CN113751059A - Catalyst for producing propylene and ethylene by directly converting tert-butyl alcohol and application thereof - Google Patents
Catalyst for producing propylene and ethylene by directly converting tert-butyl alcohol and application thereof Download PDFInfo
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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Abstract
The invention discloses a catalyst for producing propylene and ethylene by directly converting tert-butyl alcohol, wherein the catalyst is of a core-shell structure, a core is a beta molecular sieve, and a shell is aluminum oxide. The invention also discloses a method for producing propylene and ethylene by directly converting tert-butyl alcohol, which comprises the following steps: the tertiary butanol aqueous solution is used as a raw material, and the raw material is contacted with the catalyst of the invention to react to generate a product containing propylene and ethylene. The catalyst of the invention realizes the process of directly converting the tert-butyl alcohol into the propylene and the ethylene, and has the characteristics of high catalyst activity, high stability, high selectivity of the propylene and the ethylene, and the like.
Description
Technical Field
The invention relates to a catalyst for producing propylene and ethylene by directly converting tertiary butanol and a method for producing propylene and ethylene by directly converting tertiary butanol.
Background
Tert-butyl alcohol (TBA) is a colorless crystal, a colorless volatile liquid in the presence of a small amount of water, has an odor similar to camphor, is hygroscopic, flammable, and has higher toxicity and anesthetic properties than other alcohols. Tert-butanol is soluble in most organic solvents, such as alcohols, esters, ketones, aromatic and aliphatic hydrocarbons, and these properties make it a useful solvent and additive, one of the petrochemical products with a wide range of uses. The tertiary butyl alcohol can be added independently or mixed with other alcohol solvents, or can be prepared into methyl tertiary butyl ether for adding. Tert-butanol can also be used for the synthesis of organic chemicals, such as the production of high purity isobutylene, methacrolein and methacrylic acid can be sequentially prepared by oxidation of tertiary butanol, and methyl methacrylate can also be prepared by esterification of sufficiently oxidized tertiary butanol with methanol. In the industrial production of methacrylic acid in Japan, the oxidation process using t-butanol accounts for about 60%. In addition, the tertiary butanol can directly prepare water-soluble phenolic resin, tertiary butyl phenol, tertiary butylamine, tertiary butyl hydrogen and the like through corresponding chemical reactions. The tertiary butanol can be used as a solvent in the production process of synthetic resin, nitrocellulose and the like, can also be used as an antioxidant and a stabilizer, and has wide application in the synthetic plastic industry. Tert-butanol can be used for synthesizing various assistants such as fruit essence, and is widely applied to the production of medicines, pesticides and spices. The tertiary butanol products are divided into two categories: tert-butyl alcohol and anhydrous tert-butyl alcohol with the mass fraction of 85 percent. 85% of tert-butyl alcohol belongs to a micro-profit commodity in China at present, and the sale is not good, mainly because the development of downstream products of tert-butyl alcohol is not enough, so that the demand of China is increased slowly.
Propylene and ethylene are very important basic organic chemical raw materials, have very wide application in the fields of synthetic materials, fine chemical engineering and the like, and can be closely related to the daily life of human beings. In recent years, driven by the increasing demand of polyolefins and alkylaromatic compounds, the demand of propylene and ethylene has been strongly increasing year by year, and thus propylene and ethylene are considered as products with great market potential. If the tert-butyl alcohol with excessive productivity is directly converted into propylene and ethylene, the utilization problem of the tert-butyl alcohol can be solved, a new path is found for the production of the propylene and the ethylene, and the method has important practical significance.
For the catalyst and the reaction for preparing isobutene by dehydrating tert-butyl alcohol, a fixed bed process is adopted in the patent US442327, sulfonic acid resin is used as a catalyst, liquid phase reaction is carried out at the reaction temperature of 80-150 ℃ and the reaction pressure of 0.5MPa, the product enters a refined fraction separation zone, and the mass composition of the mixture of the circulating hydrous tert-butyl alcohol and the fresh hydrous tert-butyl alcohol entering a reactor is 40-90%. In the process, the water content of the recycled tertiary butanol aqueous solution is higher than that of the azeotropic point of the mixture, the recycling amount is large, the space-time yield is low, and the energy consumption is high. Patent CN201310511142.X discloses a reaction catalyst for preparing isobutene by dehydrating tert-butyl alcohol and a preparation method thereof, wherein poly tribromostyrene is melted and granulated according to a conventional melting and granulating method, the particle size is 0.5-1.2mm, and the poly tribromostyrene and sulfur trioxide are subjected to sulfonation reaction in a fixed bed. No catalyst and method for producing propylene and ethylene by converting tert-butyl alcohol are reported.
Disclosure of Invention
The invention provides a catalyst for producing propylene and ethylene by directly converting tert-butyl alcohol and application thereof, aiming at the problems of excessive tert-butyl alcohol production capacity, few downstream product types, low effective utilization rate, complex process for preparing downstream products by tert-butyl alcohol and the like in the prior art. The catalyst can directly convert the tert-butyl alcohol into propylene and ethylene, and has the characteristics of high catalyst activity, high stability, high selectivity of the products propylene and ethylene and the like.
The invention provides a catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene, wherein the catalyst is of a core-shell structure, the core is a beta molecular sieve, and the shell is aluminum oxide.
In the catalyst, the shell is preferably alumina modified by fluorine element, and the content of the fluorine element is 0.01-3%, preferably 0.1-2% by weight of the catalyst. In the catalyst, the fluorine element is preferably derived from ammonium fluoride and/or ammonium fluorosilicate.
Further, in the catalyst, the mass ratio of the core to the shell is 0.1-8: 1. in the catalyst, the relative dosage of the core shell has a large influence on the performance of the catalyst, and in the catalyst, the mass ratio of the core to the shell is preferably 0.5-4: 1, the selectivity of propylene and ethylene of the catalyst is improved. Further, the beta molecular sieve is hydrogen type molecular sieve, SiO2/Al2O3The molar ratio is 10 to 100, preferably 20 to 80.
Further, the preparation method of the catalyst comprises the following steps:
a) dissolving pseudo-boehmite in a mixed solution of 5-10 wt% of dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol is (1-5): 1, controlling the mixing temperature, and violently stirring to form aluminum hydroxide slurry;
b) optionally, uniformly mixing a fluorine-containing solution with the aluminum hydroxide slurry to prepare aluminum oxide mixed slurry modified by fluorine;
c) and b), spraying the mixed slurry prepared in the step a) or the step b) into a beta molecular sieve, drying and roasting to obtain the catalyst.
Further, in the step a), the mixing temperature is 30-80 ℃.
Further, the method for preparing the catalyst preferably comprises step b). In step b), the fluorine element can be derived from ammonium fluoride and/or ammonium fluorosilicate.
Further, the drying conditions described in step c) are as follows: drying for 5-20 hours at 80-120 ℃, wherein the roasting conditions are as follows: roasting at 450-600 ℃ for 4-12 hours.
Further, the catalyst of the present invention can be formed catalyst, and those skilled in the art can form the catalyst according to the need, and the forming method can be tabletting method.
In a second aspect, the present invention provides a method for producing propylene and ethylene by directly converting tert-butyl alcohol, comprising: the tertiary butanol aqueous solution is used as a raw material, and the raw material is in contact reaction with the catalyst to generate a product containing propylene and ethylene.
Further onIn the method for producing propylene and ethylene by directly converting tert-butyl alcohol, the reaction conditions are as follows: the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-2.0 MPa, and the weight space velocity of the tertiary butanol is 1-30 hours-1The mass ratio of water to tertiary butanol is (0.1-1.0): 1. preferably, the mass ratio of the water to the tertiary butanol is (0.2-0.8): 1.
further, the reaction is carried out in a fixed bed or a fluidized bed, preferably in a fixed bed.
The catalyst of the invention takes the beta molecular sieve as a core and the alumina as a shell, and the beta molecular sieve and the alumina are connected in a core-shell mode and interact with each other to adjust the catalytic performance, so that the catalyst can be used in the process for producing propylene and ethylene by directly converting tert-butyl alcohol and has good activity and selectivity of diene (propylene and ethylene).
Furthermore, when the catalyst adopts alumina modified by fluorine-containing element as the shell, especially when the catalyst adopts ammonium fluoride and/or ammonium fluosilicate modified alumina, the overall performance of the catalyst is further improved, and the selectivity of diene is further greatly improved.
The invention realizes the process of directly converting tert-butyl alcohol into propylene and ethylene by developing a novel catalyst, can solve the problem of utilization of tert-butyl alcohol, finds a new path for production of propylene and ethylene, and has important practical significance.
The method for producing propylene and ethylene by directly converting tert-butyl alcohol effectively overcomes the problems of few downstream products of tert-butyl alcohol, low effective utilization rate and shortage of propylene and ethylene markets in the prior art, the once-through yield of directly converting tert-butyl alcohol into propylene and ethylene can reach more than 48%, the stability of the catalyst is more than 80 hours, and a better technical effect is achieved.
Detailed Description
The invention is further illustrated by the following examples.
In the present invention,
the propylene and ethylene single-pass yield is the propylene and ethylene content in the product/(tert-butyl alcohol in the raw material — unreacted tert-butyl alcohol) × 100%.
In the invention, the yield of propylene and ethylene and the conversion rate of tert-butyl alcohol are mass fractions.
[ example 1 ]
Mixing SiO2/Al2O3Exchanging 5 wt% of ammonium nitrate with the Na beta molecular sieve with the molar ratio of 20, drying in an oven at 80 ℃ for 20 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the H beta molecular sieve for later use.
20 g of pseudo-boehmite was dissolved in 100 g of a mixed solution of 5 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol was 2: 1, controlling the mixing temperature to be 60 ℃, vigorously stirring to form aluminum hydroxide slurry, uniformly mixing 0.24 g of ammonium fluoride with the aluminum hydroxide slurry to obtain F-containing aluminum oxide slurry, spraying and soaking 80 g of prepared beta molecular sieve with the slurry, drying in an oven at 80 ℃ for 20 hours, and roasting in a muffle furnace at 600 ℃ for 4 hours to obtain core-shell beta/F-Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 0.2: 1, at the reaction temperature of 400 ℃, the reaction pressure of 0.01MPa and the weight space velocity of the tertiary butanol of 30h-1The reaction conditions of (1) and (3) were as follows, and the conversion of t-butanol was 99.9%, and the yields of propylene and ethylene were 52.6%.
[ example 2 ]
Mixing SiO2/Al2O3Exchanging 5 wt% of ammonium nitrate with the Na beta molecular sieve with the molar ratio of 60, drying the Na beta molecular sieve in a 100 ℃ oven for 8 hours, and roasting the Na beta molecular sieve in a muffle furnace at 500 ℃ for 5 hours to obtain the H beta molecular sieve for later use.
Dissolving 25 g of pseudo-boehmite in 100 g of a mixed solution of 10 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol is 5: 1, controlling the mixing temperature to be 80 ℃, vigorously stirring to form aluminum hydroxide slurry, uniformly mixing 3.1 g of ammonium fluosilicate with the aluminum hydroxide slurry to prepare F-containing aluminum oxide slurry, spraying 75 g of H beta molecular sieve prepared by the slurry, drying in an oven at 120 ℃ for 5 hours, and then drying at 500 ℃ in a horseRoasting for 6 hours in a muffle furnace to obtain the core-shell beta/F-Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 1: 1, at the reaction temperature of 500 ℃, the reaction pressure of 2MPa and the weight space velocity of the tertiary butanol of 5.0h-1The reaction conditions of (1) and (3) were such that the reaction time was 16 hours, and the conversion of t-butanol was 99.9% and the yields of propylene and ethylene were 50.3%.
[ example 3 ]
Mixing SiO2/Al2O3Exchanging 5 wt% of ammonium nitrate with the Na beta molecular sieve with the molar ratio of 80, drying in an oven at 80 ℃ for 20 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the H beta molecular sieve for later use.
67 g of pseudo-boehmite was dissolved in 100 g of a mixed solvent of 5 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol was 4: 1, controlling the mixing temperature to be 80 ℃, vigorously stirring to form aluminum hydroxide slurry, uniformly mixing 1.95 g of ammonium fluoride with the aluminum hydroxide slurry to obtain F-containing aluminum oxide slurry, spraying and soaking 33 g of prepared beta molecular sieve with the slurry, drying in a drying oven at 100 ℃ for 10 hours, and roasting in a muffle furnace at 450 ℃ for 12 hours to obtain core-shell beta/F-Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 0.8: 1, the reaction temperature is 600 ℃, the reaction pressure is 0.1MPa, and the weight space velocity of the tertiary butanol is 10h-1The reaction conditions of (1) were such that the reaction time was 20 hours, and the conversion of t-butanol was 99.8%, and the yields of propylene and ethylene were 51.7%.
[ example 4 ]
Mixing SiO2/Al2O3Exchanging Na beta molecular sieve with 100 mol ratio with 5 wt% ammonium nitrate, drying in an oven at 100 deg.C for 12 hrAnd then roasting the mixture for 5 hours at 550 ℃ in a muffle furnace to obtain the H beta molecular sieve for later use.
50 g of pseudo-boehmite is dissolved in 100 g of a mixed solvent of 10 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol is 1: 1, controlling the mixing temperature to be 30 ℃, vigorously stirring to form aluminum hydroxide slurry, uniformly mixing 0.78 g of ammonium fluosilicate with the aluminum hydroxide slurry to obtain F-containing aluminum oxide slurry, spraying and soaking 50 g of prepared beta molecular sieve with the slurry, drying in a 120 ℃ drying oven for 5 hours, and roasting in a 550 ℃ muffle furnace for 8 hours to obtain core-shell beta/F-Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 0.5: 1, at the reaction temperature of 550 ℃, the reaction pressure of 1.0MPa and the weight space velocity of the tertiary butanol of 1h-1The reaction conditions of (1) and (3) were such that the reaction time was 16 hours, and the conversion of t-butanol was 99.8% and the yields of propylene and ethylene were 50.9%.
[ example 5 ]
Mixing SiO2/Al2O3Exchanging 5 wt% of ammonium nitrate with the Na beta molecular sieve with the molar ratio of 50, drying in an oven at 120 ℃ for 6 hours, and roasting in a muffle furnace at 550 ℃ for 5 hours to obtain the H beta molecular sieve for later use.
33 g of pseudo-boehmite is dissolved in 100 g of a mixed solvent of 5 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol is 2: 1, controlling the mixing temperature to be 50 ℃, vigorously stirring to form aluminum hydroxide slurry, uniformly mixing 0.02 g of ammonium fluoride with the aluminum hydroxide slurry to obtain F-containing aluminum oxide slurry, spraying and soaking 67 g of prepared beta molecular sieve with the slurry, drying in an oven at 80 ℃ for 16 hours, and roasting in a muffle furnace at 450 ℃ for 12 hours to obtain core-shell beta/F-Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting fixed bed reaction process, tert-butyl alcohol aqueous solutionThe raw materials are water and tertiary butanol, wherein the weight ratio of water to tertiary butanol is 0.8: 1, the reaction temperature is 580 ℃, the reaction pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 10h-1The reaction conditions of (1) were such that the reaction time was 16 hours, and the conversion of t-butanol was 99.8%, and the yields of propylene and ethylene were 49.6%.
[ example 6 ]
Mixing SiO2/Al2O3Exchanging 5 wt% of ammonium nitrate with the Na beta molecular sieve with the molar ratio of 80, drying in an oven at 80 ℃ for 20 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the H beta molecular sieve for later use.
91 g of pseudo-boehmite is dissolved in 100 g of a mixed solvent of 5 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol is 4: 1, controlling the mixing temperature to be 80 ℃, vigorously stirring to form aluminum hydroxide slurry, uniformly mixing 1.95 g of ammonium fluoride with the aluminum hydroxide slurry to obtain F-containing aluminum oxide slurry, spraying and soaking 9.1 g of prepared beta molecular sieve in the slurry, drying in a drying oven at 100 ℃ for 10 hours, and roasting in a muffle furnace at 450 ℃ for 12 hours to obtain core-shell type beta/F-Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 0.8: 1, the reaction temperature is 600 ℃, the reaction pressure is 0.1MPa, and the weight space velocity of the tertiary butanol is 10h-1The reaction conditions of (1) were such that the reaction time was 20 hours, and the conversion of t-butanol was 99.5%, and the yields of propylene and ethylene were 32.3%.
[ example 7 ]
Mixing SiO2/Al2O3Exchanging 5 wt% of ammonium nitrate with the Na beta molecular sieve with the molar ratio of 80, drying in an oven at 80 ℃ for 20 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the H beta molecular sieve for later use.
Dissolving 12.5 g of pseudo-boehmite in 100 g of a mixed solvent of 5 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol is 4: 1, controlling the mixing temperature to be 80 ℃, and violently stirringTo form aluminum hydroxide slurry, 1.95 g of ammonium fluoride and the aluminum hydroxide slurry are mixed uniformly to prepare alumina slurry containing F, 87.5 g of beta molecular sieve prepared by spray-soaking the slurry is dried in a drying oven at 100 ℃ for 10 hours, and then is roasted in a muffle furnace at 450 ℃ for 12 hours to obtain core-shell beta/F-Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 0.8: 1, the reaction temperature is 600 ℃, the reaction pressure is 0.1MPa, and the weight space velocity of the tertiary butanol is 10h-1The reaction conditions of (1) were such that the reaction time was 20 hours, and the conversion of t-butanol was 98.3%, and the yields of propylene and ethylene were 37.5%.
[ example 8 ]
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 0.8: 1, the reaction temperature is 600 ℃, the reaction pressure is 0.1MPa, and the weight space velocity of the tertiary butanol is 10h-1The catalyst of example 3 was subjected to a stability test under the reaction conditions shown in Table 1.
Table 1 stability test results of the catalyst obtained in example 3
| Reaction time (h) | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 |
| Conversion of t-butanol (%) | 99.9 | 99.8 | 99.8 | 99.8 | 99.9 | 99.8 | 99.8 | 99.8 | 99.8 |
| Propylene and ethylene yields (%) | 51.8 | 51.7 | 51.5 | 51.5 | 51.3 | 51.2 | 50.9 | 50.5 | 50.2 |
[ example 9 ]
Mixing SiO2/Al2O3Exchanging Na beta molecular sieve with molar ratio of 80 by 5 wt% of ammonium nitrate, drying in an oven at 80 ℃ for 20 hours, and baking in a muffle furnace at 500 DEG CAnd (5) burning for 5 hours to obtain the H beta molecular sieve for later use.
67 g of pseudo-boehmite was dissolved in 100 g of a mixed solvent of 5 wt% dilute nitric acid and ethanol, wherein the volume ratio of the dilute nitric acid to the ethanol was 4: 1, controlling the mixing temperature to be 80 ℃, vigorously stirring to form aluminum hydroxide slurry, spraying and soaking 33 g of prepared beta molecular sieve by using the slurry, drying in a drying oven at 100 ℃ for 10 hours, and then roasting in a muffle furnace at 450 ℃ for 12 hours to obtain core-shell beta/Al2O3And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene.
Adopting a fixed bed reaction process, taking tert-butyl alcohol aqueous solution as a raw material, wherein the weight ratio of water to tert-butyl alcohol is 0.8: 1, the reaction temperature is 600 ℃, the reaction pressure is 0.1MPa, and the weight space velocity of the tertiary butanol is 10h-1The reaction conditions of (1) were such that the reaction time was 20 hours, and the conversion of t-butanol was 99.5%, and the yields of propylene and ethylene were 44.3%.
Claims (10)
1. A catalyst for directly converting tert-butyl alcohol to produce propylene and ethylene is of a core-shell structure, wherein the core is a beta molecular sieve, and the shell is aluminum oxide.
2. The catalyst of claim 1, wherein: the shell is alumina modified by fluorine element, and the content of the fluorine element is 0.01-3 percent, preferably 0.1-2 percent, based on the weight of the catalyst.
3. The catalyst according to claim 1 or 2, characterized in that: in the catalyst, the mass ratio of the core to the shell is 0.1-8: 1.
4. the catalyst according to claim 1 or 2, characterized in that: in the catalyst, the mass ratio of the core to the shell is 0.5-4: 1.
5. the catalyst of claim 3, wherein: the fluorine element is derived from ammonium fluoride and/or ammonium fluorosilicate.
6. The catalyst according to claim 1 or 2, characterized in that: the beta molecular sieve is hydrogen type molecular sieve, SiO2/Al2O3The molar ratio is 10 to 100.
7. The catalyst according to claim 1 or 2, characterized in that: the beta molecular sieve is hydrogen type molecular sieve, SiO2/Al2O3The molar ratio is 20-80.
8. A method for producing propylene and ethylene by directly converting tert-butyl alcohol is characterized in that: the method comprises the following steps: using tert-butanol aqueous solution as raw material, making the raw material contact with catalyst described in any one of claims 1-7 to make reaction so as to obtain the product containing propylene and ethylene.
9. The method of claim 8, wherein: the reaction conditions are as follows: the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-2.0 MPa, and the weight space velocity of the tertiary butanol is 1-30 hours-1The mass ratio of water to tertiary butanol is (0.1-1.0): 1.
10. the method of claim 8, wherein: the reaction is carried out in a fixed bed or a fluidized bed.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103974941A (en) * | 2011-10-17 | 2014-08-06 | 国际壳牌研究有限公司 | Process for preparing an epoxide from an oxygenate |
| CN104056652A (en) * | 2013-03-22 | 2014-09-24 | 中国石油化工股份有限公司 | Core-shell ZSM-5 molecular sieve microsphere catalyst |
| CN107999123A (en) * | 2016-10-27 | 2018-05-08 | 中国科学院大连化学物理研究所 | Methanol or/and dimethyl ether produce higher olefins catalyst and preparation method and application |
| CN109070068A (en) * | 2016-03-09 | 2018-12-21 | 巴斯夫公司 | core/shell type hydrocarbon trap catalyst and its manufacturing method |
| WO2019062815A1 (en) * | 2017-09-30 | 2019-04-04 | 株式会社模范 | Catalyst for directly preparing p-xylene by using syngas, preparation thereof, and applications thereof |
| WO2020000165A1 (en) * | 2018-06-26 | 2020-01-02 | Rhodia Operations | Process for the amination of alcohols |
| CN111116282A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method for preparing olefin from tertiary butanol |
-
2020
- 2020-06-05 CN CN202010506739.5A patent/CN113751059B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103974941A (en) * | 2011-10-17 | 2014-08-06 | 国际壳牌研究有限公司 | Process for preparing an epoxide from an oxygenate |
| CN104056652A (en) * | 2013-03-22 | 2014-09-24 | 中国石油化工股份有限公司 | Core-shell ZSM-5 molecular sieve microsphere catalyst |
| CN109070068A (en) * | 2016-03-09 | 2018-12-21 | 巴斯夫公司 | core/shell type hydrocarbon trap catalyst and its manufacturing method |
| US20190126247A1 (en) * | 2016-03-09 | 2019-05-02 | Basf Corporation | Core/shell hydrocarbon trap catalyst and method of manufacture |
| CN107999123A (en) * | 2016-10-27 | 2018-05-08 | 中国科学院大连化学物理研究所 | Methanol or/and dimethyl ether produce higher olefins catalyst and preparation method and application |
| WO2019062815A1 (en) * | 2017-09-30 | 2019-04-04 | 株式会社模范 | Catalyst for directly preparing p-xylene by using syngas, preparation thereof, and applications thereof |
| WO2020000165A1 (en) * | 2018-06-26 | 2020-01-02 | Rhodia Operations | Process for the amination of alcohols |
| CN111116282A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method for preparing olefin from tertiary butanol |
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