CN112209790B - Method for producing propylene by direct conversion of tertiary butanol - Google Patents
Method for producing propylene by direct conversion of tertiary butanol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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 invention discloses a method for producing propylene by directly converting tertiary butanol. The method comprises the following steps: the method comprises the steps of taking a tertiary butanol aqueous solution as a raw material, and enabling the raw material to contact with a catalyst for reaction to generate a propylene-containing product, wherein the catalyst comprises the following components in parts by weight: a) 30% -80% of molecular sieve; b) 20% -70% of binder; c) 0-5% rare earth element. The method directly converts the tertiary butanol into propylene, and has the characteristics of high catalyst stability, high propylene selectivity and simple preparation process.
Description
Technical Field
The invention relates to a method for producing propylene by directly converting tertiary butanol.
Background
Tert-butanol (TBA) is a colorless crystal, colorless volatile liquid in the presence of small amounts of water, has a camphor-like odor, is hygroscopic, flammable, and has higher toxicity and anesthetic properties than other alcohols. Tertiary butanol is soluble in most organic solvents such as alcohols, esters, ketones, aromatics and aliphatic hydrocarbons, which make tertiary butanol a useful solvent and additive, one of the petrochemical products with wide use. The most widely used gasoline additive is to increase the octane number of gasoline, and tert-butyl alcohol can be added alone or mixed with other alcohol solvents, or can be added as methyl tert-butyl ether. Tertiary butanol can also be used in the synthesis of organic chemicals, such as the production of high purity isobutylene, methacrolein and methacrylic acid by the sequential oxidation of tertiary butanol, and methyl methacrylate can also be produced by the esterification of fully oxidized tertiary butanol with methanol. In the industrial production of Japanese methacrylic acid, the proportion of the oxidation process using t-butanol is about 60%. In addition, the tertiary butyl alcohol can directly prepare water-soluble phenolic resin, tertiary butyl phenol, tertiary butyl amine, tertiary butyl hydrogen and other substances through corresponding chemical reaction. 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. The tertiary butanol can be used for synthesizing various auxiliary agents such as fruit extract and the like, and has a large application in the production of medicines, pesticides and spices. The t-butanol product is divided into two types: and the mass fraction of tertiary butanol and anhydrous tertiary butanol is 85 percent. At present, 85% of tertiary butanol belongs to micro-profit commodity in China, and the sales are poor, and the main reason is that the development of downstream products of tertiary butanol is insufficient, so that the demand quantity is slowly increased. Along with the upgrading of oil products and the popularization and application of ethanol gasoline, the use amount of the tert-butyl alcohol serving as a gasoline additive and a raw material for preparing the gasoline additive methyl tert-butyl ether is greatly reduced, and a new chemical utilization way is required to be searched for the tert-butyl alcohol, so that the development of the tert-butyl alcohol application market is stimulated.
Propylene is an important base stock for the petrochemical industry, driven by the rapidly growing demand for polypropylene and its derivatives, which will still grow at a faster rate in the next few years, and is therefore considered a product with great market potential. If the tert-butyl alcohol with excessive productivity is directly converted into propylene, not only can the problem of utilizing the tert-butyl alcohol be solved, but also a new path is found for the production of propylene, and the method has important practical significance.
For the catalyst and reaction of tert-butyl alcohol dehydration to prepare isobutene, a fixed bed process is widely reported in US4423271, 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 0.5-2.5 MPa, the product enters a rectification separation area, and the mass composition of the recycled water-containing tert-butyl alcohol and fresh water-containing tert-butyl alcohol which are mixed into a reactor is 40-90%. The water content of the circulating tertiary butanol aqueous solution is higher than the water content of the azeotropic point of the mixture, the circulating amount is large, the space-time yield is low, and the energy consumption is high. CN201310511142.X discloses a catalyst for preparing isobutene by dehydrating tertiary butanol and a preparation method thereof, wherein the catalyst is prepared by melting and granulating poly-tribromostyrene according to a conventional melting granulation method, and the particle size is 0.5-1.2 mm, and the catalyst is subjected to sulfonation reaction with sulfur trioxide in a fixed bed. The catalyst and the method for producing propylene by directly converting tertiary butanol are not reported.
Disclosure of Invention
The invention aims to solve the technical problems of excessive capacity, few types of downstream products, low effective utilization rate and complex process for preparing the downstream products by using the tertiary butanol. The invention provides a method for producing propylene by directly converting tertiary butanol. The method directly converts the tertiary butanol into propylene, and has the characteristics of high catalyst stability, high propylene selectivity and simple preparation process.
The invention provides a method for producing propylene by directly converting tertiary butanol, which comprises the following steps: taking tertiary butanol aqueous solution as a raw material, and reacting the raw material with a catalyst to generate a propylene-containing product, wherein the catalyst comprises the following components in parts by weight: a) 30% -80% of molecular sieve; b) 20% -70% of binder; c) 0-5% rare earth element.
In the process for producing propylene by direct conversion of t-butanol according to the present invention, the reaction is carried out in a fixed bed or a fluidized bed, preferably in a fixed bed.
In the method for producing propylene by directly converting tertiary butanol, the reaction conditions are as follows: the reaction temperature is 400-650 ℃, the reaction pressure is 0.01-5 MPa, and the weight airspeed 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 450-600 ℃, the reaction pressure is 0.01-3 MPa, and the weight space velocity of tertiary butanol is 2-8 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 tertiary butanol, the content of the catalyst and the molecular sieve is preferably 40-75% by weight. The molecular sieve is at least one selected from ZSM-5, ZSM-11 and ZSM-48, preferably ZSM-11 molecular sieve. Silicon aluminum (SiO) of the molecular sieve 2 /Al 2 O 3 ) The molar ratio is 100-600, preferably 200-600, furtherThe steps are preferably 300 to 500.
In the method for producing propylene by directly converting tert-butanol, the content of rare earth elements in the catalyst is preferably 0.01-5% by weight, and more preferably 0.1-3% by weight. The rare earth element is selected from one or more of La, ce, pr and Nd, preferably La, ce and/or a combination thereof. The content of the binder of the catalyst is preferably 20-59% by weight. The binder is selected from silicon oxide and/or aluminum oxide, or is obtained by roasting at least one component selected from silica sol, aluminum sol and aluminum phosphate.
In the method for producing propylene by directly converting tertiary butanol, the catalyst can be prepared by adopting the following method: adding a binder into the sodium ZSM-11 molecular sieve raw powder, uniformly mixing, forming, drying and roasting (preferably drying at 60-120 ℃ for 1-12h and roasting at 500-600 ℃ for 1-8 h), removing a template agent, and carrying out ammonium exchange, drying and roasting to obtain the catalyst. When the catalyst selectively contains rare earth elements, the rare earth elements can be loaded by adopting an impregnation method, and the catalyst is obtained by drying and roasting after the rare earth elements are loaded. The ammonium exchange can be performed by adopting a conventional ammonium salt solution, and can be performed by adopting one-time ammonium exchange or multiple times of ammonium exchange. Drying and baking after ammonium exchange and drying and baking after rare earth element loading can be performed by adopting conventional drying and baking conditions, such as drying at 60-120 ℃ for 1-12h and baking at 500-600 ℃ for 1-8 h.
The method of the invention has the following advantages:
1. the method for producing propylene by directly converting tertiary butanol effectively solves the problems of few types of products at the downstream of tertiary butanol, low effective utilization rate and shortage of propylene market in the prior art.
2. The method can directly convert the tertiary butanol into the propylene, has simple and feasible process, and breaks through the difficult problem that the tertiary butanol cannot be directly converted into the propylene in the prior art.
3. By adopting the method, the single pass yield of propylene can reach more than 25 percent, even more than 30 percent, and the stability of the catalyst is more than 500 hours, thus obtaining better technical effect.
Detailed Description
The technical scheme of the invention is further elaborated by the following examples.
In the present invention,
propylene single pass yield = propylene content in product/(t-butanol in feed-unreacted t-butanol) x 100%.
The catalyst stability means that the t-butanol conversion is maintained at 99% or more, and the propylene yield is 25% or more, preferably 30% or more, with the increase of the reaction time.
In the invention, the propylene yield and the tertiary butanol conversion rate are both mass fractions.
[ example 1 ]
40 g of silicon-aluminum molar ratio (SiO) 2 /Al 2 O 3 ) 200 NaZSM-11 molecular sieve, 25 g silica sol (SiO 2 40% of weight percentage) by weight, adding water, kneading, extruding with a die with the diameter of 2.0 mm, molding, airing, placing in an oven with the temperature of 80 ℃ for 8 hours, roasting in a muffle furnace with the temperature of 600 ℃ for 6 hours, removing the template agent, exchanging three times in an ammonium nitrate solution with the temperature of 90 ℃ and 5wt%, and roasting in the muffle furnace with the temperature of 550 ℃ for 4 hours after drying to obtain the HZSM-11 molecular sieve catalyst. As a catalyst for producing propylene by directly converting tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 25.6%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 2 ]
40 g of silicon-aluminum molar ratio (SiO) 2 /Al 2 O 3 ) 200 NaZSM-11 molecular sieve, 25 g silica sol (SiO 2 40% by weight), kneading with water, extruding with 2.0 mm diameter mold, shaping, air drying, baking at 80deg.C for 8 hr, baking at 600deg.C for 6 hr, removing template agent, and heating at 90deg.CExchanging in 5wt% ammonium nitrate solution for three times, baking in a muffle furnace at 550 ℃ for 4 hours, and obtaining the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in 1 weight percent lanthanum nitrate solution for 12 hours, dried in an oven at 80 ℃ and baked for 4 hours in a muffle furnace at 550 ℃ to obtain 1 percent La-ZSM-11 molecular sieve catalyst which is used as a catalyst for producing propylene by direct conversion of tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 28.7%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 3 ]
30 g of silicon-aluminum molar ratio (SiO) 2 /Al 2 O 3 ) 500 NaZSM-11 molecular sieve, 38 g silica sol (SiO 2 40% of weight percentage) and 15 g of alumina, adding water, kneading, extruding with a die with the diameter of 2.0 mm, molding, airing, placing in a 100 ℃ oven for 5 hours, roasting in a 600 ℃ muffle furnace for 4 hours, removing the template agent, exchanging three times in a 85 ℃ 10wt% ammonium chloride solution, and roasting in a 500 ℃ muffle furnace for 8 hours after drying to obtain the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in cerium nitrate solution with the weight percentage of Ce of 0.1% for 36 hours, dried in a 60 ℃ oven, and roasted in a 600 ℃ muffle furnace for 8 hours to obtain the catalyst of 0.1% Ce-ZSM-11 molecular sieve, which is used as the catalyst for producing propylene by direct conversion of tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 32.5%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 4 ]
10 g of silicon-aluminum molar ratio (SiO) 2 /Al 2 O 3 ) 600 NaZSM-11 molecular sieve, 32 g silica sol (SiO 2 40% of weight percentage) and 10 g of aluminum phosphate, adding water, kneading, extruding with a die with the diameter of 1.5 mm, molding, airing, placing in a baking oven with the temperature of 120 ℃ for 8 hours, roasting in a muffle furnace with the temperature of 500 ℃ for 8 hours, removing the template agent, exchanging three times in an ammonium nitrate solution with the weight percentage of 10% with the temperature of 80 ℃, and roasting in the muffle furnace with the temperature of 600 ℃ for 4 hours after baking to obtain the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in praseodymium nitrate solution with Pr weight percent of 0.5% for 48 hours, dried in a 100 ℃ oven, and then baked in a 450 ℃ muffle furnace for 4 hours to obtain the 0.5% Pr-ZSM-11 molecular sieve catalyst which is used as the catalyst for producing propylene by direct conversion of tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 28.9%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 5 ]
Weigh 20 grams of silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) 300 NaZSM-11 molecular sieve, 25 g silica sol (SiO 2 40% of weight percentage) by weight, adding water, kneading, extruding with a die with the diameter of 2.0 mm, molding, airing, placing in a 90 ℃ oven for 10 hours, roasting in a 550 ℃ muffle furnace for 8 hours, removing a template agent, exchanging three times in a 80 ℃ 5wt% ammonium nitrate solution, and roasting in the 550 ℃ muffle furnace for 8 hours after drying to obtain the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in neodymium nitrate solution with the weight percentage of Nd being 3% for 12 hours in an equal volume, dried in an oven with the temperature of 60 ℃ after being dried, and then baked in a muffle furnace with the temperature of 550 ℃ for 4 hours to obtain the 3% Nd-ZSM-11 molecular sieve catalyst which is used as the catalyst for producing propylene by directly converting tertiary butanol.
Adopts a fixed bed reaction process, and adopts tertiary butanol aqueous solution as the original materialThe weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 30.6%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 6 ]
30 g of silicon-aluminum molar ratio (SiO) 2 /Al 2 O 3 ) 400 NaZSM-11 molecular sieve, 28 g silica sol (SiO 2 40% of weight percentage) and 19 g of alumina, adding water, kneading, extruding with a die with the diameter of 2.0 mm, molding, airing, placing in a 100 ℃ oven for 10 hours, roasting in a 550 ℃ muffle furnace for 6 hours, removing the template agent, exchanging three times in a 85 ℃ 10wt% ammonium chloride solution, and roasting in a 500 ℃ muffle furnace for 8 hours after drying to obtain the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in lanthanum nitrate solution with the La weight percentage content of 0.5% for 24 hours in an equal volume, dried in a baking oven at 60 ℃ and baked in a muffle furnace at 600 ℃ for 8 hours to obtain the 0.5% La-ZSM-11 molecular sieve catalyst which is used as the catalyst for producing propylene by direct conversion of tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 30.8%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 7 ]
Weigh 20 grams of silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) 500 NaZSM-11 molecular sieve, 20 g silica sol (SiO 2 40% by weight) and 14.8 g of aluminum phosphate, adding water, kneading, extruding with a die with the diameter of 1.5 mm, molding, airing, placing in a baking oven at 120 ℃ for 8 hours, roasting in a muffle furnace at 550 ℃ for 8 hours, removing template agent, exchanging in 10% ammonium nitrate solution at 80 ℃ for three times, baking in a muffle furnace at 600 ℃ for 4 hours, and obtaining HZSM-11 fractionAnd (3) sub-sieving the catalyst. 10 g of the catalyst is immersed in neodymium nitrate solution with the weight percentage of Nd being 1.5% for 48 hours in an equal volume, dried in a drying oven with the temperature of 100 ℃, and then baked in a muffle furnace with the temperature of 450 ℃ for 4 hours to obtain a 1.5% Nd-ZSM-11 molecular sieve catalyst which is used as a catalyst for producing propylene by direct conversion of tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 33.5%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 8 ]
40 g of silicon-aluminum molar ratio (SiO) 2 /Al 2 O 3 ) 100 NaZSM-11 molecular sieve, 30 g silica sol (SiO 2 40% of weight percentage) by weight, adding water, kneading, extruding with a die with the diameter of 2.0 mm, molding, airing, placing in a 90 ℃ oven for 10 hours, roasting in a 550 ℃ muffle furnace for 8 hours, removing a template agent, exchanging three times in a 80 ℃ 5wt% ammonium nitrate solution, and roasting in the 550 ℃ muffle furnace for 8 hours after drying to obtain the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in praseodymium nitrate solution with Pr weight percentage content of 0.2% for 12 hours, dried in a 60 ℃ oven, and then baked in a 550 ℃ muffle furnace for 4 hours to obtain the 0.2% Pr-ZSM-11 molecular sieve catalyst which is used as the catalyst for producing propylene by direct conversion of tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 26.5%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 9 ]
Weigh 20 grams of silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) Is 4 (4)00 NaZSM-11 molecular sieve, 25 g silica sol (SiO 2 40% of weight percentage) by weight, adding water, kneading, extruding with a die with the diameter of 2.0 mm, molding, airing, placing in a 90 ℃ oven for 10 hours, roasting in a 550 ℃ muffle furnace for 8 hours, removing a template agent, exchanging three times in a 80 ℃ 5wt% ammonium nitrate solution, and roasting in the 550 ℃ muffle furnace for 8 hours after drying to obtain the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in lanthanum nitrate solution with the weight percentage of La of 2% for 12 hours in an equal volume, dried in an oven with the temperature of 60 ℃ and baked for 4 hours in a muffle furnace with the temperature of 550 ℃ to obtain 2% La-ZSM-11 molecular sieve catalyst which is used as a catalyst for producing propylene by direct conversion of tertiary butanol.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 32.3%.
The catalyst composition and the reaction results are shown in Table 1.
[ example 10 ]
Weigh 20 grams of silicon to aluminum molar ratio (SiO 2 /Al 2 O 3 ) 300 NaZSM-11 molecular sieve, 25 g silica sol (SiO 2 40% of weight percentage) by weight, adding water, kneading, extruding with a die with the diameter of 2.0 mm, molding, airing, placing in a 90 ℃ oven for 10 hours, roasting in a 550 ℃ muffle furnace for 8 hours, removing a template agent, exchanging three times in a 80 ℃ 5wt% ammonium nitrate solution, and roasting in the 550 ℃ muffle furnace for 8 hours after drying to obtain the HZSM-11 molecular sieve catalyst. 10 g of the catalyst is immersed in lanthanum nitrate solution with 0.5 percent of La by weight for 12 hours, dried in a drying oven at 60 ℃, baked for 4 hours in a muffle furnace at 550 ℃ to obtain a 0.5 percent La-ZSM-11 molecular sieve catalyst, immersed in cerium nitrate solution with 0.1 percent of Ce by weight for 36 hours, dried in a drying oven at 600 ℃ and baked for 8 hours to obtain the 0.5 percent La-0.1 percent Ce-ZSM-11 molecular sieve catalyst which is used as a catalyst for directly converting tertiary butanol into propylene.
Adopting a fixed bed reaction process, wherein a tertiary butanol aqueous solution is used as a raw material, the weight ratio of water to tertiary butanol is 0.5:1, the reaction temperature is 500 ℃, the reaction pressure is 1MPa, and the weight space velocity of tertiary butanol is 8.0h -1 The reaction conditions were as follows, the conversion of t-butanol was 99.9%, and the propylene yield was 33.8%.
The catalyst composition and the reaction results are shown in Table 1.
TABLE 1
Examples 11 to 14
Other reaction conditions were fixed using the catalyst of example 6, except that the weight ratio of t-butanol to water was varied and the reaction results are shown in Table 2.
Examples 15 to 18
Other reaction conditions were fixed using the catalyst of example 6, except that the reaction temperature was changed and the reaction results are shown in Table 2.
Examples 19 to 22
Other reaction conditions were fixed using the catalyst of example 6, except that the t-butanol weight space velocity was varied and the reaction results are set forth in Table 2.
Examples 23 to 26
Other reaction conditions were fixed using the catalyst of example 6, except that the reaction pressure was varied and the reaction results are shown in Table 2.
TABLE 2
Claims (9)
1. A process for producing propylene by direct conversion of t-butanol comprising: the aqueous solution of tertiary butanol is used as raw material, the raw material is contacted with catalyst to make reaction so as to obtain the product containing propylene, in which the mass ratio of water and tertiary butanol is (0.1-1.2): 1, and the weight space velocity of tertiary butanol is 1-10 hr -1 The catalyst used comprises the following components in parts by weight: a) 30% -80% of molecular sieve; b) 20% -70% of binder; c) 0.01% -5% of rare earth elements, wherein the molecular sieve is selected from ZSM-11, the rare earth elements are selected from La, ce and/or combinations thereof, and the reaction conditions are as follows: the reaction temperature is 400-650 ℃, and the reaction pressure is 0.01-5 MPa.
2. The method according to claim 1, characterized in that: the reaction is carried out in a fixed bed or a fluidized bed.
3. The method according to claim 1 or 2, characterized in that: the reaction conditions were as follows: the reaction temperature is 450-600 ℃, the reaction pressure is 0.01-3 MPa, and the weight airspeed of the tertiary butanol is 2-8 hours -1 The mass ratio of water to tertiary butanol is (0.2-1.2): 1.
4. The method according to claim 1, characterized in that: the catalyst comprises 40-75% of molecular sieve by weight.
5. The method according to claim 1 or 4, characterized in that: siO of the molecular sieve 2 /Al 2 O 3 The molar ratio is 100-600.
6. The method according to claim 5, wherein: siO of the molecular sieve 2 /Al 2 O 3 The molar ratio is 200-600.
7. The method according to claim 5, wherein: siO of the molecular sieve 2 /Al 2 O 3 The molar ratio is 300-500.
8. The method according to claim 1, characterized in that: the catalyst contains 0.1-3% of rare earth elements by weight.
9. The method according to claim 1, characterized in that: the binder is selected from silicon oxide and/or aluminum oxide, or is obtained by roasting at least one component selected from silica sol, aluminum sol and aluminum phosphate.
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