CN112209791B - Method for producing propylene by tert-butyl alcohol conversion - Google Patents
Method for producing propylene by tert-butyl alcohol conversion Download PDFInfo
- Publication number
- CN112209791B CN112209791B CN201910629357.9A CN201910629357A CN112209791B CN 112209791 B CN112209791 B CN 112209791B CN 201910629357 A CN201910629357 A CN 201910629357A CN 112209791 B CN112209791 B CN 112209791B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tertiary butanol
- propylene
- butanol
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for producing propylene by converting tertiary butanol. The method comprises the following steps: a) Contacting the tertiary butanol aqueous solution with a catalyst A containing alumina to produce a mixture containing isobutene and water; b) Contacting the mixture obtained in step a) with a catalyst B containing MCM-49 to produce a propylene-containing product; wherein the catalyst A comprises the following components in percentage by weight: catalyst b=1: (0.01-0.5). The method effectively solves the problems of few types of products at the downstream of the tertiary butanol, low effective utilization rate and shortage of propylene market in the prior art, can convert the tertiary butanol into propylene with high yield, has good propylene selectivity and good catalyst stability, and has good economic and social benefits.
Description
Technical Field
The invention relates to a method for producing propylene by 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 has poor sales. The main reason is that development of downstream products of tertiary butanol is insufficient, so that domestic demand is slowly increased.
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. Isobutene produced by dehydration of tertiary butanol is generally used as a raw material for producing Methyl Tertiary Butyl Ether (MTBE), and because of popularization of ethanol gasoline, MTBE cannot be blended into gasoline, the production capacity of the MTBE is greatly compressed, and reasonable utilization of isobutene serving as an MTBE raw material becomes a new problem.
There have been many reports on a catalyst and a reaction for preparing propylene from mixed carbon tetrahydrocarbons, CN104107713a discloses a catalyst for preparing propylene by cracking mixed carbon tetraolefins, the composition of the catalyst is as follows: 20 to 90 percent of ZSM-5 molecular sieve with the shape index of 3 to 100, 0.05 to 3 percent of transition metal oxide and 18 to 69 percent of binder. CN101033166a discloses a method for producing propylene by catalytic cracking of olefins with four or more carbon atoms and no diolefin, which adopts a ZSM molecular sieve modified by heteropolyacid as a catalyst, wherein the dosage of the heteropolyacid is 5% -20%. The method is used for preparing olefin by mixing carbon tetrahydrocarbon, and the sources of the carbon tetraolefin are different, the performance requirements on the catalyst are different, and the method is continuously researched and explored for how to prepare propylene with high yield aiming at specific raw materials and the catalyst has good stability.
Disclosure of Invention
Aiming at the technical problems of high yield of propylene and good catalyst stability in the production of propylene by converting tert-butyl alcohol as a raw material, the invention provides a method for producing propylene by converting tert-butyl alcohol. The method has the characteristics of good catalyst stability, high propylene yield and good selectivity.
The method for producing propylene by converting tertiary butanol comprises the following steps:
a) Contacting the tertiary butanol aqueous solution with a catalyst A containing alumina to produce a mixture containing isobutene and water;
b) Contacting the mixture obtained in step a) with a catalyst B containing MCM-49 to produce a propylene-containing product;
wherein the catalyst A comprises the following components in percentage by weight: catalyst b=1: (0.01 to 0.5), preferably 1: (0.01-0.1).
In the above technical scheme, step a) is performed in a reactor I, and the dehydration reaction of tertiary butanol mainly occurs.
In the above technical scheme, step b) is performed in a reactor II, and olefin cracking reaction mainly occurs.
In the technical scheme, the step a) and the step b) adopt fixed bed reactors, and the reactor I and the reactor II are connected in series.
In the technical scheme, the catalyst A comprises the following components in parts by weight:
1) 90% -100% of gamma-alumina, preferably 98.5% -99.7%;
2) IVA element 0-5.0%, preferably 0.2% -1.0%;
3) Rare earth elements 0 to 5.0%, preferably 0.1% to 0.5%.
In the above technical scheme, the IVA element in the catalyst A comprises one or more of Ge, sn and Pb, and the rare earth element comprises one or more of La, ce, pr, nd. Preferably, catalyst a contains at least one of the IVA elements and at least one of the rare earth elements.
The preparation method of the catalyst A comprises the following steps: first preparing gamma-Al 2 O 3 The carrier is then selectively impregnated with a supported group IVA element and a rare earth element to obtain a catalyst A in which gamma-Al 2 O 3 The carrier is prepared by conventional method, generally, pseudo-boehmite powder and extrusion aid (such as sesbania powder) are fully mixed and kneaded by peptizing acid (such as dilute nitric acid), then extruded into required shape by a strip extruder, dried and roasted (such as dried at 90-120 ℃ for 2-8 hours and roasted at 500-650 ℃ for 2-8 hours) to obtain gamma-Al 2 O 3 A carrier. The impregnation loading of the group IVA element and the rare earth element may be carried out in a plurality of times or in a single time, and when a plurality of times is carried out, drying and baking are required after each loading, and preferably: the gamma-Al is first impregnated with a solution of a soluble salt of a group IVA metal at a desired concentration 2 O 3 Drying and roasting the carrier, impregnating the above-mentioned solid body with rare earth element soluble salt solution with required concentration, drying andafter calcination, catalyst a was obtained, wherein the drying conditions were as follows: drying at 90-120 deg.c for 2-8 hr, and roasting under the following conditions: roasting for 2-8 hours at 500-650 ℃.
In the technical scheme, the catalyst B comprises the following components in parts by weight:
i)MCM-49 70.0％～88.0％，
ii) alkaline earth metal elements 0 to 2.0%, preferably 0.3 to 1.5%,
iii) 11.0 to 30.0 percent of binder.
In the above technical scheme, the alkaline earth metal element comprises one or more of Mg, ca, sr and Ba, and the binder in the catalyst B is at least one of alumina or silica. SiO of the MCM-49 molecular sieve 2 /Al 2 O 3 The molar ratio is 10-30.
The preparation method of the catalyst B comprises the following steps: adopting MCM-49 molecular sieve, adding extrusion aid (such as sesbania powder) and binder, fully mixing and kneading, extruding the required shape by using a strip extruder, drying (such as drying at 90-120 ℃ for 2-8 hours), performing ammonium ion exchange, and then selectively impregnating and supporting alkaline earth metal elements to obtain the catalyst B. The ammonium ion exchange may be performed using conventional ammonium salt (e.g., ammonium nitrate, ammonium chloride, etc.) solutions. The impregnating and supporting alkaline earth metal element can be obtained by impregnating the solid with alkaline earth metal soluble salt solution with a required concentration, drying and roasting (for example, drying at 90-120 ℃ for 2-8 hours and roasting at 500-650 ℃ for 2-8 hours) to obtain the catalyst B.
In the above technical solution, the operating conditions of step a) are: the weight ratio of water to tertiary butanol is 1: (1-5), the reaction temperature is 150-400 ℃, and the weight space velocity of tertiary butanol is 1-10 h -1 The reaction pressure is 0.05-1.0 MPa, and the preferable operation conditions are as follows: the reaction temperature is 200-380 ℃, and the weight space velocity of tertiary butanol is 3-10 h -1 The reaction pressure is 0.05-0.5 MPa.
In the above technical solution, the operating conditions of step b) are: the reaction temperature is 450-600 ℃, the pressure is 0.02-2.0 MPa, and the preferable operation conditions are as follows: the reaction temperature is 500-600 ℃ and the pressure is 0.02-1.0 MPa.
The method for producing propylene by 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, can convert tertiary butanol into propylene at high yield, has good propylene selectivity and good catalyst stability, and has good economic and social benefits.
Detailed Description
The technical scheme of the invention is further elaborated by the following examples.
[ example 1 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, grinding into 10-20 mesh particles, and taking the particles as a catalyst A for preparing isobutene by dehydrating tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =10 MCM-49 molecular sieve as active component, 40 g silica sol (SiO 2 40% by weight) of the catalyst B is formed, dried, subjected to ammonium exchange and ground into 10-20 mesh particles, and used as a catalyst B for preparing propylene by cracking isobutene.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 2 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with Ge-containing germanium nitrate solution 0.5 wt% 2 O 3 Drying for 12 hr, and roasting at 500 deg.C for 4 hr to obtain 0.5% Ge-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =20 MCM-49 molecular sieve as active component, 40 g silica sol (SiO 2 40% by weight) of the catalyst B is formed, dried, subjected to ammonium exchange and ground into 10-20 mesh particles, and used as a catalyst B for preparing propylene by cracking isobutene.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 3 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with tin nitrate solution containing Sn 1 wt% 2 O 3 12 hours, drying and roasting at 500 ℃ for 4 hours to prepare 1 percent Sn-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =30 MCM-49 molecular sieve as active component, 40 g silica sol (SiO 2 40% by weight) of the catalyst B is formed, dried, subjected to ammonium exchange and ground into 10-20 mesh particles, and used as a catalyst B for preparing propylene by cracking isobutene.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 4 ]
20 g of a ball with a diameter of 3 cm were put intoForm gamma-Al 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with Pb-containing lead nitrate solution 0.5 wt% 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, then soaking in praseodymium nitrate solution containing Pr 0.2% (weight percentage) for 12 hours in equal volume, drying, roasting at 500 ℃ for 4 hours, and preparing into 0.5% Pb-0.2% Pr-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =12 MCM-49 molecular sieve as active component, 40 g silica sol (SiO 2 40% by weight) of the catalyst B is formed, dried, subjected to ammonium exchange and ground into 10-20 mesh particles, and used as a catalyst B for preparing propylene by cracking isobutene.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 5 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with Ge-containing germanium nitrate solution 0.5 wt% 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, then soaking for 12 hours with lanthanum nitrate solution containing La 0.5% (weight percentage) in equal volume, drying, roasting at 500 ℃ for 4 hours, and preparing into 0.5% Ge-0.5% La-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =15 MCM-49 molecular sieve as active component, 40 g silica sol (SiO 2 40% by weight) is formed, dried, subjected to ammonium exchange and ground into 10-20 mesh particles serving asCatalyst B for preparing propylene by cracking isobutene.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 6 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with tin nitrate solution containing Sn 0.5 wt% 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, then soaking for 12 hours with cerium nitrate solution containing Ce 0.2 percent (weight percentage) in equal volume, drying, roasting at 500 ℃ for 4 hours, and preparing 0.5 percent Sn-0.2 percent Ce-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =25 MCM-49 molecular sieve as active component, 40 g silica sol (SiO 2 40% by weight) of the catalyst B is formed, dried, subjected to ammonium exchange and ground into 10-20 mesh particles, and used as a catalyst B for preparing propylene by cracking isobutene.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 7 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, using 0.5% (wt%) Pb-containing nitrateImpregnation of gamma-Al with lead acid solution 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, then soaking in praseodymium nitrate solution containing Pr 0.2% (weight percentage) for 12 hours in equal volume, drying, roasting at 500 ℃ for 4 hours, and preparing into 0.5% Pb-0.2% Pr-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =28 MCM-49 molecular sieve as active component, 40 g silica sol (SiO 2 40% by weight) of the catalyst B is formed, dried, subjected to ammonium exchange and ground into 10-20 mesh particles, and used as a catalyst B for preparing propylene by cracking isobutene.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 8 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with tin nitrate solution containing Sn 0.5 wt% 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, then soaking for 12 hours with cerium nitrate solution containing Ce 0.2 percent (weight percentage) in equal volume, drying, roasting at 500 ℃ for 4 hours, and preparing 0.5 percent Sn-0.2 percent Ce-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =22, adding 10 g of silicon oxide as binder, extruding 50 g of water to form, drying, exchanging ammonium, immersing 10 g of the formed product in 10 g of Mg-containing 0.5% (wt%) solution of magnesium nitrate for 4 hr, drying, roasting at 500 deg.C for 4 hr to obtain 0.5% Mg modified productDecoration, siO 2 /Al 2 O 3 (molar ratio) =22, and the MCM-49 catalyst was ground into 10-20 mesh particles as catalyst B for propylene production by isobutylene cracking.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 9 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with tin nitrate solution containing Sn 0.5 wt% 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, then soaking for 12 hours with cerium nitrate solution containing Ce 0.2 percent (weight percentage) in equal volume, drying, roasting at 500 ℃ for 4 hours, and preparing 0.5 percent Sn-0.2 percent Ce-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =18, adding 10 g of binder silica and 50 g of water, extruding, forming, drying, and making ammonium exchange, taking 10 g of the formed product, impregnating with 10 g of calcium nitrate solution containing Ca 2% (weight percentage) for 4 hr, drying, roasting at 500 deg.C for 4 hr to obtain 2% Ca modified SiO 2 /Al 2 O 3 (molar ratio) =18, and grinding into 10-20 mesh particles to obtain the catalyst B for preparing propylene by isobutene pyrolysis.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.01, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The temperature of the reactor II is 500 ℃, the reaction pressure is 0.02MPa, and the reaction is carried out under the conditionsCatalyst reactivity was evaluated.
The catalyst composition and the reaction results are shown in Table 1.
[ example 10 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with tin nitrate solution containing Sn 0.5 wt% 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, then soaking for 12 hours with cerium nitrate solution containing Ce 0.2 percent (weight percentage) in equal volume, drying, roasting at 500 ℃ for 4 hours, and preparing 0.5 percent Sn-0.2 percent Ce-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =15, adding 10 g of silicon oxide as binder, extruding 50 g of water to form, drying, exchanging ammonium, immersing 10 g of the formed product in 10 g of strontium nitrate solution containing 0.5 wt% of Sr for 4 hours, drying, roasting at 500 ℃ for 4 hours to obtain 0.5% Sr modified SiO 2 /Al 2 O 3 (molar ratio) =15, and the MCM-49 catalyst was ground into 10-20 mesh particles as catalyst B for propylene production by isobutylene cracking.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.08, reactor I temperature of 350 ℃, pressure of 0.05MPa, t-butanol weight space velocity of 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
[ example 11 ]
20 g of spherical gamma-Al with a diameter of 3 cm were introduced 2 O 3 Roasting, measuring water absorption, impregnating gamma-Al with tin nitrate solution containing Sn 0.5 wt% 2 O 3 Drying for 12 hours, roasting at 500 ℃ for 4 hours, and then soaking for 12 hours with equal volume of cerium nitrate solution containing Ce 0.2 percent (weight percentage)Oven drying, and calcining at 500 deg.C for 4 hr to obtain 0.5% Sn-0.2% Ce-gamma-Al 2 O 3 The catalyst is ground into 10-20 mesh particles and used as a catalyst A for preparing isobutene through dehydration of tertiary butanol.
At 50 g of SiO 2 /Al 2 O 3 (molar ratio) =20, adding 10 g of binder silicon oxide and 50 g of water, extruding, forming, drying, and making ammonium exchange, taking 10 g of the formed product, soaking with 10 g of barium nitrate solution containing Ba 1% (weight percentage) for 4 hr, drying, roasting at 500 deg.C for 4 hr to obtain 1% Ba modified SiO 2 /Al 2 O 3 (molar ratio) =20, and the MCM-49 catalyst was ground into 10-20 mesh particles as catalyst B for propylene production by isobutylene cracking.
Adopting a fixed bed reaction process, taking tertiary butanol aqueous solution as a raw material, wherein the weight ratio of water to tertiary butanol is 1:4, the loading ratio of the catalyst A to the catalyst B is 1:0.5, the temperature of the reactor I is 350 ℃, the pressure is 0.05MPa, and the weight space velocity of the tertiary butanol is 5h -1 The reaction performance of the catalyst was evaluated under the above conditions, with the temperature of the reactor II being 500℃and the reaction pressure being 0.02 MPa.
The catalyst composition and the reaction results are shown in Table 1.
TABLE 1
Examples 12 to 14
Other reaction conditions were fixed using the catalyst of example 10 and its loading ratio, except that the weight ratio of t-butanol to water was changed, and the reaction results are shown in Table 2.
Examples 15 to 17
Other reaction conditions were fixed using the catalyst of example 10 and its loading ratio, except that the reaction temperature of reactor I was changed, and the reaction results are shown in Table 2.
Examples 18 to 20
Other reaction conditions were fixed using the catalyst of example 10 and its loading ratio, except that the t-butanol weight space velocity of reactor I was varied and the reaction results are set forth in Table 2.
Examples 21 to 23
Other reaction conditions were fixed using the catalyst of example 10 and its loading ratio, except that the reaction pressure of reactor I was changed, and the reaction results are shown in Table 2.
Examples 24 to 26
Other reaction conditions were fixed using the catalyst of example 10 and its loading ratio, except that the reaction temperature of reactor II was changed, and the reaction results are shown in Table 2.
Examples 27 to 29
Other reaction conditions were fixed using the catalyst of example 10 and its loading ratio, except that the reaction pressure of reactor II was changed, and the reaction results are shown in Table 2.
TABLE 2
Claims (9)
1. A process for producing propylene by conversion of t-butanol comprising the steps of:
a) Contacting the tertiary butanol aqueous solution with a catalyst A containing alumina to produce a mixture containing isobutene and water;
b) Contacting the mixture obtained in step a) with a catalyst B containing MCM-49 to produce a propylene-containing product;
wherein the catalyst A comprises the following components in percentage by weight: catalyst b=1: (0.01 to 0.5);
the catalyst A comprises the following components in parts by weight:
1) 98.5% -99.7% of gamma-alumina;
2) IVA element 0.2% -1.0%;
3) 0.1 to 0.5 percent of rare earth element;
wherein the IVA element comprises one or more of Ge, sn and Pb, and the rare earth element comprises one or more of La, ce, pr, nd;
the catalyst B comprises the following components in parts by weight:
i) MCM-49 70.0%~88.0%，
ii) 0 to 2.0% of alkaline earth metal element,
iii) 11.0 to 30.0 percent of binder.
2. The process for producing propylene by conversion of t-butanol according to claim 1, wherein: the catalyst A comprises the following components in percentage by weight: catalyst b=1: (0.01 to 0.1).
3. The process for producing propylene by conversion of t-butanol according to claim 1, wherein: the catalyst B comprises the following components in parts by weight:
i) MCM-49 70.0%~88.0%，
ii) alkaline earth metal element 0.3% -1.5%,
iii) 11.0 to 30.0 percent of binder.
4. A process for the conversion of t-butanol to propylene according to claim 3 wherein: in the catalyst B, alkaline earth metal elements comprise one or more of Mg, ca, sr and Ba, and the binder in the catalyst B is at least one of alumina or silica.
5. A process for the conversion of t-butanol to propylene according to claim 1 or 3, wherein: siO of the MCM-49 molecular sieve 2 /Al 2 O 3 The molar ratio is 10-30.
6. The process for producing propylene by conversion of t-butanol according to claim 1, wherein: the reaction conditions of step a) are: the weight ratio of water to tertiary butanol is 1: (1-5), the reaction temperature is 150-400 ℃, and the weight space velocity of tertiary butanol is 1-10 h -1 The reaction pressure is 0.05-1 MPa.
7. The process for producing propylene by conversion of t-butanol according to claim 1, wherein: the reaction conditions of step a) are: reverse-rotationThe reaction temperature is 300-380 ℃, and the weight space velocity of tertiary butanol is 3-10 h -1 The reaction pressure is 0.05-0.1 MPa.
8. The process for producing propylene by conversion of t-butanol according to claim 1, wherein: the operating conditions of step b) are: the reaction temperature is 450-600 ℃ and the pressure is 0.02-2.0 MPa.
9. The process for producing propylene by conversion of t-butanol according to claim 1, wherein: the operating conditions of step b) are: the reaction temperature is 500-600 ℃ and the pressure is 0.02-1.0 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910629357.9A CN112209791B (en) | 2019-07-12 | 2019-07-12 | Method for producing propylene by tert-butyl alcohol conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910629357.9A CN112209791B (en) | 2019-07-12 | 2019-07-12 | Method for producing propylene by tert-butyl alcohol conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112209791A CN112209791A (en) | 2021-01-12 |
| CN112209791B true CN112209791B (en) | 2023-08-04 |
Family
ID=74047788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910629357.9A Active CN112209791B (en) | 2019-07-12 | 2019-07-12 | Method for producing propylene by tert-butyl alcohol conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112209791B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4207424A (en) * | 1978-08-09 | 1980-06-10 | Halcon Research & Development Corporation | Catalytic process for dehydration of alcohols |
| CN102285852A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increasing yields of ethylene and propylene by using refinery C4 |
| CN102285857A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increasing yields of propylene and ethylene |
| CN102302945A (en) * | 2011-10-04 | 2012-01-04 | 大连理工大学 | Method for preparing propene by catalytic cracking |
| CN102906053A (en) * | 2010-03-15 | 2013-01-30 | 道达尔研究技术弗吕公司 | Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103153920B (en) * | 2010-08-03 | 2015-04-15 | 道达尔研究技术弗吕公司 | Process to make olefins from isobutanol |
-
2019
- 2019-07-12 CN CN201910629357.9A patent/CN112209791B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4207424A (en) * | 1978-08-09 | 1980-06-10 | Halcon Research & Development Corporation | Catalytic process for dehydration of alcohols |
| CN102906053A (en) * | 2010-03-15 | 2013-01-30 | 道达尔研究技术弗吕公司 | Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis |
| CN102285852A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increasing yields of ethylene and propylene by using refinery C4 |
| CN102285857A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increasing yields of propylene and ethylene |
| CN102302945A (en) * | 2011-10-04 | 2012-01-04 | 大连理工大学 | Method for preparing propene by catalytic cracking |
Non-Patent Citations (1)
| Title |
|---|
| 烯烃催化裂解制低碳烯烃技术的研究进展;张远征;《石油化工》;20080815;第37卷(第08期);852-857 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112209791A (en) | 2021-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107107042B (en) | Catalyst for preparing glycol ether and preparation method and application thereof | |
| CN112209791B (en) | Method for producing propylene by tert-butyl alcohol conversion | |
| EP0224220B1 (en) | Process for the preparation of di-isobutene from isobutene | |
| CN103586045B (en) | A kind of producing light olefins Catalysts and its preparation method | |
| CN101301625B (en) | Al2O3-HZSM-5 compound solid acid catalyst prepared by mechanical mixed method | |
| CN103508885B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN101301624B (en) | Al2O3-HZSM-5 compound solid acid catalyst prepared by chemical precipitation method | |
| CN100567237C (en) | The method of acetal or ketal preparing alkenyl ether by gas phase decomposing | |
| CN1128675C (en) | Low-carbon olefine synthesized C12-C18 ZrZSM-5 molecular sieve catalyst and its prepn | |
| CN1745894A (en) | A kind of dimethyl ether by methanol dewater and preparation method and application | |
| CN112679296B (en) | Method for producing propylene by directly converting tert-butyl alcohol | |
| CN113751059B (en) | Catalyst for producing propylene and ethylene by direct conversion of tertiary butanol and application thereof | |
| KR101629003B1 (en) | Catalyst for dehydration of glycerin, method of preparing the same, and preparing method of acrolein | |
| CN107876040B (en) | Catalyst for one-step synthesis of isobutyraldehyde from methanol and ethanol and preparation method thereof | |
| CN111099969B (en) | Method for preparing p-tert-butyl catechol | |
| CN101602006B (en) | Modified aluminum oxide catalyst for synthesizing dimethyl ether and preparation method thereof | |
| CN111099972B (en) | Method for preparing p-tert-butyl catechol from MTBE (methyl tert-butyl ether) | |
| CN107915589B (en) | Method for generating polyoxymethylene dimethyl ether | |
| CN113926475B (en) | Dehydration catalyst, preparation method and application thereof in tert-butyl alcohol dehydration to produce isobutene | |
| CN112679295B (en) | Method for producing propylene by converting tert-butyl alcohol | |
| CN115477568B (en) | Method for synthesizing 2, 5-dimethyl-2, 4-hexadiene based on Prins condensation reaction catalyzed by heteropolyacid | |
| CN107915595B (en) | Method for producing polyoxymethylene dimethyl ethers | |
| CN112209790A (en) | Method for producing propylene by directly converting tert-butyl alcohol | |
| CN114436859B (en) | Method for preparing sec-butylamine through C4 after ether | |
| CN107915608B (en) | Method for synthesizing polyoxymethylene dimethyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |