CN109304216A - The catalyst of one-step method from syngas production low-carbon alkene - Google Patents

The catalyst of one-step method from syngas production low-carbon alkene Download PDF

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CN109304216A
CN109304216A CN201710628224.0A CN201710628224A CN109304216A CN 109304216 A CN109304216 A CN 109304216A CN 201710628224 A CN201710628224 A CN 201710628224A CN 109304216 A CN109304216 A CN 109304216A
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catalyst
mixture
grams
step method
parts
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CN109304216B (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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    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to the catalyst of one-step method from syngas production low-carbon alkene, mainly solve the problems, such as that CO conversion ratio is low low with selectivity of light olefin in one-step method from syngas reaction for preparing light olefins existing in the prior art.The present invention includes following components: a) 5~40 parts of iron series elements or its oxide using the catalyst of one-step method from syngas production low-carbon alkene based on parts by weight；B) 1~20 part includes at least one of Group IVB element or its oxide；C) 20~70 parts of Alpha-aluminas；D) 10~40 parts of type ZSM 5 molecular sieves；Wherein, type ZSM 5 molecular sieve is the technical solution of rare earth modified ZSM-5 molecular sieve, preferably solves the problems, such as this, can be used for the industrial production of one-step method from syngas producing light olefins.

Description

The catalyst of one-step method from syngas production low-carbon alkene
Technical field
The present invention relates to the catalyst and its preparation method and application of one-step method from syngas production 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 of 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 of 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 first technical problem to be solved by the present invention is in the prior art in one-step method from syngas producing light olefins technology The low problem low with selectivity of light olefin in product of CO conversion ratio provides the catalysis of one-step method from syngas production low-carbon alkene Agent when the catalyst is used for one-step method from syngas reaction for preparing light olefins, has low-carbon alkene choosing in CO high conversion rate and product The high advantage of selecting property.
The second technical problem to be solved by the present invention is to provide the preparation method of the catalyst of one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is to provide the application of the catalyst using one of above-mentioned technical problem.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows:
One-step method from syngas produces the catalyst of low-carbon alkene, based on parts by weight includes following components:
A) 5~40 parts of iron series elements or its oxide；
B) 1~20 part includes at least one of Group IVB element or its oxide；
C) 20~70 parts of Alpha-aluminas；
D) 10~40 parts of type ZSM 5 molecular sieves；
Wherein, type ZSM 5 molecular sieve is rare earth modified ZSM-5 molecular sieve.
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 10~30 parts.
In above-mentioned technical proposal, component b) content is preferably 5~15 parts.
In above-mentioned technical proposal, component c) content is preferably 30~60 parts.
In above-mentioned technical proposal, component d) content is preferably 20~30 parts.
In above-mentioned technical proposal, the silica alumina ratio SiO of type ZSM 5 molecular sieve2/Al2O3Preferably 50~500.Such as it is but unlimited In silica alumina ratio can be 100,150,200,250,300,350,400,450 etc..To count on year-on-year basis, embodiment of the present invention portion Divide and is all made of SiO2/Al2O3For 300 type ZSM 5 molecular sieve.
In above-mentioned technical proposal, it is also preferable to include Group IIB 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, IVB element preferably includes Zr or its oxide, at this time Zn (or its oxide) and Zr (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 Zr are not particularly limited, and Zn or its oxide are in terms of ZnO and Zr or its oxidation Object is with ZrO2Meter, Zn (or its oxide) and Zr (or its oxide) weight ratio can be but not limited to 0.51~5, more specifically Non-limiting weight ratio can be 0.61,0.71,0.81,0.91,1.01,1.11,1.21,1.51,1.61,1.71,1.81, 2.01,2.11,2.21,2.51,3.01,3.51,4.01,4.51 etc..
In above-mentioned technical proposal, by weight, rare earth element or its oxide in the rare earth modified ZSM-5 molecular sieve Content is 1~20%, and more specific unrestricted content value is 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 15% Etc..
In above-mentioned technical proposal, at least one of the preferred lanthanum of the rare earth element and gadolinium, samarium element or its oxide.
In above-mentioned technical proposal, at least two or its oxide in the more preferable lanthanum of the rare earth element and gadolinium, samarium element, At this time lanthanum (or its oxide) and gadolinium (or its oxide), samarium (or its oxide) between any two, namely lanthanum (or its oxidation Object)-gadolinium (or its oxide), lanthanum (or its oxide)-samarium (or its oxide) and gadolinium (or its oxide)-samarium (or its oxygen Compound) between, there is in terms of selectivity of light olefin synergistic effect in improving CO high conversion rate and product.Rare earth two-by-two at this time Ratio between element (or its oxide) is not particularly limited.Such as, but not limited in La is with La2O3Meter, Ga are with Gd2O3Meter, Sm is with Sm2O3, meter, lanthanum (or its oxide) and the weight ratio of gadolinium (or its oxide) can be 0.1~10, more specific ratio Such as can be 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5,6, 6.5,7,7.5,8,8.5,9,9.5 etc.；The weight ratio of lanthanum (or its oxide) and samarium (or its oxide) can for 0.1~ 10, more specific ratio for example can be 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.5,2,2.5,3,3.5,4, 4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5 etc.；The weight ratio of gadolinium (or its oxide) and samarium (or its oxide) Can be 0.1~10, more specific ratio for example can be 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.5,2, 2.5,3,3.5,4,4.5,5,5.5,6,6.5,7,7.5,8,8.5,9,9.5 etc..
In above-mentioned technical proposal, the rare earth modified ZSM-5 molecular sieve is using the method preparation included the following steps:
(i) salt of rare earth element is dissolved in water and solution D is made；
(ii) solution D is mixed into obtain mixture E with ZSM-5 hydrogen type molecular sieve；
(iii) it by mixture E, is fired, obtains required modified zsm-5 zeolite.
In above-mentioned technical proposal, the preferred scope of the maturing temperature in step (iii) is 400~600 DEG C.
In above-mentioned technical proposal, the preferred scope of the calcining time in step (iii) is 2.0~6.0 hours.
To solve above-mentioned technical problem two, technical scheme is as follows: the technical side of one of above-mentioned technical problem One-step method from syngas described in any one of case produces the preparation method of the catalyst of low-carbon alkene, comprising the following steps:
(1) solution A is made by the corresponding salt of component a) and b) is soluble in water；
(2) solution A is mixed with Alpha-alumina, obtains mixture B；
(3) it by mixture B, roasts after drying, obtains mixture C；
(4) mixture C and rare earth modified ZSM-5 molecular sieve are mixed to get required one-step method from syngas and produce low-carbon alkene The catalyst of hydrocarbon.
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.
To solve above-mentioned technical problem three, technical solution of the present invention is as follows:
The catalysis of the production low-carbon alkene of one-step method from syngas described in any one of technical solution of one of above-mentioned technical problem Agent is in one-step method from syngas C2~C4Alkene in application.
Process conditions those skilled in the art of the selection of the catalyst of key problem in technology of the invention, concrete application can close Reason selects and does not have to make the creative labor.Such as specific application conditions may is that
One-step method from syngas C2~C4Alkene method, including using synthesis gas as raw material, raw material and above-mentioned technical problem One of any one of technical solution described in catalyst haptoreaction generate and contain C2~C4Alkene.
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。
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 400~500 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 1500~6000hr-1；
The time of reduction is 6~24 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 4500 hours-1
Also Primordial Qi H2
Recovery time 12 hours.
Using catalyst of the present invention, CO conversion ratio improves 3.5% up to 99.5%, than the prior art；Low-carbon alkene is in carbon Selectivity in hydrogen compound improves 10.1% than the prior art, achieves preferable technical effect up to 78.1%.
Specific embodiment
[embodiment 1]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of La2O3Lanthanum nitrate hexahydrate, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to the zinc nitrate hexahydrate of 10 parts by weight ZnO, It is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 grams of α- Mixture B is obtained on alumina support；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, roasting temperature Degree 500 DEG C, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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, 40% α-Al2O3, 25% modified ZSM-5 (contains La2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of La2O3Lanthanum nitrate hexahydrate, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 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 ZrO2Five nitric hydrates Zirconium is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 In gram alpha-alumina supports mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, and roasts 500 DEG C of temperature, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%ZrO2, 40% α-Al2O3, 25% modified ZSM-5 (contains La2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of Gd2O3Gadolinium nitrate hexahydrate, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to the zinc nitrate hexahydrate of 10 parts by weight ZnO, It is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 grams of α- Mixture B is obtained on alumina support；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, maturing temperature 500 DEG C, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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, 40% α-Al2O3, 25% modified ZSM-5 (contains Gd2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 4]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of Gd2O3Gadolinium nitrate hexahydrate, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 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 ZrO2Five nitric hydrates Zirconium is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 In gram alpha-alumina supports catalyst precarsor B；Impregnated catalyst precarsor B is dry under the conditions of 110 DEG C, is then roasted Burn, 500 DEG C of maturing temperature, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%ZrO2, 40% α-Al2O3, 25% modified ZSM-5 (contains Gd2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to the zinc nitrate hexahydrate of 10 parts by weight ZnO, It is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 grams of α- Mixture B is obtained on alumina support；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, maturing temperature 500 DEG C, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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, 40% α-Al2O3, 25% modified ZSM-5 (contains Sm2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 6]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 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 ZrO2Five nitric hydrates Zirconium is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 In gram alpha-alumina supports mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, and roasts 500 DEG C of temperature, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%ZrO2, 40% α-Al2O3, 25% modified ZSM-5 (contains Sm2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of La2O3Lanthanum nitrate hexahydrate, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 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 4 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 40.0 grams of deionized waters and solution A be made；Vacuum degree 80kPa's Under the conditions of, above-mentioned solution A is impregnated in 40.0 grams of alpha-alumina supports and obtains mixture B；Impregnated mixture B is at 110 DEG C Under the conditions of it is dry, then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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%ZrO2, 40% α- Al2O3, 25% modified ZSM-5 is (containing La2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 8]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of Gd2O3Gadolinium nitrate hexahydrate, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 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 4 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 40.0 grams of deionized waters and solution A be made；Vacuum degree 80kPa's Under the conditions of, above-mentioned solution A is impregnated in 40.0 grams of alpha-alumina supports and obtains mixture B；Impregnated mixture B is at 110 DEG C Under the conditions of it is dry, then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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%ZrO2, 40% α- Al2O3, 25% modified ZSM-5 is (containing Gd2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 9]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 10 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams of deionized waters and solution D be made；In vacuum degree Under conditions of 80kPa, above-mentioned solution D is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 200 and obtains mixture E；It will Mixture E is dry under the conditions of 110 DEG C, is then roasted, 550 DEG C of maturing temperature, and calcining time 4h is rare earth modified to get arriving ZSM-5 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 4 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 40.0 grams of deionized waters and solution A be made；Vacuum degree 80kPa's Under the conditions of, above-mentioned solution A is impregnated in 40.0 grams of alpha-alumina supports and obtains mixture B；Impregnated mixture B is at 110 DEG C Under the conditions of it is dry, then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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%ZrO2, 40% α- Al2O3, 25% modified ZSM-5 is (containing Sm2O310%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 10]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of La2O3Lanthanum nitrate hexahydrate, be equivalent to 5 grams of Gd2O3Gadolinium nitrate hexahydrate, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to the zinc nitrate hexahydrate of 10 parts by weight ZnO, It is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 grams of α- Mixture B is obtained on alumina support；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, maturing temperature 500 DEG C, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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, 40% α-Al2O3, 25% modified ZSM-5 (contains La2O35%, Gd2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 11]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of La2O3Lanthanum nitrate hexahydrate, be equivalent to 5 grams of Gd2O3Gadolinium nitrate hexahydrate, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 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 ZrO2Six nitric hydrates Zinc is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 In gram alpha-alumina supports mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, and roasts 500 DEG C of temperature, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%ZrO2, 40% α-Al2O3, 25% modified ZSM-5 (contains La2O35%, Gd2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 12]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of La2O3Lanthanum nitrate hexahydrate, be equivalent to 5 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to the zinc nitrate hexahydrate of 10 parts by weight ZnO, It is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 grams of α- Mixture B is obtained on alumina support；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, maturing temperature 500 DEG C, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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, 40% α-Al2O3, 25% modified ZSM-5 (contains La2O35%, Sm2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 13]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of La2O3Lanthanum nitrate hexahydrate, be equivalent to 5 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 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 ZrO2Five nitric hydrates Zirconium is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 In gram alpha-alumina supports mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, and roasts 500 DEG C of temperature, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%ZrO2, 40% α-Al2O3, 25% modified ZSM-5 (contains La2O35%, Sm2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 14]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of Gd2O3Gadolinium nitrate hexahydrate, be equivalent to 5 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 molecular sieve.
2, the preparation of catalyst
It weighs and is equivalent to 25 parts by weight Fe2O3Fe(NO3)39H2O, be equivalent to the zinc nitrate hexahydrate of 10 parts by weight ZnO, It is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 grams of α- Mixture B is obtained on alumina support；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, maturing temperature 500 DEG C, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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, 40% α-Al2O3, 25% modified ZSM-5 (contains Gd2O35%, Sm2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 15]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of Gd2O3Gadolinium nitrate hexahydrate, be equivalent to 5 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 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 ZrO2Five nitric hydrates Zirconium is dissolved in 40.0 grams of deionized waters and solution A is made；Under conditions of vacuum degree 80kPa, above-mentioned solution A is impregnated in 40.0 In gram alpha-alumina supports mixture B；Impregnated mixture B is dry under the conditions of 110 DEG C, is then roasted, and roasts 500 DEG C of temperature, calcining time 6h to get arrive mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 25%Fe by weight percentage2O3, 10%ZrO2, 40% α-Al2O3, 25% modified ZSM-5 (contains Gd2O35%, Sm2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 16]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of La2O3Lanthanum nitrate hexahydrate, be equivalent to 5 grams of Gd2O3Gadolinium nitrate hexahydrate, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 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 4 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 40.0 grams of deionized waters and solution A be made；Vacuum degree 80kPa's Under the conditions of, above-mentioned solution A is impregnated in 40.0 grams of alpha-alumina supports and obtains mixture B；Impregnated mixture B is at 110 DEG C Under the conditions of it is dry, then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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%ZrO2, 40% α- Al2O3, 25% modified ZSM-5 is (containing La2O35%, Gd2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 17]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of La2O3Lanthanum nitrate hexahydrate, be equivalent to 5 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 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 4 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 40.0 grams of deionized waters and solution A be made；Vacuum degree 80kPa's Under the conditions of, above-mentioned solution A is impregnated in 40.0 grams of alpha-alumina supports and obtains mixture B；Impregnated mixture B is at 110 DEG C Under the conditions of it is dry, then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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%ZrO2, 40% α- Al2O3, 25% modified ZSM-5 is (containing La2O35%, Sm2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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 18]
1, the preparation of rare earth modified ZSM-5 molecular sieve
It weighs and is equivalent to 5 grams of Gd2O3Gadolinium nitrate hexahydrate, be equivalent to 5 grams of Sm2O3Six nitric hydrate samariums, be dissolved in 60 grams Solution D is made in deionized water；Under conditions of vacuum degree 80kPa, it is 200 that above-mentioned solution D, which is impregnated in 90 grams of silica alumina ratios, Mixture E is obtained on ZSM-5 hydrogen type molecular sieve；Mixture E is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature 550 DEG C, calcining time 4h to get arrive rare earth modified ZSM-5 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 4 parts by weight ZrO2Five nitric hydrate zirconiums, be dissolved in 40.0 grams of deionized waters and solution A be made；Vacuum degree 80kPa's Under the conditions of, above-mentioned solution A is impregnated in 40.0 grams of alpha-alumina supports and obtains mixture B；Impregnated mixture B is at 110 DEG C Under the conditions of it is dry, then roasted, 500 DEG C of maturing temperature, calcining time 6h is to get arriving mixture C.
After 75 grams of mixture Cs and 25 grams of rare earth modified ZSM-5 molecular sieves are mixed, after mill is mixed in the ball mill, tabletting at Type is crushed and sieves 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%ZrO2, 40% α- Al2O3, 25% modified ZSM-5 is (containing Gd2O35%, Sm2O35%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
325 DEG C of reaction temperature
Reaction pressure 1.5MPa
Loaded catalyst 3ml
Catalyst loading 4500 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.
Table 1

Claims (10)

  1. Based on parts by weight include following components 1. one-step method from syngas produces the catalyst of low-carbon alkene:
    A) 5~40 parts of iron series elements or its oxide；
    B) 1~20 part includes at least one of Group IVB element or its oxide；
    C) 20~70 parts of Alpha-aluminas；
    D) 10~40 parts of type ZSM 5 molecular sieves；
    Wherein, type ZSM 5 molecular sieve is rare earth modified ZSM-5 molecular sieve.
  2. 2. the catalyst of one-step method from syngas production low-carbon alkene according to claim 1, it is characterised in that the iron Series elements are selected from least one of iron, cobalt and nickel.
  3. 3. the catalyst of one-step method from syngas production low-carbon alkene according to claim 1, it is characterised in that component a) contains Amount is 10~30 parts.
  4. 4. the catalyst of one-step method from syngas production low-carbon alkene according to claim 1, it is characterised in that component b) contains Amount is 5~15 parts.
  5. 5. the catalyst of one-step method from syngas production low-carbon alkene according to claim 1, it is characterised in that component c) contains Amount is 30~60 parts.
  6. 6. the catalyst of one-step method from syngas production low-carbon alkene according to claim 1, it is characterised in that component d) contains Amount is 20~30 parts.
  7. 7. the catalyst of one-step method from syngas production low-carbon alkene according to claim 1, it is characterised in that described urges The silica alumina ratio SiO of type ZSM 5 molecular sieve in agent2/Al2O3It is 50~500.
  8. 8. the catalyst of one-step method from syngas production low-carbon alkene according to claim 1, it is characterised in that the rare earth Modified zsm-5 zeolite is using the method preparation included the following steps:
    (i) salt of rare earth element is dissolved in water and solution D is made；
    (ii) solution D is mixed into obtain mixture E with ZSM-5 hydrogen type molecular sieve；
    (iii) it by mixture E, roasts after drying, obtains required modified zsm-5 zeolite.
  9. 9. the preparation method of the catalyst of one-step method from syngas production low-carbon alkene according to any one of claims 1 to 8, including Following steps:
    (1) solution A is made by the corresponding salt of component a) and b) is soluble in water；
    (2) solution A is mixed with Alpha-alumina, obtains mixture B；
    (3) it by mixture B, roasts after drying, obtains mixture C；
    (4) mixture C and rare earth modified ZSM-5 molecular sieve are mixed to get to required one-step method from syngas production low-carbon alkene Catalyst.
  10. 10. one-step method from syngas described in any one of claim 1~8 produces the catalyst of low-carbon alkene in one-step method from syngas C processed2~C4Alkene in application.
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