CN115141086A - Methyl tert-butyl ether recycling process - Google Patents
Methyl tert-butyl ether recycling process Download PDFInfo
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- CN115141086A CN115141086A CN202210777666.2A CN202210777666A CN115141086A CN 115141086 A CN115141086 A CN 115141086A CN 202210777666 A CN202210777666 A CN 202210777666A CN 115141086 A CN115141086 A CN 115141086A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
Abstract
The invention discloses a methyl tert-butyl ether recycling process, which comprises the steps of firstly, reacting methanol and isobutene in a main reactor filled with a first catalyst to obtain a reaction product; then introducing the reaction product into a distillation tower filled with a second catalyst, and carrying out distillation separation to obtain a crude product of the methyl tert-butyl ether; and then introducing the crude product of the methyl tert-butyl ether into a remilling reactor filled with a mixed catalyst to obtain the purified methyl tert-butyl ether. The method has the advantages of simple process, low energy consumption and high purity of the obtained methyl tert-butyl ether.
Description
Technical Field
The invention relates to a methyl tert-butyl ether recycling process. Belongs to the technical field of chemical process.
Background
Methyl tert-butyl ether (MTBE) is an important chemical raw material, has low water solubility, strong acid resistance, strong oxidation resistance, low toxicity, low volatility and strong solvating capacity, has wide application in the fields of solvents and extracting agents, and can be used for producing methacrolein, methacrylic acid, high-purity isobutene and the like.
Methyl tert-butyl ether (MTBE) is a main component of clean gasoline and is a common non-hydrocarbon blending component for gasoline, and the molecular structure of MTBE contains oxygen atoms, so that the mixing of MTBE and gasoline can reduce the generation of nitrogen oxides, carbon monoxide and the like; moreover, the octane number of MTBE is high (about 118), which is also beneficial to improving the octane number of gasoline and obviously improving the quality of the gasoline.
MTBE can be prepared by reacting methanol with isobutylene in the presence of an acid catalyst. Since the reaction is an equilibrium reaction, the MTBE product obtained generally has a high residual of methanol and tert-butanol, resulting in product failure. In the prior art, a distillation tower is usually arranged at the rear end of a reactor to overcome equilibrium reaction, so that the heat energy consumption is very large, and the current green and environment-friendly concept is not met.
In addition, the MTBE product obviously contains sulfide, and the sulfur content of common products reaches 50-200 mg/kg, even 2000mg/kg. The national standard has stricter limits on the sulfur content in the gasoline, the upper limit of the sulfur content of the national standard gasoline II is 500mg/kg, the upper limit of the sulfur content of the national standard gasoline III is 150mg/kg, the upper limit of the sulfur content of the national standard gasoline IV is 50mg/kg, and the upper limit of the sulfur content of the national standard gasoline V is 10mg/kg; obviously, the sulfur content of the MTBE product is difficult to meet the national standard of the current and future gasoline, the application of the MTBE in the gasoline is seriously influenced, and the resource utilization of the refinery liquefied petroleum gas and the production supply of the gasoline are limited.
Currently, methods for reducing sulfur content in MTBE can be roughly divided into the following two types:
firstly, redistilling the mixed C4 after the fractionation of the liquefied petroleum gas to obtain light C4 and heavy C4, wherein the light C4 has higher isobutene content and lower sulfur content and can be used as raw materials for etherification or alkylation, and the sulfur content of MTBE obtained after etherification is lower. However, the method increases distillation energy consumption again, and the boiling point of sulfide in heavy C4 is close to that of light C4 such as isobutene, so that the separation is difficult to complete, and the sulfur content in the finally obtained MTBE product is difficult to reach below 10 mg/kg.
Secondly, the desulfurization treatment of the high sulfur MTBE products obtained in the prior art is carried out directly, and patent application CN101643392A discloses a method for desulfurizing methyl tert-butyl ether with high sulfur content, which adopts a redistillation method to redistilling the high sulfur MTBE, and reduces the sulfur content in the MTBE evaporated by increasing the number of plates and increasing the reflux ratio. The method also increases distillation energy consumption, and has high equipment investment and maintenance cost, thereby limiting the popularization and application value of the method.
Patent application CN108976104A discloses a synthesis method of methyl tert-butyl ether, which comprises the following steps:
s1, material taking, namely feeding isobutene into a separation reaction tank, after settling and water separation, boosting pressure through an isobutene raw material pump, and then feeding the isobutene into an isobutene-methanol mixer through a flow meter and a flow control valve;
s2, mixing, feeding methanol into a reaction device filled with a catalyst, and reacting to obtain a solution containing methanol, sulfide and methyl tert-butyl ether;
s3, pressurizing the solution of the methanol, the sulfide and the methyl tert-butyl ether obtained in the S2 from the tank area outside the device through a methanol feed pump, sending the solution to an isobutene-methanol mixer, and controlling the flow through a flow meter and a flow regulating valve;
s4, fully mixing the solution in an isobutene-methanol mixer, preheating by a raw material preheater, and feeding into an etherification reactor;
and S5, reacting under the action of a catalyst and pressure, filtering through an adsorbent column of a molecular sieve after the reaction is finished, filtering, and removing sulfides in the methyl tert-butyl ether through a rectifying section of an integrated adsorption distillation tower to obtain the methyl tert-butyl ether.
When the catalyst of the patent technology adopts the combination of the acidic styrene macroporous cation exchange resin and the furfural hydrogenation catalyst, the conversion rate of isobutene is high, but the product purification is finally realized by completely depending on the rectification section of the integrated adsorption distillation tower, and the desulfurization cost and the desulfurization effect cannot be obtained at the same time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a methyl tert-butyl ether recycling process which is simple in process, low in energy consumption and high in purity of the obtained methyl tert-butyl ether.
In order to achieve the purpose, the invention adopts the following technical scheme:
a methyl tert-butyl ether recycling process comprises the following specific steps:
(1) Firstly, in a main reactor filled with a first catalyst, methanol reacts with isobutene to obtain a reaction product;
(2) Then introducing the reaction product into a distillation tower filled with a second catalyst, and carrying out distillation separation to obtain a crude product of the methyl tert-butyl ether;
(3) Then introducing the crude product of the methyl tert-butyl ether into a remilling reactor filled with a mixed catalyst to obtain purified methyl tert-butyl ether;
wherein the first catalyst is prepared by taking gamma-alumina, cerium oxalate, ethyl orthosilicate, anhydrous formic acid, 1-2 mol/L sulfuric acid solution and methane sulfonic acid as raw materials; the second catalyst is prepared by taking a carbohydrate, zirconium citrate and yttrium isopropoxide as raw materials; the mixed catalyst is obtained by uniformly mixing the first catalyst and the second catalyst according to the mass ratio of 1: 0.5-0.7.
Preferably, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat insulation layers.
Preferably, in step (1), methanol and isobutene are mixed in a molar ratio of 1.01-1.03: 1 to obtain a mixed solution, and then the mixed solution is mixed for 1-2 h -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, the vapor is introduced into a main reactor preheated to 30-35 ℃, and the reaction is carried out under the conditions of the temperature of 63-67 ℃ and the pressure of 0.58-0.64 MPa to obtain a reaction product.
Preferably, in the step (2), the reaction product is reacted for 8 to 10 hours -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual number of tower plates of the distillation tower is 12-15, the theoretical number of tower plates is 8-10, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th-6 th tower plates from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether.
More preferably, the temperature of the bottom of the distillation tower is 120-130 ℃, the temperature of the top of the distillation tower is 50-55 ℃, the pressure of the top of the distillation tower is 0.4-0.45 MPa, the liquid level of the bottom of the distillation tower is controlled at 35-50%, and the reflux ratio of the top of the distillation tower is 2.0-2.5.
Preferably, step (3)In the method, the crude product of the methyl tert-butyl ether is added for 3 to 4 hours -1 The air speed of the reaction kettle is led into a remill reactor preheated to 30-35 ℃, remill is carried out under the conditions of 45-50 ℃ and 0.5-0.6 MPa of pressure, and a condenser condenses to obtain the purified methyl tert-butyl ether.
Preferably, the first catalyst is prepared by the following method in parts by weight: firstly, dipping 10 parts of gamma-alumina by using 100-120 parts of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; under the anhydrous condition, mixing 55-65 parts of ethyl orthosilicate and 150-170 parts of anhydrous formic acid to prepare a mixed solution, then adding 0.3-0.5 part of methane sulfonic acid and the solid into the mixed solution, fully oscillating by ultrasonic waves, and roasting to obtain the first catalyst; wherein, the cerous oxalate sulfuric acid solution is obtained by dissolving cerous oxalate in 1-2 mol/L sulfuric acid solution with the weight being 12-15 times of that of the cerous oxalate.
Further preferably, the impregnation process conditions are as follows: dipping for 5-7 hours under the ultrasonic oscillation of 200-300W.
More preferably, the tetraethoxysilane and the anhydrous formic acid are mixed and stirred for 50 to 60 minutes at the speed of 300 to 500 r/min.
Further preferably, the process conditions for sufficiently oscillating the ultrasonic waves are as follows: ultrasonic oscillation of 500-600W for 3-4 hr.
Further preferably, the roasting process conditions are as follows: roasting at 400-500 deg.c for 5-7 hr.
Preferably, the second catalyst is prepared by the following method in parts by weight: firstly, adding 10 parts of carbohydrate, 1-2 parts of zirconium citrate and 0.8-1 part of yttrium isopropoxide into 1-2 mol/L sulfuric acid solution, stirring for 2-3 hours at 300-400 r/min, transferring into a reaction kettle, stirring for 8-10 hours at 200-220 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing for 6-8 hours at 500-600 ℃ under the atmosphere of nitrogen to obtain the second catalyst.
Further preferably, the saccharide compound is selected from any one of glucose, sucrose, maltose and fructose.
The invention has the beneficial effects that:
firstly, in a main reactor filled with a first catalyst, methanol reacts with isobutene to obtain a reaction product; then introducing the reaction product into a distillation tower filled with a second catalyst, and carrying out distillation separation to obtain a crude product of the methyl tert-butyl ether; and then introducing the crude product of the methyl tert-butyl ether into a remill reactor filled with a mixed catalyst to obtain the purified methyl tert-butyl ether. The method has the advantages of simple process, low energy consumption and high purity of the obtained methyl tert-butyl ether.
The first catalyst is prepared from gamma-alumina, cerium oxalate, ethyl orthosilicate, anhydrous formic acid, sulfuric acid solution and methane sulfonic acid serving as raw materials. Tetraethoxysilane is used as a silicon source, anhydrous formic acid is used as a hydrolysis catalyst, tetraethoxysilane is promoted to be hydrolyzed to generate amorphous silicon dioxide, the effect of loading gamma-aluminum oxide and cerium oxalate is achieved, a sulfuric acid solution and methane sulfonic acid play a role in acid modification, the finally obtained first catalyst is a solid acid catalyst, the reaction of methanol and isobutene is promoted to generate methyl tert-butyl ether, the reaction is more sufficient, and a good basis is provided for the purity of the product methyl tert-butyl ether.
The second catalyst is prepared by taking carbohydrate, zirconium citrate and yttrium isopropoxide as raw materials, adding the carbohydrate, the zirconium citrate and the yttrium isopropoxide into a sulfuric acid solution, stirring, transferring into a reaction kettle, heating and stirring, filtering to obtain a solid, washing with water, drying, and carbonizing in a nitrogen atmosphere to obtain the catalyst. The carbohydrate compounds are carbonized to form a carrier, a catalytic active center of solid acid is formed under the action of sulfuric acid, and the compounds of zirconium and yttrium are used for concerted catalysis, so that methanol and isobutene in the distillation tower further react to generate methyl tert-butyl ether, the number of tower plates of the distillation tower is not large, the energy consumption is low, the discharged materials at the top of the tower are unreacted methanol and isobutene, the discharged materials at the bottom of the tower are sulfides, and the middle part of the discharged materials are crude products of the methyl tert-butyl ether.
The mixed catalyst is obtained by uniformly mixing the first catalyst and the second catalyst according to a specific mass ratio, so that the crude product of the methyl tert-butyl ether is fully recycled and purified, and the product purity is improved.
Detailed Description
The present invention will be further illustrated by the following examples, which are intended to be merely illustrative and not limitative.
Example 1:
a methyl tert-butyl ether recycling process comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.01: 1 to obtain mixed liquid, and then the mixed liquid is mixed for 1 hour -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and then the vapor is introduced into a main reactor which is preheated to 30 ℃ and is filled with a first catalyst for reaction under the conditions of 63 ℃ and 0.58MPa of pressure to obtain a reaction product;
(2) The reaction product was then reacted for 8h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual number of tower plates of the distillation tower is 12, the theoretical number of tower plates is 8, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th tower plate from the bottom of the distillation tower, namely crude methyl tert-butyl ether;
(3) Finally, the crude methyl tert-butyl ether is added for 3h -1 Introducing the air speed of the mixed catalyst into a remill reactor which is preheated to 30 ℃ and filled with the mixed catalyst, remilling at the temperature of 45 ℃ and under the pressure of 0.5MPa, and condensing by a condenser to obtain the purified methyl tert-butyl ether.
Wherein, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat preservation layers.
In the step (2), the temperature of the bottom of the distillation tower is 120 ℃, the temperature of the top of the distillation tower is 50 ℃, the pressure of the top of the distillation tower is 0.4MPa, the liquid level at the bottom of the distillation tower is controlled at 35%, and the reflux ratio at the top of the distillation tower is 2.0.
The first catalyst was prepared as follows: firstly, dipping 10g of gamma-alumina by using 100g of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; mixing 55g of tetraethoxysilane and 150g of anhydrous formic acid under the anhydrous condition to prepare a mixed solution, adding 0.3g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic wave sufficient oscillation and roasting to obtain the first catalyst; wherein, the cerous oxalate sulfuric acid solution is obtained by dissolving cerous oxalate in 1mol/L sulfuric acid solution with the weight being 12 times that of the cerous oxalate.
The technological conditions of the impregnation are as follows: the mixture was immersed in 200W ultrasonic waves for 5 hours.
Mixing ethyl orthosilicate and anhydrous formic acid, and stirring for 50 minutes at 300 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: 500W ultrasonic oscillation is carried out for 3 hours.
The roasting process conditions are as follows: roasting at 400 deg.c for 5 hr.
The second catalyst was prepared as follows: firstly, adding 10g of carbohydrate (glucose), 1g of zirconium citrate and 0.8g of yttrium isopropoxide into 1mol/L sulfuric acid solution, stirring for 2 hours at 300r/min, transferring into a reaction kettle, stirring and treating for 8 hours at 200 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing at 500 ℃ for 6 hours under the nitrogen atmosphere to obtain the second catalyst.
The mixed catalyst is obtained by uniformly mixing a first catalyst and a second catalyst in a mass ratio of 1: 0.5.
Example 2:
a methyl tert-butyl ether recycling process comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.03: 1 to obtain a mixed solution, and then the mixed solution is mixed for 2 hours -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, the vapor is introduced into a main reactor which is preheated to 35 ℃ and is filled with a first catalyst, and the reaction is carried out under the conditions of 67 ℃ and 0.64MPa of pressure to obtain a reaction product;
(2) The reaction product was then reacted for 10h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual tower plate number of the distillation tower is 15, the theoretical tower plate number is 10, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 6 th tower plate from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether;
(3) Finally, the crude methyl tert-butyl ether is added for 4h -1 Introducing the air speed of the mixed catalyst into a remill reactor which is preheated to 35 ℃ and is filled with the mixed catalyst, remilling the mixed catalyst at the temperature of 50 ℃ and the pressure of 0.6MPa, and condensing the mixed catalyst by a condenser to obtain the purified methyl tert-butyl ether.
Wherein, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat preservation layers.
In the step (2), the temperature of the bottom of the distillation tower is 130 ℃, the temperature of the top of the distillation tower is 55 ℃, the pressure of the top of the distillation tower is 0.45MPa, the liquid level of the bottom of the distillation tower is controlled at 50%, and the reflux ratio of the top of the distillation tower is 2.5.
The first catalyst was prepared as follows: firstly, dipping 10g of gamma-alumina by using 120g of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; mixing 65g of ethyl orthosilicate and 170g of anhydrous formic acid under an anhydrous condition to prepare a mixed solution, adding 0.5g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic full oscillation and roasting to obtain the first catalyst; wherein, the cerium oxalate sulfuric acid solution is obtained by dissolving cerium oxalate in 2mol/L sulfuric acid solution with 15 times weight of cerium oxalate.
The technological conditions of the impregnation are as follows: the substrate was immersed in 300W ultrasonic waves for 7 hours.
The tetraethoxysilane and the anhydrous formic acid are mixed and stirred for 60 minutes at the speed of 500 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: ultrasonic oscillation at 600W was carried out for 4 hours.
The roasting process conditions are as follows: roasting at 500 deg.c for 7 hr.
The second catalyst was prepared as follows: firstly, adding 10g of carbohydrate (sucrose), 2g of zirconium citrate and 1g of yttrium isopropoxide into 2mol/L sulfuric acid solution, stirring for 3 hours at a speed of 400r/min, transferring the mixture into a reaction kettle, stirring and treating the mixture for 10 hours at a temperature of 220 ℃, filtering the mixture to obtain a solid, washing the solid with water, drying the solid, and carbonizing the solid for 8 hours at a temperature of 600 ℃ in a nitrogen atmosphere to obtain the second catalyst.
The mixed catalyst is obtained by uniformly mixing a first catalyst and a second catalyst in a mass ratio of 1: 0.7.
Example 3:
a methyl tert-butyl ether recycling process comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.01: 1 to obtain mixed liquid, and then the mixed liquid is mixed for 2 hours -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and the vapor is introduced into a main reactor which is preheated to 30 ℃ and is filled with a first catalyst, and the temperature and the pressure are 67 ℃ and 0.58MPaCarrying out reaction to obtain a reaction product;
(2) The reaction product was then reacted for 10h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual number of tower plates of the distillation tower is 12, the theoretical number of tower plates is 10, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th tower plate from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether;
(3) Finally, the crude methyl tert-butyl ether is added for 4h -1 Introducing the air speed of the mixed catalyst into a remill reactor which is preheated to 30 ℃ and filled with the mixed catalyst, remilling at the temperature of 50 ℃ and the pressure of 0.5MPa, and condensing by a condenser to obtain the purified methyl tert-butyl ether.
Wherein, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat preservation layers.
In the step (2), the temperature of the bottom of the distillation tower is 130 ℃, the temperature of the top of the distillation tower is 50 ℃, the pressure of the top of the distillation tower is 0.45MPa, the liquid level of the bottom of the distillation tower is controlled at 35%, and the reflux ratio of the top of the distillation tower is 2.5.
The first catalyst was prepared as follows: firstly, soaking 10g of gamma-alumina in 100g of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; mixing 65g of ethyl orthosilicate and 150g of anhydrous formic acid under an anhydrous condition to prepare a mixed solution, adding 0.5g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic full oscillation and roasting to obtain the first catalyst; wherein, the cerium oxalate sulfuric acid solution is obtained by dissolving cerium oxalate in 2mol/L sulfuric acid solution with the weight being 12 times of that of the cerium oxalate.
The process conditions of the impregnation are as follows: the resultant was immersed in 200W ultrasonic waves for 7 hours.
The tetraethoxysilane and the anhydrous formic acid are mixed and stirred for 60 minutes at the speed of 300 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: 500W ultrasonic vibration was carried out for 4 hours.
The roasting process conditions are as follows: roasting at 400 deg.c for 7 hr.
The second catalyst was prepared as follows: firstly, 10g of carbohydrate (maltose), 1g of zirconium citrate and 1g of yttrium isopropoxide are added into 1mol/L sulfuric acid solution, stirred for 2 hours at a speed of 400r/min, transferred into a reaction kettle, stirred for 8 hours at a temperature of 220 ℃, filtered to obtain a solid, washed by water, dried, and carbonized at a temperature of 600 ℃ for 6 hours in a nitrogen atmosphere to obtain the second catalyst.
The mixed catalyst is obtained by uniformly mixing the first catalyst and the second catalyst according to the mass ratio of 1: 0.7.
Example 4:
a methyl tert-butyl ether recycling process comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.03: 1 to obtain a mixed solution, and then the mixed solution is mixed for 1 hour -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and then the vapor is introduced into a main reactor which is preheated to 35 ℃ and is filled with a first catalyst for reaction under the conditions of 63 ℃ and 0.64MPa of pressure to obtain a reaction product;
(2) The reaction product was then worked up for 8h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual tower plate number of the distillation tower is 15, the theoretical tower plate number is 8, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th tower plate from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether;
(3) Finally, the crude methyl tert-butyl ether is added for 3h -1 The space velocity of the catalyst is introduced into a remill reactor which is preheated to 35 ℃ and is filled with a mixed catalyst, the remill is carried out under the conditions of 45 ℃ and 0.6MPa of pressure, and a condenser is used for condensation, thus obtaining the purified methyl tert-butyl ether.
Wherein, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat preservation layers.
In the step (2), the temperature of the bottom of the distillation tower is 120 ℃, the temperature of the top of the distillation tower is 55 ℃, the pressure of the top of the distillation tower is 0.4MPa, the liquid level of the bottom of the distillation tower is controlled at 50%, and the reflux ratio of the top of the distillation tower is 2.0.
The first catalyst was prepared as follows: firstly, dipping 10g of gamma-alumina by using 120g of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; under the anhydrous condition, mixing 55g of ethyl orthosilicate and 170g of anhydrous formic acid to prepare a mixed solution, then adding 0.3g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic full oscillation and roasting to obtain the first catalyst; wherein, the cerium oxalate sulfuric acid solution is obtained by dissolving cerium oxalate in 1mol/L sulfuric acid solution with 15 times of weight.
The technological conditions of the impregnation are as follows: the mixture was immersed in 300W ultrasonic waves for 5 hours.
The tetraethoxysilane and the anhydrous formic acid are mixed and stirred for 50 minutes at 500 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: ultrasonic oscillation at 600W for 3 hours.
The roasting process conditions are as follows: roasting at 500 deg.c for 5 hr.
The second catalyst was prepared as follows: firstly, adding 10g of carbohydrate (fructose), 2g of zirconium citrate and 0.8g of yttrium isopropoxide into 2mol/L sulfuric acid solution, stirring for 3 hours at 300r/min, transferring into a reaction kettle, stirring for 10 hours at 200 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing for 8 hours at 500 ℃ in a nitrogen atmosphere to obtain the second catalyst.
The mixed catalyst is obtained by uniformly mixing a first catalyst and a second catalyst in a mass ratio of 1: 0.5.
Example 5:
a methyl tert-butyl ether recycling process comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.02: 1 to obtain a mixed solution, and then the mixed solution is mixed for 1.5h -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and then the vapor is introduced into a main reactor which is preheated to 33 ℃ and is filled with a first catalyst for reaction under the conditions of 65 ℃ and 0.61MPa of pressure to obtain a reaction product;
(2) The reaction product was then reacted for 9h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual tower plate number of the distillation tower is 13, the theoretical tower plate number is 9, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th tower plate from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether;
(3) Finally, the crude methyl tert-butyl ether is added for 3.5h -1 Space velocity of (2) introduction preheatingAnd (3) carrying out remilling in a remilling reactor filled with a mixed catalyst at the temperature of 33 ℃ and under the pressure of 0.5MPa, and condensing by a condenser to obtain the purified methyl tert-butyl ether.
Wherein, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat preservation layers.
In the step (2), the temperature of the bottom of the distillation tower is 125 ℃, the temperature of the top of the distillation tower is 53 ℃, the pressure of the top of the distillation tower is 0.4MPa, the liquid level of the bottom of the distillation tower is controlled at 42%, and the reflux ratio of the top of the distillation tower is 2.2.
The first catalyst was prepared as follows: firstly, dipping 10g of gamma-alumina by using 110g of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; mixing 60g of ethyl orthosilicate and 160g of anhydrous formic acid under an anhydrous condition to prepare a mixed solution, adding 0.4g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic full oscillation and roasting to obtain the first catalyst; wherein, the cerium oxalate sulfuric acid solution is obtained by dissolving cerium oxalate in 1.5mol/L sulfuric acid solution with 13 times of weight.
The technological conditions of the impregnation are as follows: the substrate was immersed in 300W ultrasonic waves for 6 hours.
The tetraethoxysilane and the anhydrous formic acid are mixed and stirred for 55 minutes at the speed of 400 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: ultrasonic oscillation at 600W is carried out for 3.5 hours.
The roasting process conditions are as follows: roasting at 450 deg.c for 6 hr.
The second catalyst was prepared as follows: firstly, adding 10g of carbohydrate (glucose), 1.5g of zirconium citrate and 0.9g of yttrium isopropoxide into 1.5mol/L sulfuric acid solution, stirring for 2.5 hours at 400r/min, transferring the mixture into a reaction kettle, stirring for 9 hours at the temperature of 210 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing at the temperature of 550 ℃ for 7 hours in the nitrogen atmosphere to obtain the second catalyst.
The mixed catalyst is obtained by uniformly mixing a first catalyst and a second catalyst in a mass ratio of 1: 0.6.
Comparative example 1
A preparation method of methyl tert-butyl ether comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.01: 1 to obtain a mixed solution, and then the mixed solution is mixed for 1 hour -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and then the vapor is introduced into a main reactor which is preheated to 30 ℃ and is filled with a first catalyst for reaction under the conditions of 63 ℃ and 0.58MPa of pressure to obtain a reaction product;
(2) The reaction product was then worked up for 8h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual number of tower plates of the distillation tower is 12, the theoretical number of tower plates is 8, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th tower plate from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether;
(3) Finally, the crude methyl tert-butyl ether is added for 3h -1 Introducing the air speed of the mixed catalyst into a remill reactor which is preheated to 30 ℃ and filled with the mixed catalyst, remilling at the temperature of 45 ℃ and under the pressure of 0.5MPa, and condensing by a condenser to obtain the purified methyl tert-butyl ether.
Wherein, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat preservation layers.
In the step (2), the temperature of the bottom of the distillation tower is 120 ℃, the temperature of the top of the distillation tower is 50 ℃, the pressure of the top of the distillation tower is 0.4MPa, the liquid level of the bottom of the distillation tower is controlled at 35%, and the reflux ratio of the top of the distillation tower is 2.0.
The first catalyst was prepared as follows: firstly, soaking 10g of gamma-alumina by using 100g of 1mol/L sulfuric acid solution, and filtering to obtain a solid; and mixing 55g of ethyl orthosilicate and 150g of anhydrous formic acid under an anhydrous condition to prepare a mixed solution, adding 0.3g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic full oscillation and roasting to obtain the first catalyst.
The technological conditions of the impregnation are as follows: the mixture was immersed in 200W ultrasonic waves for 5 hours.
Mixing ethyl orthosilicate and anhydrous formic acid, and stirring for 50 minutes at 300 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: 500W ultrasonic vibration was performed for 3 hours.
The roasting process conditions are as follows: roasting at 400 deg.c for 5 hr.
The second catalyst was prepared as follows: firstly, adding 10g of carbohydrate (glucose), 1g of zirconium citrate and 0.8g of yttrium isopropoxide into 1mol/L sulfuric acid solution, stirring for 2 hours at 300r/min, transferring into a reaction kettle, stirring and treating for 8 hours at 200 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing at 500 ℃ for 6 hours under the nitrogen atmosphere to obtain the second catalyst.
The mixed catalyst is obtained by uniformly mixing a first catalyst and a second catalyst in a mass ratio of 1: 0.5.
Comparative example 2
A preparation method of methyl tert-butyl ether comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.01: 1 to obtain mixed liquid, and then the mixed liquid is mixed for 1 hour -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and then the vapor is introduced into a main reactor which is preheated to 30 ℃ and is filled with a first catalyst for reaction under the conditions of 63 ℃ and 0.58MPa of pressure to obtain a reaction product;
(2) The reaction product was then worked up for 8h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual number of tower plates of the distillation tower is 12, the theoretical number of tower plates is 8, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th tower plate from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether;
(3) Finally, the crude methyl tert-butyl ether is added for 3h -1 Introducing the air speed of the mixed catalyst into a remill reactor which is preheated to 30 ℃ and filled with the mixed catalyst, remilling at the temperature of 45 ℃ and under the pressure of 0.5MPa, and condensing by a condenser to obtain the purified methyl tert-butyl ether.
Wherein, the main reactor and the recycle reactor are stainless steel fixed bed integral reactors with specification D32mm multiplied by 2mm multiplied by 600mm and provided with heat preservation layers.
In the step (2), the temperature of the bottom of the distillation tower is 120 ℃, the temperature of the top of the distillation tower is 50 ℃, the pressure of the top of the distillation tower is 0.4MPa, the liquid level of the bottom of the distillation tower is controlled at 35%, and the reflux ratio of the top of the distillation tower is 2.0.
The first catalyst was prepared as follows: firstly, dipping 10g of gamma-alumina by using 100g of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; under the anhydrous condition, mixing 55g of ethyl orthosilicate and 150g of anhydrous formic acid to prepare a mixed solution, then adding 0.3g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic full oscillation and roasting to obtain the first catalyst; wherein, the cerium oxalate sulfuric acid solution is obtained by dissolving cerium oxalate in 1mol/L sulfuric acid solution with the weight being 12 times that of the solution.
The process conditions of the impregnation are as follows: the mixture was immersed in 200W ultrasonic waves for 5 hours.
Mixing ethyl orthosilicate and anhydrous formic acid, and stirring for 50 minutes at 300 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: 500W ultrasonic vibration was performed for 3 hours.
The roasting process conditions are as follows: roasting at 400 deg.c for 5 hr.
The second catalyst was prepared as follows: firstly, adding 10g of carbohydrate (glucose) and 1g of zirconium citrate into 1mol/L sulfuric acid solution, stirring for 2 hours at the speed of 300r/min, transferring the mixture into a reaction kettle, stirring and treating for 8 hours at the temperature of 200 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing for 6 hours at the temperature of 500 ℃ in a nitrogen atmosphere to obtain the second catalyst.
The mixed catalyst is obtained by uniformly mixing the first catalyst and the second catalyst according to the mass ratio of 1: 0.5.
Comparative example 3
A preparation method of methyl tert-butyl ether comprises the following specific steps:
(1) Firstly, methanol and isobutene are mixed according to the molar ratio of 1.01: 1 to obtain a mixed solution, and then the mixed solution is mixed for 1 hour -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and then the vapor is introduced into a main reactor which is preheated to 30 ℃ and is filled with a first catalyst for reaction under the conditions of 63 ℃ and 0.58MPa of pressure to obtain a reaction product;
(2) The reaction product was then worked up for 8h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual tower plate number of the distillation tower is 12, the theoretical tower plate number is 8, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the catalyst is obtained by removing the sulfur from the top of the distillation towerDischarging from the 5 th tower plate to obtain the methyl tert-butyl ether.
Wherein, the main reactor is a stainless steel fixed bed integral reactor with specification D32mm multiplied by 2mm multiplied by 600mm and an insulating layer.
In the step (2), the temperature of the bottom of the distillation tower is 120 ℃, the temperature of the top of the distillation tower is 50 ℃, the pressure of the top of the distillation tower is 0.4MPa, the liquid level of the bottom of the distillation tower is controlled at 35%, and the reflux ratio of the top of the distillation tower is 2.0.
The first catalyst was prepared as follows: firstly, dipping 10g of gamma-alumina by using 100g of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; under the anhydrous condition, mixing 55g of ethyl orthosilicate and 150g of anhydrous formic acid to prepare a mixed solution, then adding 0.3g of methanesulfonic acid and the solid into the mixed solution, and carrying out ultrasonic full oscillation and roasting to obtain the first catalyst; wherein, the cerium oxalate sulfuric acid solution is obtained by dissolving cerium oxalate in 1mol/L sulfuric acid solution with the weight being 12 times that of the solution.
The technological conditions of the impregnation are as follows: the mixture was immersed in 200W ultrasonic waves for 5 hours.
The tetraethoxysilane is mixed with the anhydrous formic acid and stirred for 50 minutes at the speed of 300 r/min.
The process conditions of the ultrasonic wave sufficient oscillation are as follows: 500W ultrasonic vibration was performed for 3 hours.
The roasting process conditions are as follows: roasting at 400 deg.c for 5 hr.
The second catalyst was prepared as follows: firstly, adding 10g of carbohydrate (glucose), 1g of zirconium citrate and 0.8g of yttrium isopropoxide into 1mol/L sulfuric acid solution, stirring for 2 hours at 300r/min, transferring into a reaction kettle, stirring and treating for 8 hours at 200 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing at 500 ℃ for 6 hours under the nitrogen atmosphere to obtain the second catalyst.
The yields of the methyl tert-butyl ether products (prepared from the same raw material) obtained in the examples 1 to 5 and the comparative examples 1 to 3 are counted respectively, the products are analyzed and detected, and the mass contents of the methyl tert-butyl ether and the methanol in the products are determined by specifically referring to SH/T1550-2012 gas chromatography for determining the purity and the impurities of the industrial methyl tert-butyl ether (MTBE).
The sulfur content was determined with reference to SH/T0689-2000 in ppm (by weight).
The product yield and analytical test results are shown in Table 1.
TABLE 1 product yield and analytical test results
As can be seen from Table 1, the method of examples 1 to 5 has high yield of methyl tert-butyl ether and high product purity, and the content of methyl tert-butyl ether can reach 100%.
Comparative example 1 in which cerium oxalate was omitted when the first catalyst was prepared, the methyl t-butyl ether yield was significantly lowered, and the product purity was also deteriorated, and comparative example 2 in which yttrium isopropoxide was omitted when the second catalyst was prepared, demonstrated that the first catalyst, the second catalyst had a very direct effect on the product yield, and also on the product purity; comparative example 3 omits the recycle step and the methyl t-butyl ether purity significantly worsens, indicating that the recycle step is of critical importance for product purification.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Claims (10)
1. A methyl tert-butyl ether recycling process is characterized by comprising the following specific steps:
(1) Firstly, reacting methanol and isobutene in a main reactor filled with a first catalyst to obtain a reaction product;
(2) Then introducing the reaction product into a distillation tower filled with a second catalyst, and carrying out distillation separation to obtain a crude product of the methyl tert-butyl ether;
(3) Then introducing the crude product of the methyl tert-butyl ether into a remilling reactor filled with a mixed catalyst to obtain purified methyl tert-butyl ether;
wherein the first catalyst is prepared by taking gamma-alumina, cerium oxalate, ethyl orthosilicate, anhydrous formic acid, 1-2 mol/L sulfuric acid solution and methane sulfonic acid as raw materials; the second catalyst is prepared by taking a carbohydrate, zirconium citrate and yttrium isopropoxide as raw materials; the mixed catalyst is obtained by uniformly mixing a first catalyst and a second catalyst according to the mass ratio of 1: 0.5-0.7.
2. The methyl tert-butyl ether recycling process according to claim 1, wherein the main reactor and the recycling reactor are stainless steel fixed bed integral reactors with specification D32mm x 2mm x 600mm and an insulating layer.
3. A process according to claim 1, wherein in step (1), methanol and isobutylene are mixed in a molar ratio of 1.01-1.03: 1 to obtain a mixture, and the mixture is then mixed for 1-2 hours -1 The air speed of the reactor is pressed into an evaporator for gasification to obtain a vapor, and then the vapor is introduced into a main reactor preheated to 30-35 ℃ for reaction under the conditions of 63-67 ℃ and 0.58-0.64 MPa to obtain a reaction product.
4. The methyl tert-butyl ether recycling process according to claim 1, wherein in the step (2), the reaction product is reacted for 8-10 h -1 The space velocity of the catalyst is introduced into a distillation tower filled with a second catalyst, the actual number of tower plates of the distillation tower is 12-15, the theoretical number of tower plates is 8-10, unreacted methanol and isobutene are discharged from the top of the distillation tower, sulfides are discharged from the bottom of the distillation tower, and the sulfides are discharged from the 5 th-6 th tower plates from the bottom of the distillation tower, namely the crude product of the methyl tert-butyl ether.
5. A methyl tert-butyl ether recycling process according to claim 4, characterized in that the temperature of the bottom of the distillation column is 120-130 ℃, the temperature of the top of the distillation column is 50-55 ℃, the pressure of the top of the distillation column is 0.4-0.45 MPa, the liquid level of the bottom of the distillation column is controlled at 35-50%, and the reflux ratio of the top of the distillation column is 2.0-2.5.
6. The methyl tert-butyl ether recycling process according to claim 1, wherein in the step (3), the crude methyl tert-butyl ether is recycled for 3 to 4 hours -1 Introducing the air speed of the reaction kettle into a remill reactor preheated to 30-35 ℃, remilling at the temperature of 45-50 ℃ and under the pressure of 0.5-0.6 MPa, and condensing by a condenser to obtain the purified methyl tert-butyl ether.
7. The methyl tert-butyl ether recycling process according to claim 1, wherein the first catalyst is prepared by the following method in parts by weight: firstly, dipping 10 parts of gamma-alumina by using 100-120 parts of cerous oxalate sulfuric acid solution, and filtering to obtain a solid; under the anhydrous condition, mixing 55-65 parts of ethyl orthosilicate and 150-170 parts of anhydrous formic acid to prepare a mixed solution, then adding 0.3-0.5 part of methane sulfonic acid and the solid into the mixed solution, fully oscillating by ultrasonic waves, and roasting to obtain the first catalyst; wherein, the cerous oxalate sulfuric acid solution is obtained by dissolving cerous oxalate in 1-2 mol/L sulfuric acid solution with the weight being 12-15 times of that of the cerous oxalate.
8. The methyl tert-butyl ether recycling process according to claim 7, wherein the impregnation process conditions are as follows: dipping for 5-7 hours under the ultrasonic oscillation of 200-300W.
9. The methyl tert-butyl ether recycling process according to claim 1, wherein the second catalyst is prepared by the following method in parts by weight: firstly, adding 10 parts of carbohydrate, 1-2 parts of zirconium citrate and 0.8-1 part of yttrium isopropoxide into 1-2 mol/L sulfuric acid solution, stirring for 2-3 hours at 300-400 r/min, transferring the mixture into a reaction kettle, stirring for 8-10 hours at 200-220 ℃, filtering to obtain a solid, washing with water, drying, and carbonizing for 6-8 hours at 500-600 ℃ in a nitrogen atmosphere to obtain the second catalyst.
10. A process according to claim 8, wherein said sugar compound is selected from any one of glucose, sucrose, maltose or fructose.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020142A (en) * | 2007-02-12 | 2007-08-22 | 浙江大学 | Catalyst for cracking methyl tert-butyl ether to prepare isobutylene and its prepn |
| US20130245348A1 (en) * | 2010-03-15 | 2013-09-19 | Total Research & Technology Feluy | Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis |
| CN103524309A (en) * | 2012-07-03 | 2014-01-22 | 北京安耐吉能源工程技术有限公司 | Purification method of crude methyl tertiary-butyl ether product and method for producing methyl tertiary-butyl ether |
| CN203904245U (en) * | 2014-06-11 | 2014-10-29 | 中国石油化工股份有限公司 | Device for synthesizing and separating low-sulfur methyl tert-butyl ether |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020142A (en) * | 2007-02-12 | 2007-08-22 | 浙江大学 | Catalyst for cracking methyl tert-butyl ether to prepare isobutylene and its prepn |
| US20130245348A1 (en) * | 2010-03-15 | 2013-09-19 | Total Research & Technology Feluy | Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis |
| CN103524309A (en) * | 2012-07-03 | 2014-01-22 | 北京安耐吉能源工程技术有限公司 | Purification method of crude methyl tertiary-butyl ether product and method for producing methyl tertiary-butyl ether |
| CN203904245U (en) * | 2014-06-11 | 2014-10-29 | 中国石油化工股份有限公司 | Device for synthesizing and separating low-sulfur methyl tert-butyl ether |
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