CN109304220A - The catalyst of preparing low-carbon olefin - Google Patents
The catalyst of preparing low-carbon olefin Download PDFInfo
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- CN109304220A CN109304220A CN201710628268.3A CN201710628268A CN109304220A CN 109304220 A CN109304220 A CN 109304220A CN 201710628268 A CN201710628268 A CN 201710628268A CN 109304220 A CN109304220 A CN 109304220A
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- carbon olefin
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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
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to the catalyst of preparing low-carbon olefin, mainly solve the problems, such as that CO conversion ratio is low low with selectivity of light olefin in preparing low-carbon olefin reaction existing in the prior art.The present invention uses the catalyst of preparing low-carbon olefin, based on parts by weight includes following components: a) 20~50 parts of ferro elements or its oxide；B) 5~30 parts include selected from least one of VIIB race element or its oxide；C) 5~30 parts include selected from least one of VB race element or its oxide；D) 5~15 parts include selected from least one of IA race element element or its oxide；E) 10~65 parts include the technical solution selected from type ZSM 5 molecular sieve, preferably solve the problems, such as this, can be used for the industrial production of preparing low-carbon olefin.
Description
Technical field
The present invention relates to the catalyst of preparing low-carbon olefin.
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.
The direct synthesizing low-carbon alkene technique functions of synthesis gas 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 alkene 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 that F- T synthesis gas prepares low-carbon alkene is mainly iron catalyst series, direct in order to improve synthesis gas
The selectivity of preparing low-carbon olefins can carry out physics and chemical modification to fischer-tropsch synthetic catalyst, such as be suitable for using molecular sieve
Cellular structure, be conducive to low-carbon alkene and diffuse out metal active centres in time, inhibit the secondary response of low-carbon alkene；It improves
Metal ion dispersibility, also there is preferable olefine selective；Support-metal strong interaction change can also be improved low-carbon alkene
Selectivity；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
Hydrocarbon-selective；Electronics accelerating auxiliaries are added, CO chemisorption heat is promoted to increase, adsorbance also increases, and hydrogen adsorptive capacity reduces, knot
Fruit selectivity of light olefin increases；Catalyst acid center is eliminated, the secondary response of low-carbon alkene can be inhibited, improve its selection
Property.By the Support effect and the certain transition metal promoters of addition and alkali metal promoter of catalyst carrier, catalysis can obviously improve
Agent performance develops the fischer-tropsch synthetic catalyst of the highly selective producing light olefins of novel high-activity with the non-ASF distribution of product.
The direct synthesizing low-carbon alkene of synthesis gas, it has also become one of the research hotspot of fischer-tropsch synthetic catalyst exploitation.The Chinese Academy of Sciences
In patent CN1083415A disclosed in Dalian Chemical Physics Research Institute, with the Group IIAs such as MgO alkali metal oxide or silica-rich zeolite point
Iron-Mn catalyst system that son sieve (or phosphorus aluminium zeolite) supports, makees auxiliary agent with highly basic K or Cs ion, in synthesis of gas produced low-carbon alkene
Hydrocarbon reaction pressure is 1.0~5.0MPa, at 300~400 DEG C of reaction temperature, can get higher active (CO conversion ratio 90%) and
Selectivity (selectivity of light olefin 66%).But the catalyst preparation process is complicated, the especially preparation of carrier zeolite molecular sieve
Forming process higher cost, is unfavorable for industrialized production.In the number of patent application 01144691.9 that Beijing University of Chemical Technology is declared,
Laser pyrolysis processes combination solid phase reaction combination technique is used to be prepared for Fe3Fe base nano-catalyst based on C is applied to synthesis
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 that CO turns in preparing low-carbon olefin technology in the prior art
The low problem low with selectivity of light olefin in product of rate provides a kind of catalyst of new preparing low-carbon olefin,
The catalyst has the advantages that selectivity of light olefin is high in CO high conversion rate and product.
The second technical problem to be solved by the present invention is catalysis corresponding with catalyst described in one of above-mentioned technical problem
The preparation method of agent.
The third technical problem to be solved by the present invention is the application using catalyst described in one of above-mentioned technical problem.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows:
The catalyst of preparing low-carbon olefin includes following components based on parts by weight:
A) 20~50 parts of ferro elements or its oxide；
B) 5~30 parts include selected from least one of VIIB race element or its oxide；
C) 5~30 parts include selected from least one of VB race element or its oxide；
D) 5~15 parts include selected from least one of IA race element element or its oxide；
E) 10~65 include being selected from type ZSM 5 molecular sieve.
In above-mentioned technical proposal, the oxide of the iron is preferably di-iron trioxide.
In above-mentioned technical proposal, the oxide of the iron is preferably 20~40 parts.
In above-mentioned technical proposal, component b) content is preferably 10~25 parts.
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, VIIB race element preferably includes Mn or its oxide.
In above-mentioned technical proposal, Group IIB element preferably includes Zn or its oxide.
In above-mentioned technical proposal, component b) is preferably simultaneously including Mn (or its oxide) and Zn (or its oxide), at this time
Between Mn (or its oxide) and Zn (or its oxide) in improving CO high conversion rate and product in terms of selectivity of light olefin
With synergistic effect.
The ratio of Mn and Zn is not particularly limited, and manganese or its oxide are in terms of MnO and Zn or its oxide are in terms of ZnO, manganese
(or its oxide) and zinc (or zinc oxide) weight ratio can be but not limited to 0.51~5, more specific 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, component c) content is preferably 10~25 parts.The preferred vanadium of VB race element described in component c), VB
The oxide of race's element is preferably the oxide of vanadium, such as, but not limited to vanadic anhydride.
In above-mentioned technical proposal, component d) content is preferably 10~25 parts.
In above-mentioned technical proposal, d) described at least one of IA element preferred Na and K, more preferably include simultaneously Na and
The oxide of K, Na select Na2The preferred K of the oxide of O, K2O, Na (or its oxide) and K (or its oxide) are being improved at this time
There is synergistic effect in terms of the selectivity of CO conversion ratio and low-carbon alkene.
The ratio of Na and K is not particularly limited, and Na or its oxide are with Na2O meter and K or its oxide are with K2O meter, Na
(or its oxide) and K (or its oxide) weight ratio can be but not limited to 0.11~3, more specific non-limiting weight ratio
Can be 0.11,0.21,0.31,0.41,0.51,0.61,0.71,0.81,0.91,1.01,1.21,1.51,1.71,1.91,
2.01,2.51 etc..
In above-mentioned technical proposal, the silica alumina ratio SiO of type ZSM 5 molecular sieve in the catalyst2/Al2O3It is 50~500.
Such as, but not limited to, silica alumina ratio can be 100,150,200,250,300,350,400,450 etc..To count on year-on-year basis, the present invention
Embodiment part is all made of SiO2/Al2O3For 300 type ZSM 5 molecular sieve.
In above-mentioned technical proposal, type ZSM 5 molecular sieve is preferably using including at least one of IIA element element or its oxygen
Compound is the ZSM-5 molecular sieve of modifier modification.
In above-mentioned technical proposal, the ZSM-5 molecular sieve of the modification by weight, preferably contains modifying agent 1~15%.
In above-mentioned technical proposal, IIA element preferably includes at least one of Mg and Sr, the oxide of Mg preferred MgO, Sr
The preferred SrO of oxide.Mg (or its oxide) and Sr (or its oxide) are improving CO conversion ratio and low-carbon alkene at this time
Selectivity aspect has synergistic effect.
In above-mentioned technical proposal, the mutual ratio of Mg and Sr are not particularly limited, and Mg or its oxide are in terms of MgO and Sr
Or its oxide, in terms of SrO, Mg (or its oxide) and Sr (or its oxide) weight ratio can be but not limited to 0.11~3,
More specific non-limiting weight ratio can be 0.11,0.21,0.31,0.41,0.51,0.61,0.71,0.81,0.91,
1.01,1.21,1.51,1.71,1.91,2.01,2.51 etc..
To solve above-mentioned technical problem two, technical scheme is as follows:
The catalyst system of preparing low-carbon olefin described in any one of technical solution of one of above-mentioned technical problem
Preparation Method, comprising the following steps:
(1) the corresponding oxide by component a), b) and c), the corresponding carbonate of component d) and binder mixing, obtain
To granular material A；
(2) it adds water in material A, is mediated to obtain material B；
(3) material C will be obtained after the drying of material B extruded moulding；
(4) by after material C high temperature sintering, cooling crushing and screening obtains required molten state mixture D.
(5) molten state mixture D and type ZSM 5 molecular sieve are mixed to get to required catalyst.
In above-mentioned technical proposal, binder and dosage are not particularly limited in step (1), and those skilled in the art can be with
It reasonably selects.Such as, but not limited to binder can be hydroxypropyl methyl cellulose powder, hydroxyethylmethylcellulose powder, first
Base cellulose powder, carboxymethyl cellulose, starch, dextrin, polyethylene glycol, polyvinyl alcohol etc.；The dosage of binder for example but
Be not limited to component a), b), c) and d) total weight 3~6%.
In above-mentioned technical proposal, the dosage of water is not particularly limited in step (2), is can reach kneading extrusion degree
Preferably, this those skilled in the art can be reasonably selected and does not need to make the creative labor, such as, but not limited to step (2)
Middle water consumption is preferably all component a), b in step (1)), c) and d) the 5~15% of the total weight of total weight.
In above-mentioned technical proposal, dry process conditions are not particularly limited in step (3), and dry final degree does not have yet
There is special limitation.Such as, but not limited to dry temperature is 100~150 DEG C, and the dry time is 6 hours or more (such as 8 is small
When, 12 hours, 18 hours, 24 hours etc.).
In above-mentioned technical proposal, the preferred scope of step (4) high temperature sintering temperature is 1300~1700 DEG C.Such as but not
It is limited to 1350 DEG C, 1400 DEG C, 1450 DEG C, 1500 DEG C, 1550 DEG C, 1600 DEG C, 1650 DEG C etc..
In above-mentioned technical proposal, time preferably 4~10 hours of the sintering of step (4) high temperature.Such as, but not limited to 5 is small
When, 6 hours, 7 hours, 8 hours, 9 hours etc..
In above-mentioned technical proposal, the hybrid mode of step (5) is not specially required, and can obtain comparable technical effect.
But one skilled in the art will appreciate that after mill is mixed in the ball mill, compression molding, further crushing and screening effect is especially good.
It include at least one of IIA element element or its oxide when type ZSM 5 molecular sieve of the present invention uses
For modifier modification ZSM-5 molecular sieve when, modified ZSM-5 molecular sieve use include the following steps method preparation:
(i) solution E is made by the salt of IIA element is soluble in water；
(ii) solution E is mixed to obtain to mixture F with ZSM-5 molecular sieve；
(iii) it by mixture F, roasts after drying, obtains the ZSM-5 molecular sieve G of required modification.
In above-mentioned technical proposal, as non limiting example, the salt of IIA element, can be nitrate, carboxylate (such as
But it is not limited to acetate, carbonate, bicarbonate) etc..
In above-mentioned technical proposal, step (ii) preferably uses ZSM-5 hydrogen type molecular sieve.
In above-mentioned technical proposal, the hybrid mode of step (ii) is not specially required, but the mixed effect under vacuum condition
It is especially good.Solution is such as, but not limited to impregnated into corresponding solid component under the conditions of 1~80kPa of vacuum degree.
In above-mentioned technical proposal, the preferred scope of the maturing temperature in step (iii) is 400~600 DEG C, calcining time
Preferred scope is 2.0~6.0 hours.
To solve above-mentioned technical problem three, technical scheme is as follows:
Catalyst described in any one of technical solution of one of above-mentioned technical problem is in synthesis gas C2~C4Alkene in
Using.
Key problem in technology of the invention is the selection of catalyst, and process conditions those skilled in the art of concrete application can close
Reason selects and does not have to make the creative labor.Such as specific application conditions may is that
One of the method for preparing low-carbon olefin, including using synthesis gas as raw material, raw material and above-mentioned technical problem
Catalyst haptoreaction described in any one of technical solution, which generates, contains 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:
The reducing condition of above-described embodiment 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 3.7% up to 99.6%, than the prior art；Low-carbon alkene is in carbon
Selectivity in hydrogen compound improves 10.7% than the prior art, achieves preferable technical effect up to 77.8%.
Specific embodiment
[embodiment 1]
1, the preparation of modified zsm-5 zeolite
The magnesium nitrate hexahydrate for being equivalent to 10 grams of MgO is weighed, is dissolved in 60 grams of deionized waters and solution E is made；In vacuum degree
Under conditions of 80kPa, above-mentioned solution E is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 300 and obtains mixture F；It will
Catalyst precarsor F is dry under the conditions of 110 DEG C, is then roasted, 500 DEG C of maturing temperature, and calcining time 4h is to get to being modified
ZSM-5 molecular sieve G.
2, the preparation of catalyst
Weigh 35.0 parts by weight di-iron trioxide (Fe2O3), 15.0 parts by weight manganese oxide (MnO), 15.0 parts by weight five oxidation
Two vanadium (V2O5), be equivalent to 10 parts by weight Na2Sodium carbonate (the Na of O2CO3) four kinds of raw materials and based on above-mentioned four kinds of raw material total amounts plus
The hydroxypropyl methyl cellulose powder that weight percent is 4% grinds in ball mill and mixes 4 hours, obtains material A；By above-mentioned four
The deionized water that kind raw material total amount meter add weight percentage is 7% is mediated to soft shape, is obtained to grinding in mixed material A
To material B；Kneaded material B is sent into banded extruder, and diameter is made and is the strip of 5mm, and is cut into the column that length is 20mm
Shape is sent into drying equipment after natural drying, 8 hours dry in 110 DEG C, obtains material C；By dried material C, it is sent into
It in high temperature furnace, is calcined 5.0 hours in 1500 DEG C, is crushed after cooling, takes the particle by 120 mesh standard sieves, it is mixed to obtain molten state
Close object D.
After 75 grams of molten state mixture D and 25 grams of modified zsm-5 zeolite G are mixed, after mill is mixed in the ball mill, tabletting
Molding, it is broken to sieve and sieve the particle for taking 40~80 mesh, obtain catalyst of the present invention.
Obtained catalyst includes following components: 35%Fe by weight percentage2O3, 15%MnO, 15%V2O5, 10%
Na2O, 25% modified ZSM-5 (contain MgO 10%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
320 DEG C of reaction temperature
Reaction pressure 1.2MPa
Loaded catalyst 3ml
Catalyst loading 1500 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1.
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 zsm-5 zeolite
The magnesium nitrate hexahydrate for being equivalent to 10 grams of MgO is weighed, is dissolved in 60 grams of deionized waters and solution E is made；In vacuum degree
Under conditions of 80kPa, above-mentioned solution E is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 300 and obtains mixture F；It will
Mixture F is dry under the conditions of 110 DEG C, is then roasted, 500 DEG C of maturing temperature, and calcining time 4h is to get arriving modified ZSM-5-
5 molecular sieve G.
2, the preparation of catalyst
Weigh 35.0 parts by weight di-iron trioxide (Fe2O3), 15.0 part by weight of zinc oxide (ZnO), 15.0 parts by weight five oxidation
Two vanadium (V2O5), be equivalent to 10 parts by weight Na2Sodium carbonate (the Na of O2CO3) four kinds of raw materials and based on above-mentioned four kinds of raw material total amounts plus
The hydroxypropyl methyl cellulose powder that weight percent is 4% grinds in ball mill and mixes 4 hours, obtains material A；By above-mentioned four
The deionized water that kind raw material total amount meter add weight percentage is 7% is mediated to soft shape, is obtained to grinding in mixed material A
To material B；Kneaded material B is sent into banded extruder, and diameter is made and is the strip of 5mm, and is cut into the column that length is 20mm
Shape is sent into drying equipment after natural drying, 8 hours dry in 110 DEG C, obtains material C；By dried material C, it is sent into
It in high temperature furnace, is calcined 5.0 hours in 1500 DEG C, is crushed after cooling, takes the particle by 120 mesh standard sieves, it is mixed to obtain molten state
Close object D.
After 75 grams of molten state mixture D and 25 grams of modified zsm-5 zeolite G are mixed, after mill is mixed in the ball mill, tabletting
Molding is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 35%Fe by weight percentage2O3, 15%ZnO, 15%V2O5, 10%
Na2O, 25% modified ZSM-5 (contain MgO 10%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
320 DEG C of reaction temperature
Reaction pressure 1.2MPa
Loaded catalyst 3ml
Catalyst loading 1500 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1.
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 zsm-5 zeolite
The magnesium nitrate hexahydrate for being equivalent to 10 grams of MgO is weighed, is dissolved in 60 grams of deionized waters and solution E is made；In vacuum degree
Under conditions of 80kPa, above-mentioned solution E is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 300 and obtains mixture F；It will
Mixture F is dry under the conditions of 110 DEG C, is then roasted, 500 DEG C of maturing temperature, and calcining time 4h is to get arriving modified ZSM-5-
5 molecular sieve G.
2, the preparation of catalyst
Weigh 35.0 parts by weight di-iron trioxide (Fe2O3), 10.0 parts by weight manganese oxide (MnO), 5.0 part by weight of zinc oxide
(ZnO), 15.0 parts by weight vanadic anhydride (V2O5), be equivalent to 10 parts by weight Na2Sodium carbonate (the Na of O2CO3) five kinds of raw materials and
It is small to grind mixed 4 in ball mill for the hydroxypropyl methyl cellulose powder that add weight percentage is 4% based on above-mentioned five kinds of raw material total amounts
When, obtain material A；The deionized water that add weight percentage is 7% based on the above-mentioned four kinds of raw material total amounts material A mixed to mill
In, it is mediated to soft shape, obtains material B；Kneaded material B is sent into banded extruder, and the strip that diameter is 5mm is made,
And it is cut into the column that length is 20mm, and after natural drying, it is sent into drying equipment, it is 8 hours dry in 110 DEG C, obtain material
C；It is sent into dried material C in high temperature furnace, is calcined 5.0 hours in 1500 DEG C, is crushed after cooling, is taken through 120 targets standard
The particle of sieve obtains molten state mixture D.
After 75 grams of molten state mixture D and 25 grams of modified zsm-5 zeolite G are mixed, after mill is mixed in the ball mill, tabletting
Molding is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 35%Fe by weight percentage2O3, 10%MnO, 5%ZnO, 15%
V2O5, 10%Na2O, 25% modified ZSM-5 (contain MgO 10%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
320 DEG C of reaction temperature
Reaction pressure 1.2MPa
Loaded catalyst 3ml
Catalyst loading 1500 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1.
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, Mn (or its oxide) and Zn (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 zsm-5 zeolite
The magnesium nitrate hexahydrate for being equivalent to 10 grams of MgO is weighed, is dissolved in 60 grams of deionized waters and solution E is made；In vacuum degree
Under conditions of 80kPa, above-mentioned solution E is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 300 and obtains mixture F；It will
Mixture F is dry under the conditions of 110 DEG C, is then roasted, 500 DEG C of maturing temperature, and calcining time 4h is to get arriving modified ZSM-5-
5 molecular sieve G.
2, the preparation of catalyst
Weigh 35.0 parts by weight di-iron trioxide (Fe2O3), 10.0 parts by weight manganese oxide (MnO), 5.0 part by weight of zinc oxide
(ZnO), 15.0 parts by weight vanadic anhydride (V2O5), be equivalent to 10 parts by weight K2Potassium carbonate (the K of O2CO3) five kinds of raw materials and press
It is small to grind mixed 4 in ball mill for the hydroxypropyl methyl cellulose powder that above-mentioned five kinds of raw materials total amount meter add weight percentage is 4%
When, obtain material A；The deionized water that add weight percentage is 7% based on the above-mentioned four kinds of raw material total amounts material A mixed to mill
In, it is mediated to soft shape, obtains material B；Kneaded material B is sent into banded extruder, and the strip that diameter is 5mm is made,
And it is cut into the column that length is 20mm, and after natural drying, it is sent into drying equipment, it is 8 hours dry in 110 DEG C, obtain material
C；It is sent into dried material C in high temperature furnace, is calcined 5.0 hours in 1500 DEG C, is crushed after cooling, is taken through 120 targets standard
The particle of sieve obtains molten state mixture D.
After 75 grams of molten state mixture D and 25 grams of modified zsm-5 zeolite G are mixed, after mill is mixed in the ball mill, tabletting
Molding is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 35%Fe by weight percentage2O3, 10%MnO, 5%ZnO, 15%
V2O5, 10%K2O, 25% modified ZSM-5 (contain MgO 10%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
320 DEG C of reaction temperature
Reaction pressure 1.2MPa
Loaded catalyst 3ml
Catalyst loading 1500 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1.
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 zsm-5 zeolite
The magnesium nitrate hexahydrate for being equivalent to 10 grams of MgO is weighed, is dissolved in 60 grams of deionized waters and solution E is made；In vacuum degree
Under conditions of 80kPa, above-mentioned solution E is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 300 and obtains mixture F；It will
Mixture F is dry under the conditions of 110 DEG C, is then roasted, 500 DEG C of maturing temperature, and calcining time 4h is to get arriving modified ZSM-5-
5 molecular sieve G.
2, the preparation of catalyst
Weigh 35.0 parts by weight di-iron trioxide (Fe2O3), 10.0 parts by weight manganese oxide (MnO), 5.0 part by weight of zinc oxide
(ZnO), 15.0 parts by weight vanadic anhydride (V2O5), be equivalent to 4 parts by weight Na2Sodium carbonate (the Na of O2CO3), be equivalent to 6 weight
Part K2Potassium carbonate (the K of O2CO3) six kinds of raw materials and add weight percentage is 4% based on above-mentioned six kinds of raw material total amounts hydroxypropyl
Methylcellulose powder grinds in ball mill and mixes 4 hours, obtains material A；The add weight percentage based on above-mentioned four kinds of raw material total amounts
It is 7% deionized water to grinding in mixed material A, is mediated to soft shape, obtain material B；Kneaded material B is sent into
In banded extruder, diameter is made and is the strip of 5mm, and be cut into the column that length is 20mm, after natural drying, is sent into drying equipment
In, it is 8 hours dry in 110 DEG C, obtain material C；Dried material C is sent into high temperature furnace, it is small in 1500 DEG C of calcinings 5.0
When, it is crushed after cooling, takes the particle by 120 mesh standard sieves, obtain molten state mixture D.
After 75 grams of molten state mixture D and 25 grams of modified zsm-5 zeolite G are mixed, after mill is mixed in the ball mill, tabletting
Molding is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 35%Fe by weight percentage2O3, 10%MnO, 5%ZnO, 15%
V2O5, 4%Na2O, 6%K2O, 25% modified ZSM-5 (contain MgO 10%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
320 DEG C of reaction temperature
Reaction pressure 1.2MPa
Loaded catalyst 3ml
Catalyst loading 1500 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1.
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, Na (or its oxide) and K (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 zsm-5 zeolite
The strontium nitrate for being equivalent to 10 grams of SrO is weighed, is dissolved in 60 grams of deionized waters and solution E is made；Vacuum degree 80kPa's
Under the conditions of, above-mentioned solution E is impregnated on the ZSM-5 hydrogen type molecular sieve that 90 grams of silica alumina ratios are 300 and obtains mixture F；By mixture F
It is dry under the conditions of 110 DEG C, it is then roasted, 500 DEG C of maturing temperature, calcining time 4h is to get arriving modified zsm-5 zeolite
G。
2, the preparation of catalyst
Weigh 35.0 parts by weight di-iron trioxide (Fe2O3), 10.0 parts by weight manganese oxide (MnO), 5.0 part by weight of zinc oxide
(ZnO), 15.0 parts by weight vanadic anhydride (V2O5), be equivalent to 4 parts by weight Na2Sodium carbonate (the Na of O2CO3), be equivalent to 6 weight
Part K2Potassium carbonate (the K of O2CO3) six kinds of raw materials and add weight percentage is 4% based on above-mentioned six kinds of raw material total amounts hydroxypropyl
Methylcellulose powder grinds in ball mill and mixes 4 hours, obtains material A；The add weight percentage based on above-mentioned four kinds of raw material total amounts
It is 7% deionized water to grinding in mixed material A, is mediated to soft shape, obtain material B；Kneaded material B is sent into
In banded extruder, diameter is made and is the strip of 5mm, and be cut into the column that length is 20mm, after natural drying, is sent into drying equipment
In, it is 8 hours dry in 110 DEG C, obtain material C；Dried material C is sent into high temperature furnace, it is small in 1500 DEG C of calcinings 5.0
When, it is crushed after cooling, takes the particle by 120 mesh standard sieves, obtain molten state mixture D.
After 75 grams of molten state mixture D and 25 grams of modified zsm-5 zeolite G are mixed, after mill is mixed in the ball mill, tabletting
Molding is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 35%Fe by weight percentage2O3, 10%MnO, 5%ZnO, 15%
V2O5, 4%Na2O, 6%K2O, 25% modified ZSM-5 (contain SrO 10%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
320 DEG C of reaction temperature
Reaction pressure 1.2MPa
Loaded catalyst 3ml
Catalyst loading 1500 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1.
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 zsm-5 zeolite
The strontium nitrate for weighing the magnesium nitrate hexahydrate for being equivalent to 4 grams of MgO and being equivalent to 6 grams of SrO is dissolved in 60 grams of deionized waters
In mixed solution E is made；Under conditions of vacuum degree 80kPa, it is 300 that above-mentioned mixed solution E, which is impregnated in 90 grams of silica alumina ratios,
Mixture F is obtained on ZSM-5 hydrogen type molecular sieve；Mixture F is dry under the conditions of 110 DEG C, it is then roasted, maturing temperature
500 DEG C, calcining time 4h to get arrive modified zsm-5 zeolite G.
2, the preparation of catalyst
Weigh 35.0 parts by weight di-iron trioxide (Fe2O3), 10.0 parts by weight manganese oxide (MnO), 5.0 part by weight of zinc oxide
(ZnO), 15.0 parts by weight vanadic anhydride (V2O5), be equivalent to 4 parts by weight Na2Sodium carbonate (the Na of O2CO3), be equivalent to 6 weight
Part K2Potassium carbonate (the K of O2CO3) six kinds of raw materials and add weight percentage is 4% based on above-mentioned six kinds of raw material total amounts hydroxypropyl
Methylcellulose powder grinds in ball mill and mixes 4 hours, obtains material A；The add weight percentage based on above-mentioned four kinds of raw material total amounts
It is 7% deionized water to grinding in mixed material A, is mediated to soft shape, obtain material B；Kneaded material B is sent into
In banded extruder, diameter is made and is the strip of 5mm, and be cut into the column that length is 20mm, after natural drying, is sent into drying equipment
In, it is 8 hours dry in 110 DEG C, obtain material C；Dried material C is sent into high temperature furnace, it is small in 1500 DEG C of calcinings 5.0
When, it is crushed after cooling, takes the particle by 120 mesh standard sieves, obtain molten state mixture D.
After 75 grams of molten state mixture D and 25 grams of modified zsm-5 zeolite G are mixed, after mill is mixed in the ball mill, tabletting
Molding is crushed and sieves the particle for taking 40~80 mesh, obtains catalyst of the present invention.
Obtained catalyst includes following components: 35%Fe by weight percentage2O3, 10%MnO, 5%ZnO, 15%
V2O5, 4%Na2O, 6%K2O, 25% modified ZSM-5 (contain MgO 4%, SrO 6%).
3, evaluating catalyst
The evaluation condition of catalyst are as follows:
Reaction condition are as follows:
8 millimeters of fixed bed reactors of φ
320 DEG C of reaction temperature
Reaction pressure 1.2MPa
Loaded catalyst 3ml
Catalyst loading 1500 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1.
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 Mg (or its oxide) and Sr (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 (9)
1. the catalyst of preparing low-carbon olefin includes following components based on parts by weight:
A) 20~50 parts of ferro elements or its oxide；
B) 5~30 parts include selected from least one of VIIB race element or its oxide；
C) 5~30 parts include selected from least one of VB race element or its oxide；
D) 5~15 parts include selected from least one of IA race element element or its oxide；
E) 10~65 parts include being selected from type ZSM 5 molecular sieve.
2. the catalyst of preparing low-carbon olefin according to claim 1, it is characterised in that the oxidation of the iron
Object is di-iron trioxide.
3. the catalyst of preparing low-carbon olefin according to claim 1, it is characterised in that component b) content is 10
~25 parts.
4. the catalyst of preparing low-carbon olefin according to claim 1, it is characterised in that component c) content is 10
~25 parts.
5. the catalyst of preparing low-carbon olefin according to claim 1, it is characterised in that in the catalyst
The silica alumina ratio SiO of type ZSM 5 molecular sieve2/Al2O3It is 50~500.
6. the preparation method of the catalyst of the described in any item preparing low-carbon olefins of claim 1~6, including following step
It is rapid:
(1) the corresponding oxide by component a), b) and c), the corresponding carbonate of component d) and binder mixing, obtain powder
Shape material A；
(2) it adds water in material A, is mediated to obtain material B；
(3) material C will be obtained after the drying of material B extruded moulding；
(4) by after material C high temperature sintering, cooling crushing and screening obtains required molten state mixture D.
(5) molten state mixture D and type ZSM 5 molecular sieve are mixed to get to required catalyst.
7. the preparation method of the catalyst of preparing low-carbon olefin according to claim 6, it is characterised in that described
High temperature sintering temperature be 1200~1800 DEG C.
8. the preparation method of the catalyst of preparing low-carbon olefin according to claim 7, it is characterised in that high temperature
The time of sintering is 4~10 hours.
9. catalyst described in any one of claim 1~6 is in synthesis gas C2~C4Alkene in application.
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