CN112679296B - Method for producing propylene by directly converting tert-butyl alcohol - Google Patents
Method for producing propylene by directly converting tert-butyl alcohol Download PDFInfo
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Abstract
The invention discloses a method for producing propylene by directly converting tert-butyl alcohol. The method comprises the following steps: the method takes tert-butanol aqueous solution as raw material, the raw material contacts with catalyst to react to generate a product containing propylene, wherein the used catalyst is of a core-shell structure, the core is ZSM-5 molecular sieve, the shell is alumina containing rare earth elements, and the mass ratio of the core to the shell is 5-1:1. The method directly converts the tert-butyl alcohol into the propylene, and has the characteristics of high catalyst stability, high selectivity of the product propylene and simple preparation process.
Description
Technical Field
The invention relates to a method for producing propylene 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-butyl alcohol 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 reaction of tertiary butyl alcohol, and methyl methacrylate can also be prepared by esterification reaction of tertiary butyl alcohol after sufficient oxidation and 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 strong enough, so that the demand is increased slowly. With the upgrading of oil products and the popularization and application of ethanol gasoline, the use amount of tert-butyl alcohol as a gasoline additive and a raw material for preparing a gasoline additive, namely methyl tert-butyl ether, is greatly reduced, and a new chemical utilization way for the tert-butyl alcohol is urgently needed to be found, so that the development of the application market of the tert-butyl alcohol is stimulated.
Propylene is an important basic raw material for petrochemical industry, and driven by the rapid growth of the demand of polypropylene and its derivatives, the demand of propylene will still grow at a rapid rate in the next few years, and thus propylene is considered as a product having great market potential. If the tert-butyl alcohol with excessive productivity is directly converted into propylene, the utilization problem of the tert-butyl alcohol can be solved, a new path is found for the production of the propylene, and the method has important practical significance.
The catalyst and the reaction for preparing isobutene by dehydrating tertiary butanol have been reported, US4423271 adopts a fixed bed process, sulfonic acid resin is used as the catalyst, liquid phase reaction is carried out at the reaction temperature of 80-150 ℃ and the reaction pressure of 0.5-2.5 MPa, a product enters a rectification separation zone, and the mass composition of the mixture of the circulating hydrous tertiary butanol and fresh hydrous tertiary butanol 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, and the process has the advantages of large recycling amount, low space-time yield and high energy consumption. 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 0.5-1.2 mm, and the poly tribromostyrene and sulfur trioxide are subjected to sulfonation reaction in a fixed bed. However, no reports are found about the catalyst and method for producing propylene by directly converting tert-butyl alcohol.
Disclosure of Invention
The invention aims to solve the technical problems that the existing tertiary butanol has excessive production capacity, few downstream product types, low effective utilization rate and complex process for preparing downstream products by the tertiary butanol. The invention provides a method for producing propylene by directly converting tert-butyl alcohol. The method directly converts the tert-butyl alcohol into the propylene, and has the characteristics of high catalyst stability, high selectivity of the product propylene and simple preparation process.
The invention provides a method for producing propylene by directly converting tert-butyl alcohol, which comprises the following steps: the method takes tert-butanol aqueous solution as raw material, the raw material contacts with catalyst to react to generate a product containing propylene, wherein the used catalyst is of a core-shell structure, the core is ZSM-5 molecular sieve, the shell is alumina containing rare earth elements, and the mass ratio of the core to the shell is 5-1:1.
In the method for producing propylene by directly converting tertiary butanol, the catalyst takes the weight of a shell layer of the catalyst as a reference, and the content of the rare earth element is 0.01-5%, preferably 0.1-4%. The rare earth element is selected from one or more of La, ce, pr and Nd, and preferably at least one of La and Ce.
In the method for producing propylene by directly converting tert-butyl alcohol, the ZSM-5 molecular sieve is a hydrogen type molecular sieve and SiO of the hydrogen type molecular sieve 2 /Al 2 O 3 The molar ratio is 100 to 1000, preferably 200 to 800.
In the process for the direct conversion of tert-butanol to propylene according to the invention, the reaction is carried out in a fixed bed or in a fluidized bed, preferably in a fixed bed.
In the method for producing propylene by directly converting tert-butyl alcohol, the reaction conditions are as follows: the reaction temperature is 400-650 ℃, the reaction pressure is 0.01-5 MPa, and the weight space velocity of the tertiary butanol is 1-10 hours -1 The mass ratio of water to tertiary butanol is (0.1-1.2): 1. Preferably, the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-3 MPa, and the reaction is tertiaryThe weight space velocity of the butanol is 2 to 8 hours -1 The mass ratio of water to tertiary butanol is (0.2-1.2): 1.
In the method for producing propylene by directly converting tert-butyl alcohol, the catalyst can be prepared by the following method:
a) Dissolving pseudo-boehmite in a mixed solvent of water and ethanol, controlling the reaction temperature, and violently stirring, wherein the volume ratio of the water to the ethanol is 1-5:1, and the weight percentage content of the pseudo-boehmite is 20% -40%, so as to form aluminum hydroxide slurry;
b) Uniformly mixing soluble rare earth salt with the aluminum hydroxide slurry to prepare aluminum oxide mixed slurry containing rare earth elements;
c) Spraying the prepared mixed slurry into HZSM-5 molecular sieve microspheres, drying and roasting to prepare ZSM-5/Al 2 O 3 A core-shell catalyst.
In the step a), the reaction temperature is controlled to be 40-80 ℃.
The drying and roasting in the step c) can adopt conventional operation conditions, the drying can adopt drying at 80-120 ℃ for 8-20 hours, and the roasting can adopt roasting at 450-600 ℃ for 3-10 hours.
The method of the invention has the following advantages:
1. the method for producing propylene by directly converting tert-butyl alcohol effectively overcomes the problems of few types of tert-butyl alcohol downstream products, low effective utilization rate and propylene market shortage in the prior art.
2. The method can directly convert the tert-butyl alcohol into the propylene, has simple and easy technical process, and breaks through the problem that the tert-butyl alcohol cannot be directly converted into the propylene in the prior art.
3. By adopting the method, the once-through yield of the propylene can reach more than 40 percent, even can reach more than 43 percent, and a better technical effect is achieved.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
In the present invention, the first and second liquid crystal display panels,
the propylene single pass yield = the propylene content in the product/(tert-butyl alcohol in the raw material — unreacted tert-butyl alcohol) × 100%.
The catalyst stability means that the conversion of t-butanol is maintained at 99% or more and the propylene yield is 40% or more, preferably 43% or more, with the extension of the reaction time.
In the invention, the yield of propylene and the conversion rate of tert-butyl alcohol are mass fractions.
[ example 1 ]
Mixing SiO 2 /Al 2 O 3 Exchanging NaZSM-5 molecular sieve microspheres with the molar ratio of 200 by 5wt% of ammonium nitrate, drying in an oven at 80 ℃ for 20 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the HZSM-5 molecular sieve for later use.
Dissolving 30 g of pseudo-boehmite in 100 g of mixed solvent of water and ethanol, wherein the volume ratio of the water to the ethanol is 1:1, controlling the reaction temperature to be 60 ℃, violently stirring to form aluminum hydroxide slurry, uniformly mixing 0.1 g of lanthanum nitrate and the aluminum hydroxide slurry to prepare La-containing aluminum oxide slurry, spraying and soaking 30 g of HZSM-5 molecular sieve microspheres prepared by the slurry, drying in a 100 ℃ oven for 15 hours, and then roasting in a 450 ℃ muffle furnace for 10 hours to obtain ZSM-5/Al 2 O 3 And (3) tabletting, grinding and screening the core-shell type material to obtain the catalyst for producing propylene by directly converting the required tertiary butanol.
A fixed bed reaction process is adopted, tertiary butanol aqueous solution is used as a raw material, wherein the weight ratio of water to tertiary butanol is 0.2 -1 The reaction results obtained in 24 hours of the reaction under the reaction conditions of (1) were as follows, the conversion of t-butanol was 99.9%, and the yield of propylene was 43.6%.
[ example 2 ]
Mixing SiO 2 /Al 2 O 3 Exchanging NaZSM-5 molecular sieve microspheres with the molar ratio of 500 by 5wt% of ammonium nitrate, drying in an oven at 120 ℃ for 5 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the HZSM-5 molecular sieve for later use.
30 g of pseudo-boehmite is dissolved in 100 g of mixed solvent of water and ethanol, wherein the volume ratio of the water to the ethanol is 2:1,controlling the reaction temperature to be 60 ℃, violently stirring to form aluminum hydroxide slurry, uniformly mixing 3.6 g of cerium nitrate with the aluminum hydroxide slurry to prepare Ce-containing aluminum oxide slurry, spraying and soaking 60 g of HZSM-5 molecular sieve microspheres prepared by the slurry, drying in an oven at 80 ℃ for 20 hours, and roasting in a muffle furnace at 600 ℃ for 3 hours to obtain core-shell type ZSM-5/Al 2 O 3 And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for producing propylene by directly converting the required tert-butyl alcohol.
A fixed bed reaction process is adopted, tertiary butanol aqueous solution is used as a raw material, wherein the weight ratio of water to tertiary butanol is 0.5 -1 The reaction conditions of (1) were such that the reaction results obtained after 24 hours of reaction were as follows, the conversion of t-butanol was 99.9%, and the yield of propylene was 43.9%.
[ example 3 ]
Mixing SiO 2 /Al 2 O 3 Exchanging NaZSM-5 molecular sieve microspheres with the molar ratio of 800 by 5wt% of ammonium nitrate, drying in a drying oven at 100 ℃ for 8 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the HZSM-5 molecular sieve for later use.
Dissolving 30 g of pseudoboehmite in 100 g of mixed solvent of water and ethanol, wherein the volume ratio of the water to the ethanol is 5:1, controlling the reaction temperature to be 40 ℃, violently stirring to form aluminum hydroxide slurry, uniformly mixing 2 g of praseodymium nitrate and the aluminum hydroxide slurry to prepare Pr-containing alumina slurry, spray-soaking 150 g of HZSM-5 molecular sieve microspheres prepared by the slurry, drying in a 120 ℃ oven for 8 hours, and roasting in a 500 ℃ muffle furnace for 8 hours to obtain the core-shell type ZSM-5/Al 2 O 3 And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for producing propylene by directly converting the required tert-butyl alcohol.
The method adopts a fixed bed reaction process, wherein a tert-butyl alcohol aqueous solution is used as a raw material, the weight ratio of water to tert-butyl alcohol is 1.2 -1 Under the reaction conditions of (1), the reaction results obtained after 24 hours of the reaction were as follows, the conversion of t-butanol was 99.9%, and the yield of propylene was42.5％。
[ example 4 ]
Mixing SiO 2 /Al 2 O 3 Exchanging NaZSM-5 molecular sieve microspheres with the molar ratio of 300 by 5wt% of ammonium nitrate, drying in a drying oven at 100 ℃ for 8 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the HZSM-5 molecular sieve for later use.
Dissolving 30 g of pseudo-boehmite in 100 g of mixed solvent of water and ethanol, wherein the volume ratio of the water to the ethanol is 2:1, controlling the reaction temperature to be 40 ℃, violently stirring to form aluminum hydroxide slurry, uniformly mixing 1.5 g of neodymium nitrate and the aluminum hydroxide slurry to prepare the Nd-containing aluminum oxide slurry, spraying and soaking 90 g of HZSM-5 molecular sieve microspheres prepared by the slurry, drying in an oven at 80 ℃ for 20 hours, and then roasting in a muffle furnace at 600 ℃ for 5 hours to obtain the core-shell type ZSM-5/Al 2 O 3 And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for producing propylene by directly converting the required tert-butyl alcohol.
A fixed bed reaction process is adopted, tertiary butanol aqueous solution is used as a raw material, wherein the weight ratio of water to tertiary butanol is 0.5 -1 The reaction results obtained in 24 hours of the reaction under the reaction conditions of (1) were as follows, the conversion of t-butanol was 99.9%, and the yield of propylene was 41.8%.
[ example 5 ]
Mixing SiO 2 /Al 2 O 3 Exchanging NaZSM-5 molecular sieve microspheres with the molar ratio of 600 by 5wt% of ammonium nitrate, drying in a drying oven at 100 ℃ for 8 hours, and roasting in a muffle furnace at 500 ℃ for 5 hours to obtain the HZSM-5 molecular sieve for later use.
Dissolving 30 g of pseudoboehmite in 100 g of mixed solvent of water and ethanol, wherein the volume ratio of the water to the ethanol is 3:1, controlling the reaction temperature to be 80 ℃, violently stirring to form aluminum hydroxide slurry, uniformly mixing 0.5 g of lanthanum nitrate and 0.5 g of cerium nitrate with the aluminum hydroxide slurry to prepare alumina slurry containing La and Ce, spraying and soaking 120 g of the prepared HZSM-5 molecular sieve microspheres by the slurry, drying in a 120 ℃ oven for 8 hours, and roasting in a 500 ℃ muffle furnace for 6 hours to obtain core-shell type microspheresZSM-5/Al 2 O 3 And (3) tabletting, grinding and screening the core-shell material to obtain the catalyst for producing propylene by directly converting the required tert-butyl alcohol.
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, the reaction temperature is 500 ℃, the reaction pressure is 2MPa, and the weight space velocity of tert-butyl alcohol is 6.0h -1 The reaction results obtained in 24 hours of the reaction under the reaction conditions of (1) were as follows, the conversion of t-butanol was 99.9%, and the yield of propylene was 44.2%.
Claims (8)
1. A method for producing propylene by directly converting tertiary butanol, comprising the following steps: taking a tert-butyl alcohol aqueous solution as a raw material, and contacting the raw material with a catalyst to react to generate a propylene-containing product, wherein the used catalyst is of a core-shell structure, the core is a ZSM-5 molecular sieve, the shell is alumina containing rare earth elements, and the mass ratio of the core to the shell is (5) - (1);
the rare earth element is selected from one or more of La, ce, pr and Nd;
the reaction temperature is 400-650 ℃, the reaction pressure is 0.01-5 MPa, and the weight space velocity of the tertiary butanol is 1-10 hours -1 The mass ratio of water to tertiary butanol is (0.1-1.2): 1.
2. The method of claim 1, wherein: the catalyst takes the weight of a shell layer of the catalyst as a reference, and the content of the rare earth element is 0.01-5%.
3. The method of claim 1, wherein: the catalyst takes the weight of a shell layer of the catalyst as a reference, and the content of the rare earth element is 0.1-4%.
4. A method according to claim 1, 2 or 3, characterized in that: the rare earth element is selected from at least one of La and Ce.
5. The method of claim 1, wherein: the ZSM-5 molecular sieve is a hydrogen type molecular sieve and S thereofiO 2 /Al 2 O 3 The molar ratio is 100 to 1000.
6. The method of claim 1, wherein: the ZSM-5 molecular sieve is a hydrogen type molecular sieve and SiO thereof 2 /Al 2 O 3 The molar ratio is 200-800.
7. The method of claim 1, wherein: the reaction is carried out in a fixed bed or a fluidized bed.
8. The method of claim 1, wherein: the reaction conditions were as follows: the reaction temperature is 400-600 ℃, the reaction pressure is 0.01-3 MPa, and the weight space velocity of the tertiary butanol is 2-8 hours -1 The mass ratio of water to tertiary butanol is (0.2-1.2): 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4503164A (en) * | 1982-12-27 | 1985-03-05 | Idemitsu Kosan Company Limited | Zeolite-type catalyst and process for preparing same |
| 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 |
| WO2019083846A1 (en) * | 2017-10-26 | 2019-05-02 | Lyondell Chemical Technology, L.P. | Methods of producing propylene and ethylene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4503164A (en) * | 1982-12-27 | 1985-03-05 | Idemitsu Kosan Company Limited | Zeolite-type catalyst and process for preparing same |
| 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 |
| WO2019083846A1 (en) * | 2017-10-26 | 2019-05-02 | Lyondell Chemical Technology, L.P. | Methods of producing propylene and ethylene |
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