CN109384653A - High-purity MTBE production technology - Google Patents
High-purity MTBE production technology Download PDFInfo
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- CN109384653A CN109384653A CN201710652996.8A CN201710652996A CN109384653A CN 109384653 A CN109384653 A CN 109384653A CN 201710652996 A CN201710652996 A CN 201710652996A CN 109384653 A CN109384653 A CN 109384653A
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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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- 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
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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
- C07C41/36—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- 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
- Y02P20/10—Process efficiency
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the production technology of high-purity MTBE a kind of, include the following steps: to become homogeneous after a, carbon four and part methanol are sufficiently mixed；B, mixed carbon four and part methanol carry out etherification reaction；C, the mixture after reaction and remaining methanol enter the second static mixer；D, enter catalytic rectifying tower from the mixture that the second static mixer comes out, the isobutene in the effect of catalyst, mixture reacts generation MTBE with methanol continuation catalytic distillation and separates C4, methanol with MTBE by rectifying；E, the crude product that catalytic rectifying tower tower bottom obtains enters rectifying column, is further purified MTBE product by rectifying；F, the top of the distillation column product carries out adsorption refining, guarantees that product reaches quality requirement.This invention ensures that the production of high-purity MTBE, while production technology is simplified, using adsorption refining technique, the number of plates of rectifying column is reduced, thereby reduces the energy consumption of separator.
Description
Technical field
The present invention relates to the production technologies of high-purity MTBE a kind of.
Background technique
Methyl tertiary butyl ether(MTBE) MTBE is a kind of colourless, transparent, high-octane liquid, the smell with ether.It has height
Octane number, suitable oxygen content are the ideal blend components for producing unleaded gas.Gasoline can be increased as gasoline additive
Octane number, and chemical property is stablized, and high combustion efficiency can inhibit the generation of ozone, and the gasoline for adding MTBE can also improve
The cold start characteristics and accelerating ability of automobile reduce the content of CO in tail gas.In addition, MTBE or a kind of important chemical industry are former
Material, high-purity isobutene is prepared by its cracking, and then prepare the products such as isobutene rubber, in terms of fine chemistry industry apply it is more,
But purity requirement is higher.
Currently, the MTBE purity range that commercial plant obtains is 90wt%-99.5wt%, it can be used for gasoline additive.
But when it is used for medication chemistry, due to the particularity of pharmaceuticals industry, it is desirable that corresponding MTBE purity in 99.99wt% or more,
Currently, the technique for being directly etherified production MTBE to be catalyzed carbon four and cracking c_4 as raw material is unable to satisfy the quality requirement of product.
Current industrialized technique are as follows: first to be catalyzed carbon four and cracking c_4 as raw material, under the effect of the catalyst with methanol, produce
The MTBE of higher degree is obtained, then the MTBE carries out ether solution, obtain high-purity isobutene, then continue to be etherified after purification
Reaction produces high-purity MTBE.The production procedure of the technique is longer, and equipment is more, needs just to can guarantee high-purity by being etherified twice
The production of MTBE, the economy for eventually leading to the technique are poor.It is reported that raw as raw material using the tert-butyl alcohol and methanol in having for research
High-purity MTBE is produced, the process flow is opposite to be shortened, but the preparation cost of anhydrous tertiary butanol is higher, leads to the economy of the technique
It is not strong.
Summary of the invention
The object of the present invention is to provide a kind of high-purity MTBE production technologies, ensure that the production of high-purity MTBE, simplify simultaneously
Production technology using adsorption refining technique reduces the number of plates of rectifying column, thereby reduces the energy consumption of separator, mentions
The economy of device is risen.
A kind of production technology of high-purity MTBE, includes the following steps:
A, become after carbon four and part methanol are sufficiently mixed homogeneous；
B, mixed carbon four and part methanol carry out etherification reaction；
C, the mixture after reaction and remaining methanol enter the second static mixer；
D, enter catalytic rectifying tower from the mixture that the second static mixer comes out, in the effect of catalyst, mixture
Isobutene and methanol continue catalytic distillation and react generation MTBE to separate C4, methanol with MTBE by rectifying；
E, the crude product that catalytic rectifying tower tower bottom obtains enters rectifying column, is further mentioned MTBE product by rectifying
It is pure；
F, the top of the distillation column product carries out adsorption refining, guarantees that product reaches quality requirement.
The amount of methanol is the 10%--20% of methanol quality in step b in step c.
The composition of mixing carbon four for the crude product and use that catalytic rectifying tower tower bottom obtains has relationship, predominantly MTBE, still
Also have some other products, such as MSBE, methanol, light dydrocarbon etc..
The top of the distillation column product thinks similar, predominantly MTBE with catalytic rectifying tower tower bottom product, impurity MSBE, methanol,
Light dydrocarbon etc., but impurity content will be significantly less than catalytic rectifying tower tower bottom product
The carbon four is mixing carbon four, mixes carbon four by iso-butane, normal butane, isobutene, 1- butylene or 2- butylene
Several compositions.
Mixing 1- butylene and 2- butene content range in carbon four is 0-10wt%；In preferred mixing carbon four 1- butylene and
2- butene content range 0-1wt%.Mixing carbon four be made of iso-butane, normal butane and isobutene, the 1- butylene of lower content and
2- butylene.
Mixing isobutene content in carbon four is 5-95wt%.Isobutene content range 20- in preferred mixing carbon four
45wt%.
The catalyst that etherification reaction uses is solid acid catalyst, molecular sieve catalyst or ion-exchange resin catalyst.
The catalyst that preferred etherification reaction uses is cation exchange resin catalyst.
The molar ratio range of methanol and isobutene is 1.0-1.5 in static mixer.In preferred second static mixer
The molar ratio range of methanol and isobutene is 1.2-1.4.
The mass range of MTBE is 95-99.9wt% from the MTBE product that catalytic rectifying tower tower bottom obtains, and carbon four contains
Amount range is 0-0.01wt%, and the range of MSBE is 0-0.3wt%；
The preferred scope of MTBE content is 98.5-99.9wt% in catalytic rectifying tower bottom product.
The preferred scope of four content of carbon is 0-0.005wt% in catalytic rectifying tower bottom product.
The preferred scope of MSBE content is 0-0.1wt% in catalytic rectifying tower bottom product.
The mass range of MTBE is 99.9-99.99wt% in the product that rectifying column obtains, and the mass range of MSBE is 0-
0.01wt%, the mass range of methanol are 0-0.01wt%.
The preferred scope of MTBE content is 99.9-99.99wt% in the product of the top of the distillation column.
The preferred scope of MSBE content is 0-0.003wt% in the product of the top of the distillation column.
The preferred scope of methanol content is 0-0.003wt% in the product of the top of the distillation column.
The adsorbent of adsorption reaction is molecular sieve or absorption resin.Preferred adsorbent is adsorbent of molecular sieve.
Adsorbent of molecular sieve is modified 5A molecular sieve.
Modified 5A molecular sieve is to carry out impregnating active to 5A molecular sieve using alkalescent substance aqueous solution to be modified, and is then existed
2h is dried at 120 DEG C, is then placed on spare in drier；Alkalescent substance be sodium carbonate, sodium bicarbonate, sodium sulfite and
Disodium hydrogen phosphate.
Adsorption temp range is 30-50 DEG C, pressure limit 0-1MPaG, the volume ratio of fluid flow volume and adsorbent
Range is 4-20.
The production technology of high-purity MTBE specifically comprises the following steps:
A, enter after static mixer is sufficiently mixed after carbon four and methanol mixing as homogeneous；
B, the mixture come out from static mixer carries out etherification reaction into reactor, generates MTBE；
C, enter the second static mixer from the methanol of the reactor mixture come out and supplement；
D, enter catalytic rectifying tower from the mixture that the second static mixer comes out, in the effect of catalyst, mixture
Isobutene and methanol the reaction was continued generate MTBE.By rectifying, C4, methanol are separated with MTBE；
E, the product that catalytic rectifying tower tower bottom obtains enters rectifying column, is further mentioned MTBE product by rectifying
It is pure；
F, the top of the distillation column product enters the progress adsorption refining of fixed bed reaction absorber, guarantees that product reaches quality and wants
It asks.
The production technology of the high-purity MTBE of the present invention mainly includes the first static mixer, reactor, the second static mixing
Device, catalytic rectifying tower, rectifying column and fixed bed reaction absorber.
The reactor that etherification reaction uses is fixed bed reactors, mixed phase bed reactor or expanded bed reactor.
The reactor that preferred etherification reaction uses is mixed phase bed reactor.
Compared with prior art, beneficial effect possessed by the invention patent is:
Technique through the invention simplifies the technological process of production, realizes the production of high-purity MTBE, has expanded answering for MTBE
Use field.By using adsorption refining technique, reduce the number of plates of rectifying column, and then greatly reduces the energy consumption of separator
It can reduce 30-40% energy consumption, greatly improve the economy of device.
Detailed description of the invention
Fig. 1 is the flow diagram of present invention process.
Wherein: I, the first static mixer, 2, reactor, the 3, second static mixer, 4, catalytic rectifying tower, 5, rectifying
Tower, 6, fixed bed reaction absorber.
Specific embodiment
The process flow of the following example are as follows:
A, enter after static mixer I is sufficiently mixed after carbon four and methanol mixing as homogeneous；
B, from the mixture of the static mixer I methanol come out and carbon four, etherification reaction is carried out into reactor 2, is generated
MTBE；
C, enter the second static mixer 3 from the methanol of the mixture come out of reactor 2 and supplement；
D, enter catalytic rectifying tower 4 from the mixture that the second static mixer 3 comes out, in the effect of catalyst, mixture
In isobutene and methanol the reaction was continued generate MTBE.By rectifying, C4, methanol are separated with MTBE；
E, the product that catalytic rectifying tower tower bottom obtains enters rectifying column 5, is further mentioned MTBE product by rectifying
It is pure；
F, 5 overhead product of rectifying column enters the progress adsorption refining of fixed bed reaction absorber 6, guarantees that product reaches quality and wants
It asks.
Wherein, in catalytic rectifying tower 4, the reaction was continued is existed with the conversion ratio for guaranteeing isobutene for isobutene and methanol
99.5wt%, while realizing the initial gross separation of MTBE and other materials.
Comparative example 1
The composition of four raw material of carbon is as shown in table 1, and methanol is primes.In high-purity MTBE production process, reactor 2 is with sun
Ion exchange resin is catalyst, and alcohol/alkene molar ratio is 1.1, and the volume space velocity of catalyst is 1.5, and reaction pressure is
0.6atm, reaction temperature are 50 DEG C；Using cation exchange resin as catalyst, alcohol/alkene molar ratio is catalytic rectifying tower 4
1.2, the volume space velocity of catalyst is 1.0, tower top pressure 0.6-0.7atm, and reaction temperature is 55 DEG C；The reflux ratio of rectifying column 5
It is 3.5, number of theoretical plate is 135 pieces, and final MTBE product purity is 99.991wt%.
Embodiment 1
The composition of four raw material of carbon is as shown in table 1, and methanol is primes.In high-purity MTBE production process, reactor 2 is with sun
Ion exchange resin is catalyst, and alcohol/alkene molar ratio is 1.1, and the volume space velocity of catalyst is 1.5, and reaction pressure is
0.6atm, reaction temperature are 50 DEG C；Using cation exchange resin as catalyst, alcohol/alkene molar ratio is catalytic rectifying tower 4
1.2, the volume space velocity of catalyst is 1.0, tower top pressure 0.6-0.7atm, and reaction temperature is 65 DEG C；The reflux ratio of rectifying column 5
It is 3.5, number of theoretical plate is 20 pieces, and the adsorbent of VI adsorptive reactor is modified 5A molecular sieve, and air speed 10, temperature is 40 DEG C,
Pressure is 0.8MPa, and the composition of different location MTBE product is as shown in table 2.
1 carbon of table, four raw material forms wt%
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Iso-butane | 58.7 | 43.4 | 26.0 | 45.6 | 58.7 | 43.4 | 26.0 | 45.6 |
| Normal butane | 2.3 | 17.3 | 34.5 | 6.4 | 2.3 | 17.3 | 34.5 | 6.4 |
| 1- butylene | 0.3 | 0.2 | 2.3 | 5.2 | 0.3 | 0.2 | 2.3 | 5.2 |
| 2- butylene | 0.5 | 0.2 | 1.2 | 1.8 | 0.5 | 0.2 | 1.2 | 1.8 |
| Isobutene | 39.0 | 39.3 | 36.0 | 41.0 | 39.0 | 39.3 | 36.0 | 41.0 |
| It is total | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
The composition wt% of 2 different location MTBE product of table
As shown in Table 2, the purity of MTBE final products is 99.9937wt%.It is compared with comparative example it is found that by absorption essence
Technique processed significantly reduces the number of plates of rectifying column, reduces the energy consumption of device, improves the economy of device.
Comparative example 2
The composition of four raw material of carbon is as shown in table 1, and methanol is top grade product.In high-purity MTBE production process, reactor 2 is with sun
Ion exchange resin is catalyst, and alcohol/alkene molar ratio is 1.05, and the volume space velocity of catalyst is 2.0, and reaction pressure is
0.6atm, reaction temperature are 52 DEG C；Using cation exchange resin as catalyst, alcohol/alkene molar ratio is catalytic rectifying tower 4
1.25, the volume space velocity of catalyst is 1.2, tower top pressure 0.6-0.7atm, and reaction temperature is 55 DEG C；The reflux of rectifying column 5
Than being 3.5, number of theoretical plate is 107 pieces, and final MTBE product purity is 99.9919wt%.
Embodiment 2
The composition of four raw material of carbon is as shown in table 1, and methanol is top grade product.In high-purity MTBE production process, reactor 2 is with sun
Ion exchange resin is catalyst, and alcohol/alkene molar ratio is 1.05, and the volume space velocity of catalyst is 2.0, and reaction pressure is
0.6atm, reaction temperature are 52 DEG C；Using cation exchange resin as catalyst, alcohol/alkene molar ratio is catalytic rectifying tower 4
1.25, the volume space velocity of catalyst is 1.2, tower top pressure 0.6-0.7atm, and reaction temperature is 55 DEG C；The reflux of rectifying column 5
Than being 3.5, number of theoretical plate is 12 pieces；The adsorbent of VI adsorptive reactor is modified 5A molecular sieve, air speed 13, temperature 40
DEG C, the composition of pressure 0.8MPa, different location MTBE product are as shown in table 3.
The composition wt% of 3 different location MTBE product of table
As shown in Table 2, the purity of MTBE final products is 99.9952wt%.It is compared with comparative example it is found that by absorption essence
Technique processed significantly reduces the number of plates of rectifying column, reduces the energy consumption of device, improves the economy of device.
Comparative example 3
The composition of four raw material of carbon is as shown in table 1, and methanol is primes.In high-purity MTBE production process, reactor 2 is to divide
Son sieve is catalyst, and alcohol/alkene molar ratio is 1.05, and the volume space velocity of catalyst is 1.0, reaction pressure 0.6atm, instead
Answering temperature is 60 DEG C；For catalytic rectifying tower 4 using molecular sieve as catalyst, alcohol/alkene molar ratio is 1.15, and the volume of catalyst is empty
Speed is 0.5, tower top pressure 0.6-0.7atm, and reaction temperature is 65 DEG C；The reflux ratio of rectifying column 5 is 4.5, and number of theoretical plate is
247 pieces, final MTBE product purity is 99.9905wt%.
Embodiment 3
The composition of four raw material of carbon is as shown in table 1, and methanol is primes.In high-purity MTBE production process, reactor 2 is to divide
Son sieve is catalyst, and alcohol/alkene molar ratio is 1.05, and the volume space velocity of catalyst is 1.0, reaction pressure 0.6atm, instead
Answering temperature is 60 DEG C；For catalytic rectifying tower 4 using molecular sieve as catalyst, alcohol/alkene molar ratio is 1.15, and the volume of catalyst is empty
Speed is 0.5, tower top pressure 0.6-0.7atm, and reaction temperature is 65 DEG C；The reflux ratio of rectifying column 5 is 4.5, number of theoretical plate 35
Block；The adsorbent of VI adsorptive reactor is modified 5A molecular sieve, and air speed 8, temperature is 40 DEG C, pressure 0.7MPa, different positions
The composition for setting MTBE product is as shown in table 4.
The composition wt% of 4 different location MTBE product of table
As shown in Table 4, the purity of MTBE final products is 99.997wt%.It is compared with comparative example it is found that by absorption essence
Technique processed significantly reduces the number of plates of rectifying column, reduces the energy consumption of device, improves the economy of device.
Comparative example 4
The composition of four raw material of carbon is as shown in table 1, and methanol is top grade product.In high-purity MTBE production process, reactor 2 is with solid
For body acid as catalyst, alcohol/alkene molar ratio is 1.1, and the volume space velocity of catalyst is 0.8, reaction pressure 0.6atm, instead
Answering temperature is 55 DEG C；Catalytic rectifying tower 4 is using solid acid as catalyst, and alcohol/alkene molar ratio is 1.2, the volume of catalyst
Air speed is 0.8, tower top pressure 0.6-0.7atm, and reaction temperature is 60 DEG C；The reflux ratio of rectifying column 5 is 6.5, and number of theoretical plate is
273 pieces, final MTBE product purity is 99.9925wt%.
Embodiment 4
The composition of four raw material of carbon is as shown in table 1, and methanol is top grade product.In high-purity MTBE production process, reactor 2 is with solid
For body acid as catalyst, alcohol/alkene molar ratio is 1.1, and the volume space velocity of catalyst is 0.8, reaction pressure 0.6atm, instead
Answering temperature is 55 DEG C；Catalytic rectifying tower 4 is using solid acid as catalyst, and alcohol/alkene molar ratio is 1.2, the volume of catalyst
Air speed is 0.8, tower top pressure 0.6-0.7atm, and reaction temperature is 60 DEG C；The reflux ratio of rectifying column 5 is 5.5, and number of theoretical plate is
33 pieces；The adsorbent of VI adsorptive reactor is modified 5A molecular sieve, and air speed 3, temperature is 35 DEG C, pressure 0.6MPa, different
The composition of position MTBE product is as shown in table 5.
The composition wt% of 5 different location MTBE product of table
As shown in Table 5, the purity of MTBE final products is 99.995wt%.It is compared with comparative example it is found that by absorption essence
Technique processed significantly reduces the number of plates of rectifying column, reduces the energy consumption of device, improves the economy of device.
Claims (10)
1. a kind of high-purity MTBE production technology, which comprises the steps of:
A, become after carbon four and part methanol are sufficiently mixed homogeneous；
B, mixed carbon four and part methanol carry out etherification reaction；
C, the mixture after reaction and part methanol enter the second static mixer (3)；
D, enter catalytic rectifying tower (4) from the mixture that the second static mixer (3) come out, in the effect of catalyst, mixture
In isobutene with remaining methanol continue catalytic distillation and react generation MTBE to be divided C4, methanol and MTBE by rectifying
From；
E, the crude product that catalytic rectifying tower (4) tower bottom obtains enters rectifying column (5), is carried out MTBE product further by rectifying
Purification；
F, the top of the distillation column product carries out adsorption refining, guarantees that product reaches quality requirement.
2. high-purity MTBE production technology according to claim 1, which is characterized in that the carbon four is mixing carbon four, is mixed
Carbon four is closed to be made of several in iso-butane, normal butane, isobutene, 1- butylene or 2- butylene.
3. high-purity MTBE production technology according to claim 2, which is characterized in that 1- butylene and 2- butylene in mixing carbon four
Content range is 0-10wt%；Mixing isobutene content in carbon four is 5-95wt%.
4. high-purity MTBE production technology according to claim 1, which is characterized in that the catalyst that etherification reaction uses is solid
Body acid catalyst, molecular sieve catalyst or ion-exchange resin catalyst.
5. high-purity MTBE production technology according to claim 1, which is characterized in that methanol and isobutene in static mixer
Molar ratio range be 1.0-1.5.
6. high-purity MTBE production technology according to claim 1, which is characterized in that from catalytic rectifying tower (4), tower bottom is obtained
MTBE product in the mass range of MTBE be 95-99.9wt%, the content range of carbon four is 0-0.01wt%, the range of MSBE
For 0-0.3wt%；The mass range of MTBE is 99.9-99.99wt%, the quality model of MSBE in the product that rectifying column (5) obtains
It encloses for 0-0.01wt%, the mass range of methanol is 0-0.01wt%.
7. high-purity MTBE production technology according to claim 1, which is characterized in that the adsorbent of adsorption reaction is molecular sieve
Or absorption resin.
8. high-purity MTBE production technology according to claim 1, which is characterized in that adsorbent of molecular sieve is modified 5A points
Son sieve.
9. high-purity MTBE production technology according to claim 1, which is characterized in that modified 5A molecular sieve is using alkalescent
Substance aqueous solution carries out impregnating active to 5A molecular sieve and is modified, and 2h is then dried at 120 DEG C, is then placed in drier
It is spare；Alkalescent substance is sodium carbonate, sodium bicarbonate, sodium sulfite and disodium hydrogen phosphate.
10. high-purity MTBE production technology according to claim 1, which is characterized in that adsorption temp range is 30-50 DEG C,
Pressure limit is 0-1MPaG, and the volume ratio range of fluid flow volume and adsorbent is 4-20.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1694859A (en) * | 2002-11-21 | 2005-11-09 | 阿克奥化学技术有限公司 | Purification of methyl tertiary butyl ether |
| CN104829436A (en) * | 2015-05-12 | 2015-08-12 | 中建安装工程有限公司 | Device and method for deeply removing organic sulphides in methyl tertiary butyl ether (MTBE) |
| CN104892369A (en) * | 2015-05-22 | 2015-09-09 | 西安元创化工科技股份有限公司 | Production process of high-purity ethyl tert-butyl ether |
| CN105085198A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of chromatographic grade methyl tert-butyl ether |
| CN105582885A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Adsorbent prepared by utilizing molecular sieve contained waste catalyst, and removal method for methanol by using adsorbent |
-
2017
- 2017-08-02 CN CN201710652996.8A patent/CN109384653B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1694859A (en) * | 2002-11-21 | 2005-11-09 | 阿克奥化学技术有限公司 | Purification of methyl tertiary butyl ether |
| CN105085198A (en) * | 2014-05-16 | 2015-11-25 | 上海星可高纯溶剂有限公司 | Purification method of chromatographic grade methyl tert-butyl ether |
| CN105582885A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Adsorbent prepared by utilizing molecular sieve contained waste catalyst, and removal method for methanol by using adsorbent |
| CN104829436A (en) * | 2015-05-12 | 2015-08-12 | 中建安装工程有限公司 | Device and method for deeply removing organic sulphides in methyl tertiary butyl ether (MTBE) |
| CN104892369A (en) * | 2015-05-22 | 2015-09-09 | 西安元创化工科技股份有限公司 | Production process of high-purity ethyl tert-butyl ether |
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