide is the SBA-15 molecular sieve of modifier modification.
In above-mentioned technical proposal, the SBA-15 molecular sieve of the modification by weight, preferably containing modifier content be 1~ 15%, more specific unrestricted content value is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14% Etc..
In above-mentioned technical proposal, rare earth element preferably includes Nd or its oxide.
In above-mentioned technical proposal, IA element preferably includes Cs or its oxide, at this time Nd (or its oxide) and Cs (or its Oxide) between there is in terms of selectivity of light olefin synergistic effect in improving CO high conversion rate and product.
Nd (or its oxide) and the ratio of Cs are not particularly limited, and Nd or its oxide are with Nd2O3Meter and Cs or its oxygen Compound is with Cs2O meter, Nd (or its oxide) and Cs (or its oxide) weight ratio can be but not limited to 0.1~5, more specifically Non-limiting weight ratio can be 0.1,0.2,0.3,0.4,0.5,0.6,0.8,1.0,1.2,1.4,1.6,1.8,2.0, 2.2,2.5,3.0,3.5,4.0,4.5 etc..
In above-mentioned technical proposal, the modified SBA-15 molecular sieve is using the method preparation included the following steps:
(i) salt of rare earth element and/or IA element is dissolved in water and solution D is made；
(ii) solution D is mixed into obtain mixture E with SBA-15 molecular sieve；
(iii) it by mixture E, is fired, obtains required modification SBA molecular sieve.
In above-mentioned technical proposal, the preferred scope of the maturing temperature in step (iii) is 400~800 DEG C.
In above-mentioned technical proposal, the preferred scope of the calcining time in step (iii) is 2.0~8.0 hours.
In above-mentioned technical proposal, the catalyst can use method comprising the following steps to prepare:
(1) by component a), b) and c), corresponding salt is soluble in water is made solution A；
(2) solution A is mixed with silica, obtains mixture B；
(3) it by mixture B, roasts after drying, obtains mixture C；
(4) mixture C and modified SBA molecular sieve are mixed to get the catalysis that required synthesis gas directly prepares low-carbon alkene Agent.
In above-mentioned technical proposal, the preferred scope of the temperature roasted in step (3) is 400~800 DEG C.
In above-mentioned technical proposal, the preferred scope of the time roasted in step (3) is 4.0~8.0 hours.
In above-mentioned technical proposal, the hybrid mode of step (ii) and/or step (2) is not specially required, but in vacuum feelings Mixed effect is especially good under condition.Such as, but not limited under the conditions of 1~80kPa of vacuum degree by solution impregnate corresponding solid at Point.
After in above-mentioned technical proposal, the hybrid mode of step (4) is not specially required, but mill is mixed in the ball mill, tabletting Molding, further crushing and screening effect are especially good.
One skilled in the art will appreciate that catalyst of the invention is being used for synthesis gas C2~C4Olefine reaction before, it is best Online reduction treatment step is first undergone, specific reducing condition those skilled in the art can reasonably select and not need to pay Creative work, the condition such as, but not limited to restored are as follows:
The temperature of reduction is 400~600 DEG C；
Reducing agent is H2And/or CO；
The pressure of reduction is normal pressure~2MPa (in terms of gauge pressure)；
The volume space velocity of reducing agent is 1500~10000hr-1；
The time of reduction is 6~72 hours.
For convenient for year-on-year, the reducing condition in the embodiment of the present invention is equal are as follows:
450 DEG C of temperature
Pressure normal pressure
Loaded catalyst 3ml
The volume space velocity of reducing agent 6000 hours-1
Also Primordial Qi H2
Recovery time 24 hours.
Using catalyst of the present invention, CO conversion ratio improves 3.7% up to 99.7%, than the prior art；Low-carbon alkene is in carbon Selectivity in hydrogen compound improves 11.0% than the prior art, achieves preferable technical effect up to 79.0%.
Specific embodiment
[embodiment 1]
1, the preparation of modified SBA-15 molecular sieve
It weighs and is equivalent to 8 grams of Nd2O3Six nitric hydrate neodymiums, be dissolved in 50 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on 92 grams of SBA-15 molecular sieves and obtains mixture E；By mixture E in 110 DEG C of items It is dry under part, it is then roasted, 550 DEG C of maturing temperature, calcining time 4h is to get arriving modified SBA-15 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to 10 parts by weight ZnO zinc nitrate hexahydrate, It is equivalent to 10 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 20.0 grams of deionized waters and solution A be made；In vacuum degree 80kPa Under conditions of, above-mentioned solution A is impregnated on 25.0 grams of silica supports and obtains mixture B；Impregnated mixture B exists It is dry under the conditions of 110 DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 70 grams of mixture Cs and 30 grams of modified SBA-15 molecular sieves are mixed, after mill is mixed in the ball mill, compression molding, It is crushed and is sieved the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%ZnO, 10%ZrO2, 25% SiO2, 30% modified SBA-15 is (containing Nd2O38%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 6000 hours-1
Raw material proportioning (mole) H2/ CO=2.0/1.
For convenient for year-on-year, the composition of catalyst of the present invention and evaluation result are listed in table 1.
[embodiment 2]
1, the preparation of modified SBA-15 molecular sieve
It weighs and is equivalent to 8 grams of Nd2O3Six nitric hydrate neodymiums, be dissolved in 50 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on 92 grams of SBA-15 molecular sieves and obtains mixture E；By mixture E in 110 DEG C of items It is dry under part, it is then roasted, 550 DEG C of maturing temperature, calcining time 4h is to get arriving modified SBA-15 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to 10 parts by weight MgO magnesium nitrate hexahydrate, It is equivalent to 10 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 20.0 grams of deionized waters and solution A be made；In vacuum degree 80kPa Under conditions of, above-mentioned solution A is impregnated on 25.0 grams of silica supports and obtains mixture B；Impregnated mixture B exists It is dry under the conditions of 110 DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 70 grams of mixture Cs and 30 grams of modified SBA-15 molecular sieves are mixed, after mill is mixed in the ball mill, compression molding, It is crushed and is sieved the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%MgO, 10%ZrO2, 25% SiO2, 30% modified SBA-15 is (containing Nd2O38%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 6000 hours-1
Raw material proportioning (mole) H2/ CO=2.0/1.
For convenient for year-on-year, the composition of catalyst of the present invention and evaluation result are listed in table 1.
[embodiment 3]
1, the preparation of modified SBA-15 molecular sieve
It weighs and is equivalent to 8 grams of Nd2O3Six nitric hydrate neodymiums, be dissolved in 50 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on 92 grams of SBA-15 molecular sieves and obtains mixture E；By mixture E in 110 DEG C of items It is dry under part, it is then roasted, 550 DEG C of maturing temperature, calcining time 4h is to get arriving modified SBA-15 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to 6 parts by weight ZnO zinc nitrate hexahydrate, It is equivalent to the magnesium nitrate hexahydrate of 4 parts by weight MgO, is equivalent to 10 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 20.0 grams and go Solution A is made in ionized water；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated on 25.0 grams of silica supports Obtain mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, 500 DEG C of maturing temperature, roasts Time 6h to get arrive mixture C.
After 70 grams of mixture Cs and 30 grams of modified SBA-15 molecular sieves are mixed, after mill is mixed in the ball mill, compression molding, It is crushed and is sieved the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 6%ZnO, 4%MgO, 10% ZrO2, 25%SiO2, 30% modified SBA-15 is (containing Nd2O38%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 6000 hours-1
Raw material proportioning (mole) H2/ CO=2.0/1.
For convenient for year-on-year, the composition of catalyst of the present invention and evaluation result are listed in table 1.
Find out on year-on-year basis from embodiment 3 and embodiment 1 and embodiment 2, Zn (or its oxide) and Mg (or its oxide) it Between there is in terms of selectivity of light olefin synergistic effect in improving CO high conversion rate and product.
[embodiment 4]
1, the preparation of modified SBA-15 molecular sieve
It weighs and is equivalent to 8 grams of Nd2O3Six nitric hydrate neodymiums, be dissolved in 50 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on 92 grams of SBA-15 molecular sieves and obtains mixture E；By mixture E in 110 DEG C of items It is dry under part, it is then roasted, 550 DEG C of maturing temperature, calcining time 4h is to get arriving modified SBA-15 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to 6 parts by weight ZnO zinc nitrate hexahydrate, It is equivalent to the magnesium nitrate hexahydrate of 4 parts by weight MgO, is equivalent to 10 parts by weight V2O5Ammonium metavanadate, be dissolved in 20.0 grams of deionized waters In solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated on 25.0 grams of silica supports and is mixed Close object B；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, 500 DEG C of maturing temperature, calcining time 6h, Obtain mixture C.
After 70 grams of mixture Cs and 30 grams of modified SBA-15 molecular sieves are mixed, after mill is mixed in the ball mill, compression molding, It is crushed and is sieved the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 6%ZnO, 4%MgO, 10% V2O5, 25%SiO2, 30% modified SBA-15 is (containing Nd2O38%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 6000 hours-1
Raw material proportioning (mole) H2/ CO=2.0/1.
For convenient for year-on-year, the composition of catalyst of the present invention and evaluation result are listed in table 1.
[embodiment 5]
1, the preparation of modified SBA-15 molecular sieve
It weighs and is equivalent to 8 grams of Nd2O3Six nitric hydrate neodymiums, be dissolved in 50 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on 92 grams of SBA-15 molecular sieves and obtains mixture E；By mixture E in 110 DEG C of items It is dry under part, it is then roasted, 550 DEG C of maturing temperature, calcining time 4h is to get arriving modified SBA-15 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to 6 parts by weight ZnO zinc nitrate hexahydrate, It is equivalent to the magnesium nitrate hexahydrate of 4 parts by weight MgO, is equivalent to 4 parts by weight ZrO2Five nitric hydrate zirconiums, be equivalent to 6 parts by weight V2O5Ammonium metavanadate, be dissolved in 20.0 grams of deionized waters and solution A be made；Under conditions of vacuum degree 80kPa, by above-mentioned solution A It is impregnated on 25.0 grams of silica supports and obtains mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, then into Row roasting, 500 DEG C of maturing temperature, calcining time 6h to get arrive mixture C.
After 70 grams of mixture Cs and 30 grams of modified SBA-15 molecular sieves are mixed, after mill is mixed in the ball mill, compression molding, It is crushed and is sieved the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 6%ZnO, 4%MgO, 4%ZrO2, 6%V2O5, 25%SiO2, 30% modified SBA-15 is (containing Nd2O38%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 6000 hours-1
Raw material proportioning (mole) H2/ CO=2.0/1.
For convenient for year-on-year, the composition of catalyst of the present invention and evaluation result are listed in table 1.
Find out on year-on-year basis from embodiment 5 and embodiment 3 and embodiment 4, Zr (or its oxide) and V (or its oxide) are being mentioned There is synergistic effect in terms of the selectivity of high CO conversion ratio and low-carbon alkene.
[embodiment 6]
1, the preparation of modified SBA-15 molecular sieve
It weighs and is equivalent to 8 grams of Cs2The cesium nitrate of O is dissolved in 50 grams of deionized waters and solution D is made；Vacuum degree 80kPa's Under the conditions of, above-mentioned solution D is impregnated on 92 grams of SBA-15 molecular sieves and obtains mixture E；Mixture E is done under the conditions of 110 DEG C It is dry, then roasted, 550 DEG C of maturing temperature, calcining time 4h to get arrive modified SBA-15 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to 6 parts by weight ZnO zinc nitrate hexahydrate, It is equivalent to the magnesium nitrate hexahydrate of 4 parts by weight MgO, is equivalent to 4 parts by weight ZrO2Five nitric hydrate zirconiums, be equivalent to 6 parts by weight V2O5Ammonium metavanadate, be dissolved in 20.0 grams of deionized waters and solution A be made；Under conditions of vacuum degree 80kPa, by above-mentioned solution A It is impregnated on 25.0 grams of silica supports and obtains mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, then into Row roasting, 500 DEG C of maturing temperature, calcining time 6h to get arrive mixture C.
After 70 grams of mixture Cs and 30 grams of modified SBA-15 molecular sieves are mixed, after mill is mixed in the ball mill, compression molding, It is crushed and is sieved the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 6%ZnO, 4%MgO, 4%ZrO2, 6%V2O5, 25%SiO2, 30% modified SBA-15 is (containing Cs2O 8%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 6000 hours-1
Raw material proportioning (mole) H2/ CO=2.0/1.
For convenient for year-on-year, the composition of catalyst of the present invention and evaluation result are listed in table 1.
[embodiment 7]
1, the preparation of modified SBA-15 molecular sieve
It weighs and is equivalent to 4 grams of Nd2O3Six nitric hydrate neodymiums, be equivalent to 4 grams of Cs2The cesium nitrate of O is dissolved in 50 grams of deionizations Solution D is made in water；Under conditions of vacuum degree 80kPa, above-mentioned solution D, which is impregnated on 92 grams of SBA-15 molecular sieves, to be mixed Object E；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, 550 DEG C of maturing temperature, calcining time 4h is to get to changing Property SBA-15 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to 6 parts by weight ZnO zinc nitrate hexahydrate, It is equivalent to the magnesium nitrate hexahydrate of 4 parts by weight MgO, is equivalent to 4 parts by weight ZrO2Five nitric hydrate zirconiums, be equivalent to 6 parts by weight V2O5Ammonium metavanadate, be dissolved in 20.0 grams of deionized waters and solution A be made；Under conditions of vacuum degree 80kPa, by above-mentioned solution A It is impregnated on 25.0 grams of silica supports and obtains mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, then into Row roasting, 500 DEG C of maturing temperature, calcining time 6h to get arrive mixture C.
After 70 grams of mixture Cs and 30 grams of modified SBA-15 molecular sieves are mixed, after mill is mixed in the ball mill, compression molding, It is crushed and is sieved the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 6%ZnO, 4%MgO, 4%ZrO2, 6%V2O5, 25%SiO2, 30% modified SBA-15 is (containing Nd2O34%, Cs2O 4%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
350 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 6000 hours-1
Raw material proportioning (mole) H2/ CO=2.0/1.
For convenient for year-on-year, the composition of catalyst of the present invention and evaluation result are listed in table 1.
From embodiment 7 and embodiment 5 and embodiment 6 on year-on-year basis it is found that Nd (or its oxide) and Cs (or its oxide) exist There is synergistic effect in terms of improving the selectivity of CO conversion ratio and low-carbon alkene.Table 1

Claims (10)

1. the method that synthesis gas directly prepares low-carbon alkene, including using synthesis gas as raw material, raw material and catalyst haptoreaction are raw At containing C2~C4Alkene, the catalyst includes following components based on parts by weight:
A) 5~40 parts of iron series elements or its oxide；
B) 1~20 part includes at least one of Group IIB element or its oxide；
C) 1~20 part includes at least one of Group IVB element or its oxide；
D) 10~40 parts of silica；
E) 10~50 parts of SBA-15 type molecular sieves.
2. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that H in synthesis gas2And CO Molar ratio be 1~3.
3. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that reaction temperature 250 ~400 DEG C.
4. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that reaction pressure 1.0 ~3.0MPa.
5. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that feed gas volume is empty Speed is 500~5000h-1。
6. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that component a) content is 10~35 parts.
7. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that component b) content is 5 ~15 parts.
8. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that component c) content is 5 ~15 parts.
9. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that component d) content is 15~35 parts.
10. the method that synthesis gas according to claim 1 directly prepares low-carbon alkene, it is characterised in that component e) content is 15~45 parts.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234212A (en) * 2010-04-20 2011-11-09 中国石油化工股份有限公司 Method for directly converting synthetic gas into low-carbon olefins
CN103990464A (en) * 2014-05-13 2014-08-20 宁夏大学 A preparing method of a catalyst used for preparing low-carbon olefins from synthetic gas and applications of the catalyst
CN104437524A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Iron-based catalyst for preparing low-carbon alkane as well as preparation method and using method of iron-based catalyst for preparing low-carbon alkane
CN104437532A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Catalyst for preparing low carbon olefin by fixed bed, preparation method as well as use thereof
WO2017000427A1 (en) * 2015-07-02 2017-01-05 中国科学院大连化学物理研究所 Catalyst and method of preparing light olefin directly from synthesis gas by one-step process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234212A (en) * 2010-04-20 2011-11-09 中国石油化工股份有限公司 Method for directly converting synthetic gas into low-carbon olefins
CN104437524A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Iron-based catalyst for preparing low-carbon alkane as well as preparation method and using method of iron-based catalyst for preparing low-carbon alkane
CN104437532A (en) * 2013-09-24 2015-03-25 中国石油化工股份有限公司 Catalyst for preparing low carbon olefin by fixed bed, preparation method as well as use thereof
CN103990464A (en) * 2014-05-13 2014-08-20 宁夏大学 A preparing method of a catalyst used for preparing low-carbon olefins from synthetic gas and applications of the catalyst
WO2017000427A1 (en) * 2015-07-02 2017-01-05 中国科学院大连化学物理研究所 Catalyst and method of preparing light olefin directly from synthesis gas by one-step process

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