CN108440255A - A kind of synthetic method of high-purity methyl tertbutyl ether - Google Patents
A kind of synthetic method of high-purity methyl tertbutyl ether Download PDFInfo
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- CN108440255A CN108440255A CN201810378751.5A CN201810378751A CN108440255A CN 108440255 A CN108440255 A CN 108440255A CN 201810378751 A CN201810378751 A CN 201810378751A CN 108440255 A CN108440255 A CN 108440255A
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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
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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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
Abstract
The invention discloses a kind of synthetic methods of high-purity methyl tertbutyl ether, are related to chemical raw material synthesis field；It is raw material, the obtained thick methyl tertiary butyl ether(MTBE) of catalyst reaction by isobutene and methanol, thick methyl tertiary butyl ether(MTBE) sum aggregate sulphur agent is uniformly mixed, baking is stirred in vacuum drying oven, mixed liquor after baking is sent into destilling tower, the sulfur-containing mixture of collection is flowed out from bottom of tower, and methyl tertiary butyl ether(MTBE) after purification is flowed out from tower top；Sulfur impurity is absorbed with collection sulphur agent; it is simple for process controllable; good impurity removing effect, in collecting sulphur agent ingredient, part ferrous oxalate can be by potassium permanganate oxidation at ferric oxalate; carbon nanotube is sintered through special atmosphere oven, after reaction kettle processing; surface will produce rough shape, and subregion can form crackle, increase the adsorption activity and adsorption surface area of carbon nanotube; silver chlorate and cobalt nitrate, silica gel are used cooperatively, and desulfurization can be made more thorough.
Description
Technical field：
The present invention relates to chemical raw material synthesis fields, and in particular to a kind of synthetic method of high-purity methyl tertbutyl ether.
Background technology：
Methyl tertiary butyl ether(MTBE) (MTBE) is a kind of high-octane rating (research octane number (RON) 115) gasoline additive, and chemistry is oxygen-containing
Amount is much lower compared with methanol, is conducive to warming up and saves fuel, evaporation latent heat is low, advantageous to cold start-up, is usually used in unleaded gas and low
The blending of lead oil.Methyl tertiary butyl ether(MTBE) can also be cracked into isobutene again, as rubber and the raw material of other chemical products.Matter
Best methyl tertiary butyl ether(MTBE) is measured, medicine is may be used as, is medicine intermediate.
Octane enhancing additives of the MTBE as gasoline may additionally facilitate cleaning burning, reduce in addition to it can increase gasoline oxygen content
Automobile hazardous emission pollutes.MTBE has certain solubility in water, therefore, mainly due to letting out for underground and aboveground gasoline basin
Leakage, the U.S. is found that MTBE more and more in underground drinking water body.Even if MTBE will also result in water quality in very low concentrations and dislike
It is smelly.MTBE is classified as the possible carcinogen of the mankind by U.S.EPA.
The methyl tertiary butyl ether(MTBE) impurity content produced at present is more, needs by multiple tracks removal of impurities process so that production cost
Height, low production efficiency, especially sulfide content are more, seriously affect the use of methyl tertiary butyl ether(MTBE).
Invention content：
Technical problem to be solved by the present invention lies in a kind of synthetic method of high-purity methyl tertbutyl ether is provided, prepare
Methyl tertiary butyl ether(MTBE) impurity content it is few, purity is high, simple production process, controllable.
The technical problems to be solved by the invention are realized using technical solution below：
A kind of synthetic method of high-purity methyl tertbutyl ether, includes the following steps：
(1) thick methyl tertiary butyl ether(MTBE) sum aggregate sulphur agent is uniformly mixed, the stirring baking 1-2h in 50-60 DEG C of vacuum drying oven；
(2) mixed liquor after toasting step (1) is sent into destilling tower, and control column bottom temperature is 85-125 DEG C, tower top temperature
Degree is 130-150 DEG C, and the sulfur-containing mixture of collection is flowed out from bottom of tower, and methyl tertiary butyl ether(MTBE) after purification is flowed out from tower top；
The collection sulphur agent is made of the raw material of following parts by weight：30-50 parts of ferrous oxalate, 26-42 parts of cobalt nitrate, potassium chloride
23-25 parts, 12-14 parts of silver chlorate, 6-8 parts of copper sulphate, 10-12 parts of silica gel, 20-30 parts of potassium permanganate, 50-70 parts of hexamethylene,
30-40 parts of acetophenone, 3-5 parts of carbon nanotube, 35-55 parts of ethyl alcohol.
Preferably, the preparation method of the collection sulphur agent is：
(1) ferrous oxalate, cobalt nitrate, potassium chloride, silver chlorate, copper sulphate are dissolved in deionized water, magnetic agitation
30min；
(2) silica gel and potassium permanganate are added in the mixed solution of step (1) preparation, react 1-2h at 45-55 DEG C；
(3) carbon nanotube is put into hydrogen atmosphere stove and is sintered 2-3h at 300-400 DEG C, natural cooling is added to 2-
In the hydrochloric acid solution of 4% mass concentration, the processing 10h at 120-150 DEG C is put into reaction kettle；
(4) hexamethylene, acetophenone and ethyl alcohol are uniformly mixed, sequentially add step (2), (3) prepare mixed solution and
Carbon nanotube stirs evenly, and the collection sulphur agent is made.
Preferably, the preparation method of the thick methyl tertiary butyl ether(MTBE) includes the following steps：
(1) isobutene decompression is cooled to liquid, is mixed with methanol, then mixed liquor is sent into expanded bed and reacts 2-3h；
(2) catalyst is added in the expanded bed after being reacted to step (1) and carries out catalysis reaction；
(3) product after reacting step (2) is sent into distillation column distillation, controls destilling tower temperature, is received at the top of destilling tower
Collect unreacted methanol, destilling tower bottom collection catalyst, methyl tertiary butyl ether(MTBE) is collected in destilling tower side.
Preferably, the preparation method of catalyst includes the following steps in the step (2)：
(1) mix 50-80 parts of styrene, 50-80 parts of divinylbenzenes, 60-100 parts of ethyl alcohol and 40-60 parts of deionized waters,
It is heated to 45-55 DEG C and stirs 20min, it is very fast to be cooled to 15-20 DEG C；
(2) 25-35 parts of sodium ethoxides, 20-30 parts of benzoyls and 35-50 parts of acetone, mixing are added into step (1) mixture
Uniformly, it is warming up to 80-85 DEG C of reaction 6-8h, polystyrene is made in washing, dry, filtering；
(3) 10-15 parts of catalysis sulfonating agents are added in the polystyrene prepared to step (2) and react 3-5h, polyphenyl second is made
Alkene ion exchange resin；
(4) polystyrene ion-exchange resin prepared by step (3) is added in the salpeter solution of 20% concentration and is stirred
20min, then 5-10 parts of hydrofluoric acid, 3-5 parts of potassium chloride, 5-8 parts of ammonium acetates are added into mixed liquor and are uniformly mixed, it is put into reaction kettle
In 5-7h is reacted at 120-130 DEG C, it is cooling, wash, it is dry, the catalyst is made.
Preferably, the catalysis sulfonating agent is made of the raw material of following parts by weight：20-30 parts of deionized waters, 12-15 parts of Asias
Sodium sulphate, 30-40 part ethyl alcohol, 18-20 parts of bromines, 13-15 parts of sulfuric acid, 16-20 parts of n-hexanes, 30-50 parts of dimethylformamides；Its
Preparation method is：
(1) deionized water and bromine are uniformly mixed, are put at -2 DEG C~-3 DEG C and freeze 2-3h；
(2) step (1) ice cube is thawed rapidly and is warming up to 55-60 DEG C, n-hexane and dimethyl formyl are added while stirring
Amine, after mixing, it is 6-8% to be warming up to 120-130 DEG C of heat preservation to mixture water content, cooling；
(3) sodium sulfite, ethyl alcohol, sulfuric acid are uniformly mixed, step (2) system is added drop-wise to dropwise using No. 10 needle applicators
It in standby mixture, is stirred when being added dropwise, rate of addition is 120 drops/minute, and 20min is stirred after being added dropwise, and is made described and urges
Change sulfonating agent.
The beneficial effects of the invention are as follows：The present invention provides a kind of synthetic methods of high-purity methyl tertbutyl ether, use
In destilling tower distillation process, sulfur impurity is absorbed with collection sulphur agent, simple for process controllable, good impurity removing effect, in collection sulphur agent
In ingredient, part ferrous oxalate can be by potassium permanganate oxidation at ferric oxalate, and carbon nanotube is sintered through special atmosphere oven, at reaction kettle
After reason, surface will produce rough shape, and subregion can form crackle, increase adsorption activity and the suction of carbon nanotube
Surface area, silver chlorate and cobalt nitrate, silica gel are used cooperatively, and can make the desulfurization more thorough.
Isobutene and the catalyst of methanol reaction select styrene in divinylbenzene, ethyl alcohol, deionized water, sodium ethoxide, benzene
Polystyrene is made in the mixed solution of formyl and acetone, polystyrene and catalysis sulfonating agent reaction are made polystyrene ion and hand over
Resin is changed, polystyrene ion-exchange resin is added in nitric acid, hydrofluoric acid, potassium chloride, ammonium acetate solution and is modified, is made
Isobutene and methanol can be reacted more thorough, product by the catalyst of isobutene and methanol reaction, the method for preparing catalyst
Impurity content is few, and purity is high, and polystyrene ion-exchange resin prepared by used catalysis sulfonating agent is catalyzed work after modified
Property increase so that final product methyl tertiary butyl ether(MTBE) purity is high, and by-product is few.
Specific implementation mode：
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below
Specific embodiment is closed, the present invention is further explained.
Embodiment 1：
A kind of synthetic method of high-purity methyl tertbutyl ether, includes the following steps：
(1) thick methyl tertiary butyl ether(MTBE) sum aggregate sulphur agent is uniformly mixed, the stirring baking 1h in 50 DEG C of vacuum drying ovens；
(2) mixed liquor after toasting step (1) is sent into destilling tower, and control column bottom temperature is 125 DEG C, and tower top temperature is
140 DEG C, the sulfur-containing mixture of collection is flowed out from bottom of tower, and methyl tertiary butyl ether(MTBE) after purification is flowed out from tower top；
The collection sulphur agent is made of the raw material of following parts by weight：50 parts of ferrous oxalate, 26 parts of cobalt nitrate, 25 parts of potassium chloride,
13 parts of silver chlorate, 8 parts of copper sulphate, 11 parts of silica gel, 30 parts of potassium permanganate, 50 parts of hexamethylene, 40 parts of acetophenone, 4 parts of carbon nanotube,
55 parts of ethyl alcohol.
It is described collection sulphur agent preparation method be：
(1) ferrous oxalate, cobalt nitrate, potassium chloride, silver chlorate, copper sulphate are dissolved in deionized water, magnetic agitation
30min；
(2) silica gel and potassium permanganate are added in the mixed solution of step (1) preparation, react 1h at 45 DEG C；
(3) carbon nanotube is put into hydrogen atmosphere stove and is sintered 3h at 300 DEG C, it is dense to be added to 2% mass for natural cooling
In the hydrochloric acid solution of degree, the processing 10h at 135 DEG C is put into reaction kettle；
(4) hexamethylene, acetophenone and ethyl alcohol are uniformly mixed, sequentially add step (2), (3) prepare mixed solution and
Carbon nanotube stirs evenly, and the collection sulphur agent is made.
The preparation method of the thick methyl tertiary butyl ether(MTBE) includes the following steps：
(1) isobutene decompression is cooled to liquid, is mixed with methanol, then mixed liquor is sent into expanded bed and reacts 2h；
(2) catalyst is added in the expanded bed after being reacted to step (1) and carries out catalysis reaction；
(3) product after reacting step (2) is sent into distillation column distillation, controls destilling tower temperature, is received at the top of destilling tower
Collect unreacted methanol, destilling tower bottom collection catalyst, methyl tertiary butyl ether(MTBE) is collected in destilling tower side.
The preparation method of catalyst includes the following steps in the step (2)：
(1) 75 parts of styrene, 75 parts of divinylbenzenes, 100 parts of ethyl alcohol and 50 parts of deionized waters mixed, be heated to 50 DEG C and stir
20min is mixed, it is very fast to be cooled to 15 DEG C；
(2) 35 parts of sodium ethoxides, 20 parts of benzoyls and 40 parts of acetone are added into step (1) mixture, are uniformly mixed, heating
To 80 DEG C of reaction 8h, polystyrene is made in washing, dry, filtering；
(3) 10 parts of catalysis sulfonating agents are added in the polystyrene prepared to step (2) and react 5h, polystyrene ion is made
Exchanger resin；
(4) polystyrene ion-exchange resin prepared by step (3) is added in the salpeter solution of 20% concentration and is stirred
20min, then 5 parts of hydrofluoric acid, 5 parts of potassium chloride, 6 parts of ammonium acetates are added into mixed liquor and are uniformly mixed, it is put into reaction kettle 125
5h is reacted at DEG C, it is cooling, it washs, it is dry, the catalyst is made.
The catalysis sulfonating agent is made of the raw material of following parts by weight：25 parts of deionized waters, 13 parts of sodium sulfites, 35 parts of second
Alcohol, 19 parts of bromines, 14 parts of sulfuric acid, 18 parts of n-hexanes, 40 parts of dimethylformamides；Preparation method is：
(1) deionized water and bromine are uniformly mixed, are put at -2 DEG C and freeze 3h；
(2) step (1) ice cube is thawed rapidly and is warming up to 55 DEG C, n-hexane and dimethylformamide are added while stirring,
After mixing, it is 6% to be warming up to 125 DEG C of heat preservations to mixture water content, cooling；
(3) sodium sulfite, ethyl alcohol, sulfuric acid are uniformly mixed, step (2) system is added drop-wise to dropwise using No. 10 needle applicators
It in standby mixture, is stirred when being added dropwise, rate of addition is 120 drops/minute, and 20min is stirred after being added dropwise, and is made described and urges
Change sulfonating agent.
Embodiment 2：
A kind of synthetic method of high-purity methyl tertbutyl ether, includes the following steps：
(1) thick methyl tertiary butyl ether(MTBE) sum aggregate sulphur agent is uniformly mixed, the stirring baking 2h in 55 DEG C of vacuum drying ovens；
(2) mixed liquor after toasting step (1) is sent into destilling tower, and control column bottom temperature is 85 DEG C, and tower top temperature is
130 DEG C, the sulfur-containing mixture of collection is flowed out from bottom of tower, and methyl tertiary butyl ether(MTBE) after purification is flowed out from tower top；
The collection sulphur agent is made of the raw material of following parts by weight：40 parts of ferrous oxalate, 42 parts of cobalt nitrate, 24 parts of potassium chloride,
12 parts of silver chlorate, 7 parts of copper sulphate, 10 parts of silica gel, 20 parts of potassium permanganate, 60 parts of hexamethylene, 35 parts of acetophenone, 3 parts of carbon nanotube,
45 parts of ethyl alcohol.
It is described collection sulphur agent preparation method be：
(1) ferrous oxalate, cobalt nitrate, potassium chloride, silver chlorate, copper sulphate are dissolved in deionized water, magnetic agitation
30min；
(2) silica gel and potassium permanganate are added in the mixed solution of step (1) preparation, react 2h at 55 DEG C；
(3) carbon nanotube is put into hydrogen atmosphere stove and is sintered 2h at 400 DEG C, it is dense to be added to 3% mass for natural cooling
In the hydrochloric acid solution of degree, the processing 10h at 150 DEG C is put into reaction kettle；
(4) hexamethylene, acetophenone and ethyl alcohol are uniformly mixed, sequentially add step (2), (3) prepare mixed solution and
Carbon nanotube stirs evenly, and the collection sulphur agent is made.
The preparation method of the thick methyl tertiary butyl ether(MTBE) includes the following steps：
(1) isobutene decompression is cooled to liquid, is mixed with methanol, then mixed liquor is sent into expanded bed and reacts 2h；
(2) catalyst is added in the expanded bed after being reacted to step (1) and carries out catalysis reaction；
(3) product after reacting step (2) is sent into distillation column distillation, controls destilling tower temperature, is received at the top of destilling tower
Collect unreacted methanol, destilling tower bottom collection catalyst, methyl tertiary butyl ether(MTBE) is collected in destilling tower side.
The preparation method of catalyst includes the following steps in the step (2)：
(1) 80 parts of styrene, 80 parts of divinylbenzenes, 80 parts of ethyl alcohol and 40 parts of deionized waters mixed, be heated to 55 DEG C and stir
20min is mixed, it is very fast to be cooled to 20 DEG C；
(2) 30 parts of sodium ethoxides, 25 parts of benzoyls and 50 parts of acetone are added into step (1) mixture, are uniformly mixed, heating
To 85 DEG C of reaction 7h, polystyrene is made in washing, dry, filtering；
(3) 10 parts of catalysis sulfonating agents are added in the polystyrene prepared to step (2) and react 4h, polystyrene ion is made
Exchanger resin；
(4) polystyrene ion-exchange resin prepared by step (3) is added in the salpeter solution of 20% concentration and is stirred
20min, then 8 parts of hydrofluoric acid, 3 parts of potassium chloride, 5 parts of ammonium acetates are added into mixed liquor and are uniformly mixed, it is put into reaction kettle 130
6h is reacted at DEG C, it is cooling, it washs, it is dry, the catalyst is made.
The catalysis sulfonating agent is made of the raw material of following parts by weight：30 parts of deionized waters, 15 parts of sodium sulfites, 40 parts of second
Alcohol, 20 parts of bromines, 15 parts of sulfuric acid, 20 parts of n-hexanes, 50 parts of dimethylformamides；Preparation method is：
(1) deionized water and bromine are uniformly mixed, are put at -3 DEG C and freeze 2h；
(2) step (1) ice cube is thawed rapidly and is warming up to 60 DEG C, n-hexane and dimethylformamide are added while stirring,
After mixing, it is 7% to be warming up to 120 DEG C of heat preservations to mixture water content, cooling；
(3) sodium sulfite, ethyl alcohol, sulfuric acid are uniformly mixed, step (2) system is added drop-wise to dropwise using No. 10 needle applicators
It in standby mixture, is stirred when being added dropwise, rate of addition is 120 drops/minute, and 20min is stirred after being added dropwise, and is made described and urges
Change sulfonating agent.
Embodiment 3：
A kind of synthetic method of high-purity methyl tertbutyl ether, includes the following steps：
(1) thick methyl tertiary butyl ether(MTBE) sum aggregate sulphur agent is uniformly mixed, the stirring baking 1h in 60 DEG C of vacuum drying ovens；
(2) mixed liquor after toasting step (1) is sent into destilling tower, and control column bottom temperature is 105 DEG C, and tower top temperature is
150 DEG C, the sulfur-containing mixture of collection is flowed out from bottom of tower, and methyl tertiary butyl ether(MTBE) after purification is flowed out from tower top；
The collection sulphur agent is made of the raw material of following parts by weight：30 parts of ferrous oxalate, 34 parts of cobalt nitrate, 23 parts of potassium chloride,
14 parts of silver chlorate, 6 parts of copper sulphate, 12 parts of silica gel, 25 parts of potassium permanganate, 70 parts of hexamethylene, 30 parts of acetophenone, 5 parts of carbon nanotube,
35 parts of ethyl alcohol.
It is described collection sulphur agent preparation method be：
(1) ferrous oxalate, cobalt nitrate, potassium chloride, silver chlorate, copper sulphate are dissolved in deionized water, magnetic agitation
30min；
(2) silica gel and potassium permanganate are added in the mixed solution of step (1) preparation, react 1h at 50 DEG C；
(3) carbon nanotube is put into hydrogen atmosphere stove and is sintered 2h at 350 DEG C, it is dense to be added to 4% mass for natural cooling
In the hydrochloric acid solution of degree, the processing 10h at 120 DEG C is put into reaction kettle；
(4) hexamethylene, acetophenone and ethyl alcohol are uniformly mixed, sequentially add step (2), (3) prepare mixed solution and
Carbon nanotube stirs evenly, and the collection sulphur agent is made.
The preparation method of the thick methyl tertiary butyl ether(MTBE) includes the following steps：
(1) isobutene decompression is cooled to liquid, is mixed with methanol, then mixed liquor is sent into expanded bed and reacts 3h；
(2) catalyst is added in the expanded bed after being reacted to step (1) and carries out catalysis reaction；
(3) product after reacting step (2) is sent into distillation column distillation, controls destilling tower temperature, is received at the top of destilling tower
Collect unreacted methanol, destilling tower bottom collection catalyst, methyl tertiary butyl ether(MTBE) is collected in destilling tower side.
The preparation method of catalyst includes the following steps in the step (2)：
(1) 50 parts of styrene, 50 parts of divinylbenzenes, 60 parts of ethyl alcohol and 60 parts of deionized waters mixed, be heated to 45 DEG C and stir
20min is mixed, it is very fast to be cooled to 18 DEG C；
(2) 25 parts of sodium ethoxides, 30 parts of benzoyls and 35 parts of acetone are added into step (1) mixture, are uniformly mixed, heating
To 80 DEG C of reaction 6h, polystyrene is made in washing, dry, filtering；
(3) 12 parts of catalysis sulfonating agents are added in the polystyrene prepared to step (2) and react 3h, polystyrene ion is made
Exchanger resin；
(4) polystyrene ion-exchange resin prepared by step (3) is added in the salpeter solution of 20% concentration and is stirred
20min, then 10 parts of hydrofluoric acid, 4 parts of potassium chloride, 8 parts of ammonium acetates are added into mixed liquor and are uniformly mixed, it is put into reaction kettle
7h is reacted at 120 DEG C, it is cooling, it washs, it is dry, the catalyst is made.
The catalysis sulfonating agent is made of the raw material of following parts by weight：20 parts of deionized waters, 12 parts of sodium sulfites, 30 parts of second
Alcohol, 18 parts of bromines, 13 parts of sulfuric acid, 16 parts of n-hexanes, 30 parts of dimethylformamides；Preparation method is：
(1) deionized water and bromine are uniformly mixed, are put at -2 DEG C and freeze 2h；
(2) step (1) ice cube is thawed rapidly and is warming up to 55 DEG C, n-hexane and dimethylformamide are added while stirring,
After mixing, it is 8% to be warming up to 130 DEG C of heat preservations to mixture water content, cooling；
(3) sodium sulfite, ethyl alcohol, sulfuric acid are uniformly mixed, step (2) system is added drop-wise to dropwise using No. 10 needle applicators
It in standby mixture, is stirred when being added dropwise, rate of addition is 120 drops/minute, and 20min is stirred after being added dropwise, and is made described and urges
Change sulfonating agent.
Comparative example：
The 3kg tert-butyl alcohols are weighed, 3g p-methyl benzenesulfonic acid (TsOH), 3kgCaO is added in the reaction vessel of 5L, is warming up to 100
DEG C start that 1.5kg methanol is added dropwise, time for adding keep the temperature 4 hours open steams and distills, obtains at 100-105 DEG C after 2 hours
3.35kg crude products, stratification, upper layer ether further obtain 3.2kg methyl tertiary butyl ether(MTBE)s by rectification and purification.
Composition detection is carried out to methyl tertiary butyl ether(MTBE) prepared by the above various embodiments and comparative example, it is as a result as follows：
By above table it is found that the impurity content that contains of methyl tertiary butyl ether(MTBE) prepared by the present invention is few, purity is high, yield
It is high.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (5)
1. a kind of synthetic method of high-purity methyl tertbutyl ether, which is characterized in that include the following steps：
(1) thick methyl tertiary butyl ether(MTBE) sum aggregate sulphur agent is uniformly mixed, the stirring baking 1-2h in 50-60 DEG C of vacuum drying oven；
(2) mixed liquor after toasting step (1) is sent into destilling tower, and control column bottom temperature is 85-125 DEG C, and tower top temperature is
130-150 DEG C, the sulfur-containing mixture of collection is flowed out from bottom of tower, and methyl tertiary butyl ether(MTBE) after purification is flowed out from tower top；
The collection sulphur agent is made of the raw material of following parts by weight：30-50 parts of ferrous oxalate, 26-42 parts of cobalt nitrate, potassium chloride 23-
25 parts, 12-14 parts of silver chlorate, 6-8 parts of copper sulphate, 10-12 parts of silica gel, 20-30 parts of potassium permanganate, 50-70 parts of hexamethylene, benzene second
30-40 parts of ketone, 3-5 parts of carbon nanotube, 35-55 parts of ethyl alcohol.
2. the synthetic method of high-purity methyl tertbutyl ether according to claim 1, which is characterized in that the collection sulphur agent
Preparation method is：
(1) ferrous oxalate, cobalt nitrate, potassium chloride, silver chlorate, copper sulphate are dissolved in deionized water, magnetic agitation 30min；
(2) silica gel and potassium permanganate are added in the mixed solution of step (1) preparation, react 1-2h at 45-55 DEG C；
(3) carbon nanotube is put into hydrogen atmosphere stove and is sintered 2-3h at 300-400 DEG C, natural cooling is added to 2-4% matter
In the hydrochloric acid solution for measuring concentration, the processing 10h at 120-150 DEG C is put into reaction kettle；
(4) hexamethylene, acetophenone and ethyl alcohol are uniformly mixed, sequentially add step (2), mixed solution prepared by (3) and carbon and receives
Mitron stirs evenly, and the collection sulphur agent is made.
3. the synthetic method of high-purity methyl tertbutyl ether according to claim 1, which is characterized in that the thick methyl- tert
The preparation method of butyl ether includes the following steps：
(1) isobutene decompression is cooled to liquid, is mixed with methanol, then mixed liquor is sent into expanded bed and reacts 2-3h；
(2) catalyst is added in the expanded bed after being reacted to step (1) and carries out catalysis reaction；
(3) by step (2) react after product be sent into distillation column distillation, control destilling tower temperature, destilling tower collected overhead not
Methyl tertiary butyl ether(MTBE) is collected in the methanol of reaction, destilling tower bottom collection catalyst, destilling tower side.
4. the synthetic method of high-purity methyl tertbutyl ether according to claim 3, which is characterized in that the step (2)
The preparation method of middle catalyst includes the following steps：
(1) 50-80 parts of styrene, 50-80 parts of divinylbenzenes, 60-100 parts of ethyl alcohol and 40-60 parts of deionized waters are mixed, heating
20min is stirred to 45-55 DEG C, it is very fast to be cooled to 15-20 DEG C；
(2) 25-35 parts of sodium ethoxides, 20-30 parts of benzoyls and 35-50 parts of acetone are added into step (1) mixture, mixing is equal
It is even, it is warming up to 80-85 DEG C of reaction 6-8h, polystyrene is made in washing, dry, filtering；
(3) 10-15 part catalysis sulfonating agents are added in the polystyrene prepared to step (2) and react 3-5h, obtained polystyrene from
Sub-exchange resin；
(4) polystyrene ion-exchange resin prepared by step (3) is added in the salpeter solution of 20% concentration and stirs 20min,
5-10 parts of hydrofluoric acid, 3-5 parts of potassium chloride, 5-8 parts of ammonium acetates are added into mixed liquor again to be uniformly mixed, are put into reaction kettle
5-7h is reacted at 120-130 DEG C, it is cooling, it washs, it is dry, the catalyst is made.
5. the synthetic method of high-purity methyl tertbutyl ether according to claim 4, which is characterized in that the catalysis sulfonation
Agent is made of the raw material of following parts by weight：20-30 parts of deionized waters, 12-15 parts of sodium sulfites, 30-40 parts of ethyl alcohol, 18-20 parts
Bromine, 13-15 part sulfuric acid, 16-20 parts of n-hexanes, 30-50 parts of dimethylformamides；Preparation method is：
(1) deionized water and bromine are uniformly mixed, are put at -2 DEG C~-3 DEG C and freeze 2-3h；
(2) step (1) ice cube is thawed rapidly and is warming up to 55-60 DEG C, n-hexane and dimethylformamide are added while stirring, mixed
After closing uniformly, it is 6-8% to be warming up to 120-130 DEG C of heat preservation to mixture water content, cooling；
(3) sodium sulfite, ethyl alcohol, sulfuric acid are uniformly mixed, step (2) preparation is added drop-wise to dropwise using No. 10 needle applicators
It in mixture, is stirred when being added dropwise, rate of addition is 120 drops/minute, and 20min is stirred after being added dropwise, and the catalysis sulphur is made
Agent.
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