CN103949282B - A kind of Catalysts and its preparation method and application of producing low-carbon alkene - Google Patents
A kind of Catalysts and its preparation method and application of producing low-carbon alkene Download PDFInfo
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- CN103949282B CN103949282B CN201410194222.1A CN201410194222A CN103949282B CN 103949282 B CN103949282 B CN 103949282B CN 201410194222 A CN201410194222 A CN 201410194222A CN 103949282 B CN103949282 B CN 103949282B
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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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
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Abstract
The invention discloses a kind of Catalysts and its preparation method producing low-carbon alkene, and it produces the application in the process of low-carbon alkene at methyl alcohol or dimethyl ether.This catalyst composition comprises ZSM-5 molecular sieve, IM-5 molecular sieve and binding agent, and with the weight of catalyst for benchmark, the content of IM-5 molecular sieve and ZSM-5 molecular sieve is 60wt% ~ 90wt%, and the content of binding agent is 10wt% ~ 40wt%; The weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:1.5 ~ 10.Compared with the catalyst of existing employing ZSM-5 molecular sieve, catalyst of the present invention is used for methyl alcohol or dimethyl ether and produces in the process of low-carbon alkene, and Propylene Selectivity is high, ethene and propylene total recovery high, side reaction product is few, good stability.
Description
Technical field
The present invention relates to a kind of catalyst, particularly relate to a kind of Catalysts and its preparation method for the production of low-carbon alkene and application.
Background technology
Low-carbon alkene typically refers to the alkene that carbon number is less than 4, as ethene, propylene and butylene etc.Low-carbon alkene is that petrochemical industry produces the most basic raw material, may be used for producing the organic compound as polyethylene, polypropylene, acrylonitrile, oxirane or ethylene glycol and so on.
The raw material of current production low-carbon alkene is divided into petroleum and non-petroleum feedstocks, and wherein non-petroleum feedstocks is mainly coal and natural gas.The method of producing low-carbon alkene with non-petroleum feedstocks mainly contains: preparing light olefins from methanol, dimethyl ether low-carbon alkene, preparation of low carbon olefines by synthetic gas.
The catalyst that current methyl alcohol or dimethyl ether reaction for preparing light olefins mainly adopt has two large classes, one class take SAPO-34 as the small pore molecular sieve catalyst of representative, wherein the total recovery of ethene and propylene is higher, and yield of ethene is higher in product, due to its coking speed when being catalyst with it, usually adopt the fluidized-bed process of successive reaction-regeneration.Another kind of is catalyst based on ZSM-5 mesoporous molecular sieve (MFI-type molecular sieve).Compared with SAPO-34, ZSM-5 has larger aperture, be conducive to the diffusion of product low-carbon alkene, and there is certain anti-coking performance and hydrothermal stability, with it for adopting fixed-bed process during catalyst, but the total recovery of its low-carbon alkene is lower, and in product, Propylene Selectivity is lower, coking speed, catalyst still needs further raising service life.
IM-5 molecular sieve is a kind of molecular sieve with the IMF configuration of topological structure.The unique distinction of IM-5 molecular sieve is to have respectively along the ten-ring duct that a axle and c-axis direction two dimension interlock, and the effective dimensions in duct is 4.8 ~ 5.5
.Also have one in addition along the axial short duct of b, this duct is connected with the duct in two other direction is vertical, and pore size is about 2.5nm.Pore passage structure due to IM-5 molecular sieve uniqueness makes it in catalytic reaction process, both have two-dimensional channel to limit the diffusion of molecule, can adapt to again larger transition intermediate simultaneously.The application of current IM-5 molecular sieve is still in the exploratory stage.
Summary of the invention
The object of the invention is to overcome weak point of the prior art, a kind of Catalysts and its preparation method producing low-carbon alkene is provided, and produced the application in low-carbon alkene by methyl alcohol (dimethyl ether).When this catalyst is for the production of low-carbon alkene, Propylene Selectivity is high, and diene (ethene and propylene) total recovery is high, and byproduct is few, and catalyst stability is good.
A kind of catalyst producing low-carbon alkene provided by the invention, its component comprises: ZSM-5 molecular sieve, IM-5 molecular sieve and binding agent, with the weight of catalyst for benchmark, the total content of IM-5 molecular sieve and ZSM-5 molecular sieve is 60wt% ~ 90wt%, and surplus is binding agent; The weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:1.5 ~ 10.
In catalyst of the present invention, the total content of IM-5 molecular sieve and ZSM-5 molecular sieve is preferably 60wt% ~ 85wt%, more preferably 60wt% ~ 80wt%.
In catalyst of the present invention, the weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is preferably 1:4 ~ 8.
Described IM-5 molecular sieve is the IM-5 molecular sieve of modification, and method of modifying is as follows: IM-5 molecular screen primary powder obtains through sodium carbonate and/or sodium bicarbonate solution process, steam treatment and acid solution process successively, the SiO of wherein said IM-5 molecular screen primary powder
2/ Al
2o
3mol ratio is 20 ~ 30.Described sodium carbonate and/or sodium bicarbonate solution treatment conditions are: the concentration of sodium carbonate and/or sodium acid carbonate is 0.5 ~ 3.0mol/L, the liquid-solid volume ratio 4 ~ 6:1 of sodium carbonate and/or sodium bicarbonate solution and IM-5 molecular sieve, temperature 70 ~ 80 DEG C, processing time 1 ~ 4h.Steam treatment condition is: temperature 450 ~ 480 DEG C, and pressure is normal pressure, processing time 12 ~ 24h.The condition of acid solution process is: the concentration of acid: 0.1 ~ 0.6mol/L, temperature 70 ~ 80 DEG C, the liquid-solid volume ratio 4 ~ 6:1 of acid solution and IM-5 molecular sieve, processing time 1 ~ 4h.Wherein said acid is one or both in hydrochloric acid, nitric acid etc.Described IM-5 molecular screen primary powder can adopt method disclosed in prior art to prepare, such as the method preparation of IM-5 molecular sieve disclosed in reference CN103466652A.
ZSM-5 molecular sieve used in the present invention is hydrogen type molecular sieve, its SiO
2/ Al
2o
3mol ratio is 120 ~ 300.The Hydrogen ZSM-5 molecular sieve of preferred employing additive modification, modified additive is thulium and gallium.In the ZSM-5 molecular sieve of additive modification, rare earth metal in the content of element for 0.1wt% ~ 1.0wt%, gallium in the content of element for 0.1wt% ~ 1.0wt%.Above-mentioned modified additive can adopt the method for dipping or ion-exchange to be incorporated in Hydrogen ZSM-5 molecular sieve.
Binding agent of the present invention is derived from one or more in boehmite, Alumina gel.
The preparation method of catalyst of the present invention, step comprises: by IM-5 molecular sieve, ZSM-5 molecular sieve, binder component Homogeneous phase mixing, then kneading and compacting, and drying and roasting, obtain described catalyst.
In the present invention, preferably add acetone and/or propyl alcohol when IM-5 molecular sieve, ZSM-5 molecular sieve, binder component Homogeneous phase mixing, wherein the addition of acetone and/or propyl alcohol is the 0.5wt% ~ 5.0wt% of IM-5 molecular sieve, ZSM-5 molecular sieve and binder component butt weight.
In the preparation method of catalyst of the present invention, when IM-5 molecular sieve, ZSM-5 molecular sieve and binder component Homogeneous phase mixing, the shaping assistants such as peptization acid, extrusion aid can be added as required.
The preparation method of catalyst of the present invention is preferably as follows: by the Hydrogen ZSM-5 molecular sieve of the IM-5 molecular sieve of modification, additive modification, binder component and acetone and/or propyl alcohol Homogeneous phase mixing, then kneading and compacting, and drying and roasting, obtain described catalyst.
In the preparation method of catalyst of the present invention, described drying condition: baking temperature is 100 ~ 120 DEG C, drying time 2 ~ 12h, roasting condition: sintering temperature is 500 ~ 600 DEG C, roasting time 4 ~ 10h.
Catalyst of the present invention is applicable to methyl alcohol or dimethyl ether is produced in the process of low-carbon alkene.This catalyst is applicable in fixed-bed process, and the operating condition that above-mentioned methyl alcohol or dimethyl ether produce low-carbon alkene is as follows: methyl alcohol or dimethyl ether liquid quality air speed 0.5 ~ 2.0h
-1, water liquid quality air speed 0.5 ~ 2.0h
-1, reaction temperature is 450 ~ 480 DEG C, and pressure is 0.1 ~ 1.0MPa.
Compared with the catalyst of existing employing ZSM-5 molecular sieve, catalyst of the present invention is used for methyl alcohol or dimethyl ether is produced in the process of low-carbon alkene, and Propylene Selectivity is high, and diene total recovery is high, and side reaction product is few, long service life.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed explanation.Wherein, wt% is mass fraction.
Embodiment 1
The preparation of the IM-5 molecular sieve-4 A of modification:
The SiO of IM-5 molecular screen primary powder
2/ Al
2o
3mol ratio is 20, adopt modification with the following method: IM-5 molecular screen primary powder is first the aqueous sodium carbonate process of 1.0mol/L by concentration, the liquid-solid volume ratio of aqueous sodium carbonate and IM-5 Molecular sieve raw material is 5, treatment temperature is 75 DEG C, process 2h, then through steam treatment, treatment conditions are temperature 460 DEG C, pressure is normal pressure, processing time 15h, then through salpeter solution process, the concentration of salpeter solution: 0.2mol/L, treatment temperature 75 DEG C, the liquid-solid volume ratio 5:1 of salpeter solution and IM-5 molecular sieve, processing time 2h.
The preparation of the IM-5 molecular sieve B of modification:
The SiO of IM-5 molecular screen primary powder
2/ Al
2o
3mol ratio is 25, adopt modification with the following method: IM-5 molecular screen primary powder is first the aqueous sodium carbonate process of 1.5mol/L by concentration, the liquid-solid volume ratio of aqueous sodium carbonate and IM-5 Molecular sieve raw material is 5, treatment temperature is 78 DEG C, process 2.5h, then through steam treatment, treatment conditions are temperature 470 DEG C, pressure is normal pressure, processing time 18h, then through salpeter solution process, the concentration of salpeter solution: 0.3mol/L, treatment temperature 75 DEG C, the liquid-solid volume ratio 5:1 of salpeter solution and IM-5 molecular sieve, processing time 2h.
Embodiment 2
By the IM-5 molecular sieve-4 A of modification, ZSM-5 molecular sieve (SiO through lanthanum and gallium modification
2/ Al
2o
3mol ratio is 150, containing lanthanum in the content of element for 0.1wt%, gallium in the content of element for 0.2wt%), boehmite, add the acetone of the 1.0wt% accounting for above-mentioned molecular sieve and boehmite butt weight, and add appropriate salpeter solution kneading, extruded moulding, through 100 DEG C drying time 5h, through 550 DEG C of roasting time 4h, obtain catalyst A.With the weight of catalyst for benchmark, the content of IM-5 molecular sieve and modified zsm-5 zeolite is 70wt%, and wherein the weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:6, and surplus is aluminium oxide.
The raw material that production low-carbon alkene adopts is the mixture of dimethyl ether and water, the reaction condition of employing: catalyst sample 2
g, be loaded on self-control Pulse Micro-Chromatography device and evaluate the catalytic performance of catalyst, reaction temperature is 470 DEG C, and pressure is normal pressure, feedstock quality air speed: dimethyl ether: 1h
-1, water: 1h
-1.With this understanding, dimethyl ether charging 1400
gafter reaction result in table 1.Wherein fuel gas composition is methane and ethane, and the composition of liquefied petroleum gas is C3 and the C4 hydrocarbon except propylene; The composition of raw gasoline is C5-C10 hydrocarbon.
Table 1 adopts catalyst A to be 1400 in dimethyl ether inlet amount
gtime reaction result
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 0.00 |
| Water | 28.2 | 56.30 |
| Propylene | 0.00 | 25.67 |
| Ethene | 0.00 | 4.02 |
| Fuel gas | 0.00 | 0.20 |
| Liquefied petroleum gas | 0.00 | 8.49 |
| Raw gasoline | 0.00 | 5.04 |
As can be seen from table 1 data, use catalyst of the present invention, when dimethyl ether treating capacity is 1400g, the conversion ratio 100% of dimethyl ether, propene yield reaches more than 25%, and diene total recovery reaches more than 29%, and raw gasoline yield is below 6%.Show that catalyst of the present invention has excellent Propylene Selectivity, diene total recovery and catalytic stability.
Embodiment 3
By the IM-5 molecular sieve B of modification, the ZSM-5 molecular sieve (SiO through lanthanum and gallium modification
2/ Al
2o
3mol ratio is 180, containing lanthanum in the content of element for 0.1wt%, gallium is 0.2wt% in the content of element, boehmite, adds the propyl alcohol of the 1.0wt% accounting for above-mentioned molecular sieve and boehmite butt weight, and add appropriate salpeter solution kneading, extruded moulding, through 100 DEG C drying time 5h, through 550 DEG C of roasting time 4h, obtain catalyst B.With the weight of catalyst for benchmark, the content of IM-5 molecular sieve and modified zsm-5 zeolite is 75wt%, and wherein the weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:7, and surplus is aluminium oxide.
Carry out reaction evaluating by the reaction condition described in embodiment 2, the yield of dimethyl ether charging 1400g afterproduct is in table 2.
The yield of table 2 catalyst B product when dimethyl ether inlet amount is 1400g
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 0.00 |
| Water | 28.2 | 56.30 |
| Propylene | 0.00 | 27.98 |
| Ethene | 0.00 | 3.61 |
| Fuel gas | 0.00 | 0.20 |
| Liquefied petroleum gas | 0.00 | 7.01 |
| Raw gasoline | 0.00 | 4.35 |
Embodiment 4
By the IM-5 molecular sieve B of modification, the ZSM-5 molecular sieve (SiO through lanthanum and gallium modification
2/ Al
2o
3mol ratio is 180, containing lanthanum in the content of element for 0.1wt%, gallium is 0.2wt% in the content of element, boehmite, adds the propyl alcohol of the 2.0wt% accounting for above-mentioned molecular sieve and boehmite butt weight, and add appropriate salpeter solution kneading, extruded moulding, through 100 DEG C drying time 5h, through 550 DEG C of roasting time 4h, obtain catalyst C.With the weight of catalyst for benchmark, the content of IM-5 molecular sieve and modified zsm-5 zeolite is 70wt%, and wherein the weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:4, and surplus is aluminium oxide.
Carry out reaction evaluating by the reaction condition described in embodiment 2, the yield of dimethyl ether charging 1400g afterproduct is in table 3.
The yield of table 3 catalyst C product when dimethyl ether inlet amount is 1400g
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 0.00 |
| Water | 28.2 | 56.30 |
| Propylene | 0.00 | 26.24 |
| Ethene | 0.00 | 4.43 |
| Fuel gas | 0.00 | 0.40 |
| Liquefied petroleum gas | 0.00 | 7.51 |
| Raw gasoline | 0.00 | 4.42 |
Embodiment 5
By the IM-5 molecular sieve B of modification, the ZSM-5 molecular sieve (SiO through lanthanum and gallium modification
2/ Al
2o
3mol ratio is 280, containing lanthanum in the content of element for 0.1wt%, gallium is 0.2wt% in the content of element, boehmite, adds the propyl alcohol of the 1.0wt% accounting for above-mentioned molecular sieve and boehmite butt weight, and add appropriate salpeter solution kneading, extruded moulding, through 100 DEG C drying time 5h, through 550 DEG C of roasting time 4h, obtain catalyst D.With the weight of catalyst for benchmark, the content of IM-5 molecular sieve and modified zsm-5 zeolite is 70wt%, and wherein the weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:5, and surplus is aluminium oxide.
Carry out reaction evaluating by the reaction condition described in embodiment 2, the yield of dimethyl ether charging 1400g afterproduct is in table 4.
The yield of table 4 catalyst D product when dimethyl ether inlet amount is 1400g
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 0.00 |
| Water | 28.2 | 56.30 |
| Propylene | 0.00 | 25.85 |
| Ethene | 0.00 | 3.21 |
| Fuel gas | 0.00 | 0.30 |
| Liquefied petroleum gas | 0.00 | 8.43 |
| Raw gasoline | 0.00 | 5.22 |
Comparative example 1
By HZSM-5 molecular sieve (SiO
2/ Al
2o
3mol ratio is 280), boehmite, add the propyl alcohol of the 1.0wt% accounting for above-mentioned molecular sieve and boehmite butt weight, and add appropriate salpeter solution kneading, extruded moulding, through 100 DEG C drying time 5h, through 550 DEG C of roasting time 4h, obtain catalyst E.With the weight of catalyst for benchmark, the content of ZSM-5 molecular sieve is 70wt%, and surplus is aluminium oxide.
Carry out reaction evaluating by the reaction condition described in embodiment 2, the yield of dimethyl ether charging 1400g afterproduct is in table 5.
The yield of table 5 catalyst E product when dimethyl ether inlet amount is 1400g
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 11.83 |
| Water | 28.2 | 51.67 |
| Propylene | 0.00 | 9.35 |
| Ethene | 0.00 | 4.74 |
| Fuel gas | 0.00 | 0.80 |
| Liquefied petroleum gas | 0.00 | 9.53 |
| Raw gasoline | 0.00 | 10.40 |
Comparative example 2
By the ZSM-5 molecular sieve (SiO through lanthanum and gallium modification
2/ Al
2o
3mol ratio is 280, containing lanthanum in the content of element for 0.1wt%, gallium is 0.2wt% in the content of element, boehmite, adds the propyl alcohol of the 1.0wt% accounting for above-mentioned molecular sieve and boehmite butt weight, and add appropriate salpeter solution kneading, extruded moulding, through 100 DEG C drying time 5h, through 550 DEG C of roasting time 4h, obtain catalyst F.With the weight of catalyst for benchmark, the content of modified zsm-5 zeolite is 70wt%, and surplus is aluminium oxide.
Carry out reaction evaluating by the reaction condition described in embodiment 2, the yield of dimethyl ether charging 1400g afterproduct is in table 6.
The yield of table 6 catalyst F product when dimethyl ether inlet amount is 1400g
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 8.20 |
| Water | 28.2 | 53.09 |
| Propylene | 0.00 | 10.17 |
| Ethene | 0.00 | 6.64 |
| Fuel gas | 0.00 | 0.80 |
| Liquefied petroleum gas | 0.00 | 8.52 |
| Raw gasoline | 0.00 | 11.10 |
Comparative example 3
By in embodiment 1, SiO
2/ Al
2o
3mol ratio be 25 IM-5 molecular screen primary powder adopt and conventional make HIM-5 molecular sieve C through ammonium exchange process.
By HIM-5 molecular sieve C, boehmite, add the propyl alcohol of the 1.0wt% accounting for above-mentioned molecular sieve and boehmite butt weight, and add appropriate salpeter solution kneading, extruded moulding, through 100 DEG C drying time 5h, through 550 DEG C of roasting time 4h, obtain catalyst G.With the weight of catalyst for benchmark, the content of IM-5 molecular sieve is 70wt%, and surplus is aluminium oxide.
Carry out reaction evaluating by the reaction condition described in embodiment 2, the yield of dimethyl ether charging 1400g afterproduct is in table 7.
The yield of table 7 catalyst G product when dimethyl ether inlet amount is 1400g
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 0.00 |
| Water | 28.2 | 56.30 |
| Propylene | 0.00 | 15.76 |
| Ethene | 0.00 | 8.83 |
| Fuel gas | 0.00 | 0.90 |
| Liquefied petroleum gas | 0.00 | 7.97 |
| Raw gasoline | 0.00 | 9.35 |
Comparative example 4
By in embodiment 1, SiO
2/ Al
2o
3mol ratio be 25 IM-5 molecular screen primary powder adopt and conventional make HIM-5 molecular sieve C through ammonium exchange process.
Change the IM-5 molecular sieve B of the modification in embodiment 5 into HIM-5 molecular sieve C, other make catalyst H with embodiment 5.With the weight of catalyst for benchmark, the content of HIM-5 molecular sieve and modified zsm-5 zeolite is 70wt%, and wherein the weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:5, and surplus is aluminium oxide.
Carry out reaction evaluating by the reaction condition described in embodiment 2, the yield of dimethyl ether charging 1400g afterproduct is in table 8.
The yield of table 8 catalyst H product when dimethyl ether inlet amount is 1400g
| Raw material (wt%) | Product (wt%) | |
| Dimethyl ether | 71.8 | 3.60 |
| Water | 28.2 | 54.89 |
| Propylene | 0.00 | 14.60 |
| Ethene | 0.00 | 7.83 |
| Fuel gas | 0.00 | 0.90 |
| Liquefied petroleum gas | 0.00 | 8.23 |
| Raw gasoline | 0.00 | 9.43 |
Claims (10)
1. produce a catalyst for low-carbon alkene, it consists of: ZSM-5 molecular sieve, IM-5 molecular sieve and binding agent, and with the weight of catalyst for benchmark, the total content of IM-5 molecular sieve and ZSM-5 molecular sieve is 60wt% ~ 90wt%, and surplus is binding agent; The weight ratio of IM-5 molecular sieve and ZSM-5 molecular sieve is 1:1.5 ~ 10, described IM-5 molecular sieve is the IM-5 molecular sieve of modification, and method of modifying is as follows: IM-5 molecular screen primary powder obtains through sodium carbonate and/or sodium bicarbonate solution process, steam treatment and acid solution process successively; The SiO of described IM-5 molecular screen primary powder
2/ Al
2o
3mol ratio is 20 ~ 30;
The condition of described sodium carbonate and/or sodium bicarbonate solution process IM-5 molecular screen primary powder is: the concentration of sodium carbonate and/or sodium bicarbonate solution is 0.5 ~ 3.0mol/L, the liquid-solid volume ratio 4 ~ 6:1 of sodium carbonate and/or sodium bicarbonate solution and IM-5 molecular sieve, temperature 70 ~ 80 DEG C, processing time 1 ~ 4h; Steam treatment condition is: temperature 450 ~ 480 DEG C, and pressure is normal pressure, processing time 12 ~ 24h; The condition of acid solution process is: the concentration of acid solution is 0.1 ~ 0.6mol/L, temperature 70 ~ 80 DEG C, the liquid-solid volume ratio 4 ~ 6:1 of acid solution and IM-5 molecular sieve, processing time 1 ~ 4h; Wherein said acid is one or both in hydrochloric acid, nitric acid.
2. according to catalyst according to claim 1, it is characterized in that in described catalyst, the total content of IM-5 molecular sieve and ZSM-5 molecular sieve is 60wt% ~ 85wt%.
3., according to catalyst according to claim 2, it is characterized in that the total content of described IM-5 molecular sieve and ZSM-5 molecular sieve is 60wt% ~ 80wt%.
4., according to catalyst according to claim 1, it is characterized in that the weight ratio of described IM-5 molecular sieve and ZSM-5 molecular sieve is 1:4 ~ 8.
5., according to catalyst according to claim 1, it is characterized in that described ZSM-5 molecular sieve is hydrogen type molecular sieve, its SiO
2/ Al
2o
3mol ratio is 120 ~ 300.
6., according to the catalyst described in claim 1 or 5, it is characterized in that described ZSM-5 molecular sieve adopts the Hydrogen ZSM-5 molecular sieve of additive modification, modified additive is thulium and gallium; In the ZSM-5 molecular sieve of additive modification, rare earth metal in the content of element for 0.1wt% ~ 1.0wt%, gallium in the content of element for 0.1wt% ~ 1.0wt%.
7. the preparation method of the arbitrary described catalyst of claim 1 ~ 6, step comprises: by IM-5 molecular sieve, ZSM-5 molecular sieve, binder component Homogeneous phase mixing, then kneading, shaping, and drying and roasting, obtain catalyst.
8. in accordance with the method for claim 7, it is characterized in that, add acetone and/or propyl alcohol by when IM-5 molecular sieve, ZSM-5 molecular sieve, binder component Homogeneous phase mixing, wherein the addition of acetone and/or propyl alcohol is the 0.5wt% ~ 5.0wt% of IM-5 molecular sieve, ZSM-5 molecular sieve and binder component wgt dry basis by total.
9. in accordance with the method for claim 7, it is characterized in that described drying condition is: baking temperature is 100 ~ 120 DEG C, drying time 2 ~ 12h, roasting condition: sintering temperature is 500 ~ 600 DEG C, roasting time 4 ~ 10h.
10. according to the application of the arbitrary catalyst described in claim 1 ~ 6 in methyl alcohol or dimethyl ether production low-carbon alkene.
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| CN103263947A (en) * | 2013-06-03 | 2013-08-28 | 神华集团有限责任公司 | Composite molecular sieve for preparing catalyst for producing light olefins from organic oxygen-containing compound, and preparation method thereof |
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