CN104250205B - The preparation method of methyl tertiary butyl ether and device thereof - Google Patents
The preparation method of methyl tertiary butyl ether and device thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
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- 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
- C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- 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
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- 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
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
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Abstract
The present invention relates to a kind of production technique of ethers, particularly a kind of method and production equipment thereof adopting the trimethyl carbinol and methyl alcohol reaction to prepare methyl tertiary butyl ether.The method is that the trimethyl carbinol and methanol mixed reaction generate gas mixture; Gas mixture enters into extraction tower and extracts, and iso-butylene, MTBE distillate from tower top, and the trimethyl carbinol, methyl alcohol, micro-MTBE, water and extraction agent flow out from tower reactor; Extraction tower overhead components enters catalytic distillation tower after supplementing methyl alcohol, and catalytic distillation column overhead contains methyl alcohol, the product of iso-butylene turns back in reactor and continues reaction, and MTBE is by the discharging of catalytic distillation tower tower reactor; The discharging of extraction tower reactor enters the first extraction agent recovery tower, the MTBE of the trimethyl carbinol, methyl alcohol and trace distillates from the first extraction agent recovery tower tower top, get back to reactor to react, extraction agent and water flow out from tower reactor, enter into the second extraction agent recovery tower, reclaim extraction agent by underpressure distillation and recycle.The invention solves the azeotropic problem of the trimethyl carbinol, water, make the trimethyl carbinol transformation efficiency reach 87% ~ 94%.
Description
Technical field
The present invention relates to a kind of production technique of ethers, particularly a kind of method and device thereof adopting the trimethyl carbinol and methyl alcohol reaction to prepare methyl tertiary butyl ether.
Background technology
Methyl tertiary butyl ether (MTBE) main application is: (1) is a kind of excellent stop bracket gasoline additive and octane promoter.(2) also can be used as chemical reagent, reaction solvent.Such as, as tert-butylation reagent in tertiary butyl reaction process, Anaesthetie Ether or tetrahydrofuran (THF) also can be replaced as reaction solvent.(3) also can be used for decomposing high-purity iso-butylene.
The existing refinery facilities structure of China can not meet the production of high-grade gasoline, namely catalytically cracked gasoline accounts for the ratio of about 80% in all kinds of gasoline, main production plant-catalytic reforming unit the proportion of high-grade gasoline is obviously on the low side, causes the high-octane number component of China's major part refinery not enough.It is most economical, effective means that MTBE raising catalytically cracked gasoline octane value is added in current employing.2011, domestic MTBE Apparent con-sumption was about 5.20Mt.
The prevailing technology of current production MTBE is that iso-butylene and methyl alcohol react, and employing Zeo-karb is catalyzer.Before and after 2012, the production equipment of propylene oxide is gone into operation at home successively, the output of the by product trimethyl carbinol also will increase, the production equipment of a set of annual output propylene oxide 253kt, annual coproduction trimethyl carbinol 332kt, this will cause the production capacity surplus of the trimethyl carbinol, and developing with the trimethyl carbinol is that the MTBE non-iso-butylene preparation technology of raw material has better future.
In prior art, EP0659722A1 for raw material with the trimethyl carbinol and methyl alcohol, adopts two methyltertiarvbutyl ether reactors to react, generates and the MTBE that purifies.This technique does not consider the recovery of unreacted methyl alcohol, the trimethyl carbinol, water, and using water as extraction agent, do not consider the azeotropic problem of the trimethyl carbinol, water, and how to dewater, these all result in lower reaction conversion ratio.After the second methyltertiarvbutyl ether reactor reaction, isobutene conversion also can only reach about 81%.
US5741953 describes the technique of a kind of trimethyl carbinol and methyl alcohol reaction generation MTBE.This patent employs two reactors and a catalytic distillation tower, and technical process is complicated, and investment cost is large.In a second reactor, the transformation efficiency of the trimethyl carbinol is the highest can only reach 84%, and the load of subsequent catalyst distillation tower is larger.This patent uses water as extraction agent, does not also consider the azeotropic problem of the trimethyl carbinol, water, thus the balance of impact reaction.
Summary of the invention
The object of this invention is to provide a kind of method adopting the trimethyl carbinol and methyl alcohol reaction to prepare methyl tertiary butyl ether, the method achieve the conversion completely of iso-butylene, improve the yield of MTBE, avoid and make to use water as the trimethyl carbinol of extraction agent generation, the azeotropic problem of water, invention also provides production equipment.
The preparation method of methyl tertiary butyl ether of the present invention is as follows:
(1) react: enter into reactor after the trimethyl carbinol and methanol mixed and carry out reacting the gas mixture generated containing the trimethyl carbinol, methyl alcohol, MTBE, iso-butylene and water;
(2) extract: the gas mixture that step (1) obtains enters into extraction tower and extracts, and iso-butylene, MTBE distillate from extraction tower tower top, the trimethyl carbinol, methyl alcohol, micro-MTBE, water and extraction agent flow out from extraction tower reactor;
(3) catalytic distillation: the iso-butylene that step (2) obtains, MTBE enter into catalytic distillation tower together and carry out catalytic distillation after supplementing methyl alcohol, catalytic distillation column overhead contains methyl alcohol, the product of iso-butylene turns back in reactor and continues reaction, and the outlet of MTBE autocatalysis distillation tower tower reactor is flowed out;
(4) extraction agent reclaims: the trimethyl carbinol that step (2) obtains, methyl alcohol, micro-MTBE, water and extraction agent enter the first extraction agent recovery tower after extraction tower reactor flows out, the MTBE of the trimethyl carbinol, methyl alcohol and trace distillates from the first extraction agent recovery tower tower top, get back to reactor to react, extraction agent and water flow out from tower reactor, enter into the second extraction agent recovery tower, by underpressure distillation, water distillates from tower top, and extraction agent is got back to extraction tower and recycled.
Described reactor is the fixed-bed reactor of one or more parallel connections.
Adopt method provided by the invention, the transformation efficiency of the trimethyl carbinol and yield are all very high, substantially do not lose.Extraction agent and water are by underpressure distillation, and good separating effect, does not exist azeotropic composition, separate substantially completely.Technical process is simple, and production cost is low, can obtain qualified MTBE product.
The described device realizing aforesaid method, comprises the reactor of one or more parallel connection, an extraction tower, the first extraction agent recovery tower, the second extraction agent recovery tower and a catalytic distillation tower; Wherein reactor is connected successively with extraction tower, catalytic distillation tower, and extraction tower is also connected successively with the first extraction agent recovery tower, the second extraction agent recovery tower, and catalytic distillation tower is connected with reactor, and the first extraction agent recovery tower is connected with reactor.
The gas-liquid extraction tower that described extraction tower is made up of column plate or filler.
The first described extraction agent recovery tower is the distillation tower of the normal pressure of column plate or filler composition.
The second described extraction agent recovery tower is the distillation tower of the decompression of column plate or filler composition.
The gas liquid reaction distillation tower that described catalytic distillation tower is made up of column plate or filler.
The gas liquid reaction distillation tower that described catalytic distillation tower is made up of column plate or filler.
The preferred fixed-bed reactor of described reactor.
In technique scheme:
Described extraction tower operational condition is: solvent molar ratio (i.e. extraction agent and mixed gas mol ratio) 2:1 ~ 10:1, preferred 3:1 ~ 5:1; Tower top pressure is 0.2 ~ 1.5Mpa, preferably 0.5 ~ 1.2Mpa; Extraction temperature 20 ~ 120 DEG C, preferably 40 ~ 80 DEG C.
Extraction tower extraction agent used have in ethylene glycol or octanol one or both, preferred ethylene glycol.
The first described extraction agent recovery tower operational condition is: tower top pressure is normal pressure, preferably 0.05 ~ 0.2Mpa; Tower top temperature is 30 ~ 80 DEG C, preferably 40 ~ 55 DEG C; The reflux ratio of tower is 0.1 ~ 25, preferably 2 ~ 5; Tower reactor pressure 0.1 ~ 0.3Mpa, preferably 0.1 ~ 0.2Mpa; Bottom temperature is 85 ~ 115 DEG C, preferably 90 ~ 110 DEG C.
The second described extraction agent recovery tower operational condition is: tower top pressure vacuum tightness 10-30KPa, preferably 15 ~ 25KPa; Tower top temperature is 30 ~ 80 DEG C, preferably 45 ~ 60 DEG C; The reflux ratio of tower is 0.1 ~ 25, preferably 0.5 ~ 3; Pressure reduction 5 ~ the 20KPa of tower, preferably 8 ~ 12KPa; Bottom temperature is 90 ~ 180 DEG C, preferably 130 ~ 150 DEG C.
Described fixed-bed reactor operational condition is: temperature of reaction 80 ~ 150 DEG C, preferably 120 ~ 140 DEG C; Reaction pressure 0.8 ~ 2.3MPa, preferably 1.3 ~ 1.8MPa; Air speed 0.2 ~ 5h
-1, preferably 0.5 ~ 1.5h
-1.The raw materials components mole ratio of methyl alcohol and the trimethyl carbinol is 1 ~ 5:1, preferably 2 ~ 3:1.
Described catalytic distillation tower operational condition is: tower top pressure is 0.3 ~ 0.8MPa, preferably 0.5 ~ 0.6MPa; Air speed 0.2 ~ 5h
-1, preferably 0.5 ~ 1.5h
-1, tower top temperature 50 ~ 80 DEG C, preferably 55 ~ 65 DEG C; The reflux ratio of tower is 0.1 ~ 25, preferably 5 ~ 8; Tower reactor pressure 0.1 ~ 1.0MPa, preferably 0.55 ~ 0.65MPa; Bottom temperature is 90 ~ 150 DEG C, preferably 115 ~ 135 DEG C.
Main containing the trimethyl carbinol, methyl alcohol, MTBE, iso-butylene and water in product mixtures after fixed bed reaction.
Through overhead product mainly MTBE, the iso-butylene of extraction tower, tower reactor extraction liquid main ingredient is MTBE, the water of methyl alcohol, the trimethyl carbinol, extraction agent, trace.
Top gaseous phase product through catalytic distillation tower is methyl alcohol, iso-butylene, and tower kettle product is MTBE.
Overhead product through the first extraction agent recovery tower is methyl alcohol, the trimethyl carbinol, micro-MTBE, and tower kettle product is extraction agent and water.
Overhead product through the second extraction agent recovery tower is water, and tower kettle product is extraction agent.
In technique scheme, processing parameter by adjustment fixed-bed reactor, catalytic distillation tower controls etherification reaction process, and in fixed-bed reactor, the transformation efficiency of the trimethyl carbinol can reach 87% ~ 94%, in catalytic distillation tower, the transformation efficiency of iso-butylene can reach 95% ~ 99%.
Iso-butylene is converted mainly into MTBE, and iso-butylene is here that tert-butyl alcohol dehydration generates, and be by product, but iso-butylene generates MTBE under the reaction conditions.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention is by the processing parameter of adjustment fixed-bed reactor, the trimethyl carbinol transformation efficiency can be made to reach 87% ~ 94%, decrease equipment investment, reduce material consumption energy consumption, improve the transformation efficiency of the trimethyl carbinol.
(2) adopt ethylene glycol as extraction agent, be compared to water and make extraction agent, the azeotropic problem of the trimethyl carbinol, water can be solved, water base in system is removed, carrying out of main reaction can be impelled to the right, effectively improve the transformation efficiency of the trimethyl carbinol.
Accompanying drawing explanation
Fig. 1 is present invention process schematic flow sheet;
In figure: 1, fixed-bed reactor; 2, extraction tower; 3, the first extraction agent recovery tower; 4, the second extraction agent recovery tower; 5, catalytic distillation tower; 6, the trimethyl carbinol and methanol mixed raw material; 7, reactor tower top reaction product; 8, extraction agent; 9, tower kettle product is extracted; 10, overhead product is extracted; 11, the top gaseous phase product of catalytic distillation tower; 12, MTBE product; 13, the first extraction agent recovery tower overhead product; 14, the first extraction agent recovery tower tower kettle product; 15, water; 16, second extraction agent recovery tower tower kettle product-extraction agent; 17, the methyl alcohol supplemented in catalytic distillation tower.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
The preparation method of the methyl tertiary butyl ether described in the embodiment of the present invention is as follows:
The mixing raw material 6 of the trimethyl carbinol and methyl alcohol enters into fixed-bed reactor 1, reactor tower top reaction product 7 enters into extraction tower 2, act on the extraction agent 8 of tower top, extraction overhead product 10 containing iso-butylene, MTBE flows out from tower top, catalytic distillation tower 5 is entered into the methyl alcohol 17 supplemented, the top gaseous phase product 11 of the catalytic distillation tower containing methyl alcohol and micro-iso-butylene turns back to fixed-bed reactor 1 entrance and continues reaction, and MTBE product 12 flows out from tower reactor outlet.The extraction tower kettle product 9 of the trimethyl carbinol, methyl alcohol, water and extraction agent flows out from extraction tower reactor, enters the first extraction agent recovery tower 3.The first extraction agent recovery tower overhead product 13 of the MTBE containing the trimethyl carbinol, methyl alcohol and trace flows out from the first extraction agent recovery tower 3 tower top, enter fixed-bed reactor 1 to react, the first extraction agent recovery tower tower kettle product 14 containing extraction agent and water flows out from tower reactor, enter into the second extraction agent recovery tower 4, pass through underpressure distillation, water 15 flows out from tower top, and second extraction agent recovery tower tower kettle product-extraction agent 16 is got back to extraction tower and recycled.
The mixture of methyl alcohol and the trimethyl carbinol adopts mol ratio to be 3:1, air speed 1h in the examples below
-1, investigating the impact of different catalysts on the trimethyl carbinol, iso-butylene, determine that fixed-bed reactor adopt beta-zeolite catalyzer, catalytic distillation tower adopts strong acid cation exchange resin catalyst, and each component concentration of analytical results is mass percent.
Embodiment 1-3
The component of the outlets products obtained under fixed-bed reactor differing temps is as following table 1, and pressure is 1.5MPa:
Fixed-bed reactor reaction result table under table 1 differing temps
Embodiment 4-6
By the middle part charging of the reaction product gas phase of the fixed reactor of embodiment 3 from extraction tower, extraction agent ethylene glycol injects in tower with the top of liquid form from extraction tower, and extraction results is in table 2.
Table 2 extraction tower data sheet
Embodiment 7-9
The extraction tower tower reactor material of embodiment 5 enters the first extraction agent recovery tower, and extraction tower tower reactor material consists of methyl alcohol, the trimethyl carbinol, ethylene glycol, MTBE, water.
First extraction agent recovery tower tower top pressure is normal pressure, tower top temperature 45 DEG C, bottom temperature 100 DEG C, all the other operational conditions and analytical data 3 as follows:
Table 3 first extraction agent recovery tower operational condition and analytical results table
| Embodiment | Reflux ratio | Tower reactor pressure/MPa | Tower reactor t butanol content % | Tower top ethylene glycol content, % |
| 7 | 1 | 0.1 | 0.003 | 0.008 |
| 8 | 2 | 0.1 | - | - |
| 9 | 3 | 0.1 | - | - |
Embodiment 10-12
The tower reactor composition of embodiment 9 enters the second extraction agent recovery tower, and adopt underpressure distillation mode, ethylene glycol separates completely with water.Operational condition and the analytical results of the second extraction agent recovery tower are as follows, and tower top temperature is 55 DEG C, the pressure reduction 15KPa of tower, and bottom temperature is 140 DEG C:
Table 4 second extraction agent recovery tower operational condition and analytical results table
Embodiment 13-16
Overhead product mainly MTBE, the iso-butylene of extraction tower, the overhead product of embodiment 5 enters into catalytic distillation tower, and employing storng-acid cation exchange resin is catalyzer, tower top pressure 0.65MPa, tower reactor pressure 0.6MPa, air speed 1h
-1, service temperature (i.e. sensitive spot temperature) is under 98 ~ 102 DEG C of conditions, and operational condition and the analytical results of catalytic distillation tower are as shown in table 5.
The operational condition of table 5 catalytic distillation tower and analytical results table
Embodiment 17
Embodiment 2 enter the operational condition of each tower and analytical results as follows, all the other are as the process of embodiment 1.
Table 6 extraction tower data sheet
| Solvent ratio | Pressure/MPa | Temperature | Tower top t butanol content, % | Tower reactor iso-butylene content, % |
| 2 | 0.5 | 60 | 0.023 | 0.003 |
Table 7 first extraction agent recovery tower operational condition and analytical results table
| Reflux ratio | Pressure/MPa | Tower reactor t butanol content % | Tower top ethylene glycol content, % |
| 2 | 0.1 | 0.002 | 0.003 |
Note: tower top temperature 40 DEG C, bottom temperature 110 DEG C
The operational condition of table 8 second extraction agent recovery tower and analytical results table
| Reflux ratio | Vacuum tightness/KPa | Tower reactor water-content % | Tower top ethylene glycol content, % |
| 0.5 | 15 | - | - |
Note: tower top temperature is 45 DEG C, the pressure reduction 10KPa of tower, bottom temperature is 130 DEG C
The operational condition of table 9 catalytic distillation tower and analytical results table
Note: tower top pressure 0.6MPa, tower reactor pressure 0.8MPa
Embodiment 18
Embodiment 3 enter into the operational condition of each tower and analytical results as follows, all the other are as the process of embodiment 1.
Table 10 extraction tower data sheet
| Solvent ratio | Pressure/MPa | Temperature | Tower top t butanol content, % | Tower reactor iso-butylene content, % |
| 3 | 0.6 | 60 | 0.008 | 0.05 |
Table 11 first extraction agent recovery tower operational condition and analytical results table
| Reflux ratio | Pressure/MPa | Tower reactor t butanol content % | Tower top ethylene glycol content, % |
| 1 | 0.1 | 0.003 | 0.008 |
Note: tower top temperature 55 DEG C, bottom temperature 90 DEG C
The operational condition of table 12 second extraction agent recovery tower and analytical results table
| Reflux ratio | Vacuum tightness/KPa | Tower reactor water-content % | Tower top ethylene glycol content, % |
| 1 | 15 | - | - |
Note: tower top temperature is 60 DEG C, the pressure reduction 12KPa of tower, bottom temperature is 150 DEG C
The operational condition of table 13 catalytic distillation tower and analytical results table
Note: tower top pressure 0.5MPa, tower reactor pressure 0.5MPa.
Claims (10)
1. a preparation method for methyl tertiary butyl ether, is characterized in that comprising the following steps:
(1) react: enter into reactor after the trimethyl carbinol and methanol mixed and carry out reacting the gas mixture generated containing the trimethyl carbinol, methyl alcohol, MTBE, iso-butylene and water;
(2) extract: the gas mixture that step (1) obtains enters into extraction tower and extracts, and iso-butylene, MTBE distillate from extraction tower tower top, the trimethyl carbinol, methyl alcohol, micro-MTBE, water and extraction agent flow out from extraction tower reactor;
(3) catalytic distillation: the iso-butylene that step (2) obtains, MTBE enter into catalytic distillation tower together and carry out catalytic distillation after supplementing methyl alcohol, catalytic distillation column overhead contains methyl alcohol, the product of iso-butylene turns back in reactor and continues reaction, and the outlet of MTBE autocatalysis distillation tower tower reactor is flowed out;
(4) extraction agent reclaims: the trimethyl carbinol that step (2) obtains, methyl alcohol, micro-MTBE, water and extraction agent enter the first extraction agent recovery tower after extraction tower reactor flows out, the MTBE of the trimethyl carbinol, methyl alcohol and trace distillates from the first extraction agent recovery tower tower top, get back to reactor to react, extraction agent and water flow out from tower reactor, enter into the second extraction agent recovery tower, by underpressure distillation, water distillates from tower top, and extraction agent is got back to extraction tower and recycled;
Described extraction agent is ethylene glycol.
2. the preparation method of methyl tertiary butyl ether according to claim 1, is characterized in that: described reactor operating condition is: temperature of reaction 80 ~ 150 DEG C, reaction pressure 0.8 ~ 2.3MPa, air speed 0.2 ~ 5h
-1, methyl alcohol and trimethyl carbinol raw materials components mole ratio are 1 ~ 5:1, and described reactor is the fixed-bed reactor of one or more parallel connections.
3. the preparation method of methyl tertiary butyl ether according to claim 1, is characterized in that: described extraction tower operational condition is: solvent molar ratio is 2:1 ~ 10:1, and tower top pressure is 0.2 ~ 1.5Mpa, and extraction temperature is 20 ~ 120 DEG C.
4. the preparation method of methyl tertiary butyl ether according to claim 1, it is characterized in that: the first described extraction agent recovery tower operational condition is: tower top pressure is normal pressure, tower top temperature is 30 ~ 80 DEG C, the reflux ratio of tower is 0.1 ~ 25, tower reactor pressure 0.1 ~ 0.3Mpa, bottom temperature is 85 ~ 115 DEG C.
5. the preparation method of methyl tertiary butyl ether according to claim 1, it is characterized in that: the second described extraction agent recovery tower operational condition is: tower top pressure vacuum tightness 10-30KPa, tower top temperature is 30 ~ 80 DEG C, the reflux ratio of tower is 0.1 ~ 25, pressure reduction 5 ~ the 20KPa of tower, bottom temperature is 90 ~ 180 DEG C.
6. the preparation method of methyl tertiary butyl ether according to claim 1, is characterized in that: described catalytic distillation tower operational condition is: tower top pressure is 0.3 ~ 0.8MPa, air speed 0.2 ~ 5h
-1, tower top temperature 50 ~ 80 DEG C, the reflux ratio of tower is 0.1 ~ 25; Tower reactor pressure 0.1 ~ 1.0MPa, bottom temperature is 90 ~ 150 DEG C.
7. realize a device for method described in claim 1, it is characterized in that: the reactor comprising one or more parallel connection, an extraction tower, the first extraction agent recovery tower, the second extraction agent recovery tower and a catalytic distillation tower; Wherein reactor is connected successively with extraction tower, catalytic distillation tower, and extraction tower is also connected successively with the first extraction agent recovery tower, the second extraction agent recovery tower, and catalytic distillation tower is connected with reactor, and the first extraction agent recovery tower is connected with reactor.
8. device according to claim 7, is characterized in that: the gas-liquid extraction tower that described extraction tower is made up of column plate or filler; The first described extraction agent recovery tower is the distillation tower of the normal pressure of column plate or filler composition; The second described extraction agent recovery tower is the distillation tower of the decompression of column plate or filler composition.
9. device according to claim 7, is characterized in that: the gas liquid reaction distillation tower that described catalytic distillation tower is made up of column plate or filler.
10. device according to claim 7, is characterized in that: described reactor is fixed-bed reactor.
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| JP6440882B1 (en) * | 2018-03-30 | 2018-12-19 | 住友化学株式会社 | MTBE manufacturing apparatus, isobutylene manufacturing apparatus, MTBE manufacturing method, and isobutylene manufacturing method |
| CN108774100B (en) * | 2018-04-28 | 2020-01-21 | 信汇科技有限公司 | Combined method for preparing methyl tert-butyl ether and isobutene from tert-butyl alcohol and methanol |
| WO2022018600A1 (en) * | 2020-07-21 | 2022-01-27 | Sabic Global Technologies B.V. | System and method for production of mtbe |
| CN112062660A (en) * | 2020-09-21 | 2020-12-11 | 浙江信汇新材料股份有限公司 | Method for recycling low-concentration tert-butyl alcohol dehydration reaction by-product |
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