CN104478644A - Method for preparing isobutylene from tert-butanol - Google Patents
Method for preparing isobutylene from tert-butanol Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity isobutylene from a low-concentration tert-butanol aqueous solution. The method comprises the following steps: (1) firstly respectively filling catalyst sections arranged in the middle of a catalytic distillation tower with theta-ring packing; and sectioning the catalyst and filling each catalyst section with the catalyst; (2) introducing the tert-butanol aqueous solution and deionized water into the catalytic distillation tower; carrying out heating distillation on the tert-butanol aqueous solution by virtue of a tower bottom reboiler to form a tert-butanol-water azeotrope, dehydrating tert-butanol in the tert-butanol-water azeotrope by virtue of a catalyst layer to generate isobutylene, enabling unreacted tert-butanol to be absorbed by virtue of deionized water to reach the catalyst layer and further dehydrating to generate isobutylene; and (3) producing high-purity isobutene at the top and ionized water at the tower bottom. The method has the advantages of simplicity in operation flow, low cost and high conversion rate and selectivity and the produced isobutylene is high in purity and the preparation efficiency is high.
Description
Technical field
The present invention relates to iso-butylene preparing technical field, particularly relate to a kind of method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution.
Background technology
Iso-butylene is a kind of important basic organic chemical industry raw material, and especially the research and development of the industrial chemicals that isoprene-isobutylene rubber, polyisobutene, methacrylonitrile etc. are important, make the demand of main raw material high-purity isobutylene increasing.
In industry, iso-butylene generally mixes with other isomeric butylene, occurs with the form of mixed c 4 or carbon-4.Boiling point difference wherein due to iso-butylene and n-butene is very little, to be separated by iso-butylene and uneconomical with the distillating method of routine from carbon four, and generally carbon four is all directly used as fuel and is burnt, and causes the waste of resource.
One of main method of existing production high-purity isobutylene obtains iso-butylene and methyl alcohol by methyl tertiary butyl ether (MTBE) ether solution.The method adopts the technique of traditional " an anti-multitower ", and namely a reactor is in order to the scission reaction of MTBE, and multitower is in order to refine and reclaim product and reactant MTBE.A kind of method of being produced isobutene polymer grade by methyl tertiary butyl ether ether solution is disclosed in Chinese patent CN103772113A.The method changes the iso-butylene weight-removing column in traditional ether solution and iso-butylene lightness-removing column into adsorption tower, and wherein, the sorbent material loaded in adsorption tower is LTA molecular sieve, amorphous silicon aluminium and FAU molecular sieve.But it is high still to there is temperature of reaction, in thick iso-butylene, by-products content is more, and later stage separating difficulty is large, and the shortcoming that Methanol product easily pollutes.
One of main method of existing production high-purity isobutylene is tert-butyl alcohol dehydration method.The method for raw material with high purity tert-butyl alcohol or lower concentration tertiary butanol aqueous solution, is made catalyzer with macropore sulfonic acid ion exchange resin, in fixed bed or catalytic rectifying tower, is carried out dehydration reaction.
In Chinese patent CN102633588A, disclose a kind of separation from carbon-4 prepare the method for high-purity isobutylene.In the method, from carbon-4, isobutylene separation is divided into three steps: in the first step carbon-4, iso-butylene hydration generates the trimethyl carbinol; Second step trimethyl carbinol dilute solution is refining obtains the highly purified trimethyl carbinol; 3rd Bushu's butanols generates high-purity isobutylene in catalytic rectifying tower dehydration.In the method, the second step trimethyl carbinol passes into catalytic distillation dehydration tower after trimethyl carbinol refining spearation tower is refining, increases cost of equipment; And adopt reflux type in catalytic distillation dehydration tower in the method, increase iso-butylene and the trimethyl carbinol in backflow material and react the chance of the by product such as Formed eight and carbon eight ether in catalytic reaction zone, the selectivity of the trimethyl carbinol reduces greatly.
A kind of method that dehydration of low-concentration tert butyl alcohol prepares iso-butylene is disclosed in Chinese patent CN102690159A.First the method utilizes rectifying tower to be separated the lower concentration trimethyl carbinol, directly enters fixed-bed reactor from side take-off tertiary butanol and water mixture.Reaction product returns rectifying tower again, the condensation of rectifying tower top portion, and liquid phase all refluxes, and gas phase extraction obtains iso-butylene product.Well solve the problem of by product carbon eight enrichment in the method, but use two complete equipments, add equipment and process cost.
Summary of the invention
The object of the present invention is to provide a kind of operating process simple, cost is low, transformation efficiency and selectivity high, the iso-butylene purity of generation is high, the method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution that preparation efficiency is high, to solve the problem.
In order to achieve the above object, technical scheme of the present invention is achieved in that
The above-mentioned method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, it comprises following concrete steps: (1) is first respectively to more than the catalyst section in the middle part of catalytic distillation tower and following filling θ ring filler; Then again with glass filler by catalyst segments and to loading catalyst in every section of catalyst section; (2) tertiary butanol aqueous solution is passed into catalytic distillation tower by tower middle feed fresh feed pump, and the top of deionized water via overhead water fresh feed pump autocatalysis distillation tower is entered; By tower reactor reboiler, thermal distillation is added to tertiary butanol aqueous solution, to form tertiary butanol and water azeotrope, catalyst layer in the middle part of tertiary butanol and water azeotrope and catalytic distillation tower is reacted, the trimethyl carbinol in tertiary butanol and water azeotrope is generated iso-butylene by catalyst layer dehydration, the unreacted trimethyl carbinol continues to rise and is absorbed by the deionized water lower from tower top in the process risen with gas at epimere θ ring filler layer, arrives catalyst layer and continues the generation iso-butylene that dewaters; (3) at the high-purity isobutylene product that overhead extraction gas phase obtains, at tower reactor extraction deionized water.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: described in described step (1), catalyzer is large hole cation exchanger resin, its diameter is φ 0.45 ~ 1.25, water content is 40 ~ 50%, functional group >=3.10 [H+], maximum operating temperature is 180 DEG C.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: more than catalyst section described in described step (1) loading number of theoretical plate is 5 ~ 40, diameter is the θ ring filler of Ф 3; Loading number of theoretical plate below described catalyst section is 10 ~ 60, and diameter is the θ ring filler of Ф 3; Described catalyzer is divided into 3 ~ 12 sections and according to the standard loading catalyst of every section of loading catalyst quality 5 ~ 50g.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: described in described step (2), the massfraction of tertiary butanol aqueous solution is 2% ~ 70%.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: tertiary butanol aqueous solution described in described step (2) is that 0.06 ~ 1.20kg/h passes into described catalytic distillation tower according to flow velocity.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: the described deionized water in described step (2) is that 0.00 ~ 0.30kg/h passes into described catalytic distillation tower according to flow velocity.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: the pressure-controlling of the described catalytic distillation tower in described step (2) is at 0.05 ~ 0.7Mpa, and temperature controls at 80 ~ 200 DEG C.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: in described step (2), catalyzer lower floor temperature of reaction is 60 ~ 120 DEG C.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: in described step (2), catalyzer upper strata and lower floor's temperature head are 1 ~ 80 DEG C.
The described method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution, wherein: described in described step (2), the air speed of the trimethyl carbinol is 0.05 ~ 0.60h-1.
Compared with prior art, the advantage of the embodiment of the present invention is:
The method operating process that the present invention prepares high-purity isobutylene by lower concentration tertiary butanol aqueous solution is simple, and cost is low, transformation efficiency and selectivity high, the iso-butylene purity of generation is high, and preparation efficiency is high;
Also have the following advantages:
1) tertiary butanol aqueous solution of the present invention enters from catalyst layer lower floor in the middle part of tower, and the iso-butylene of generation directly rises, and does not react with the trimethyl carbinol in raw material and generates by product carbon eight ether, improves tertiary butanol selectivity;
2) tower top of the present invention directly passes into deionized water in order to absorb the trimethyl carbinol in residual gas, improves trimethyl carbinol transformation efficiency, and contributes to the distribution of catalyst layer homogeneous temperature, reduces the generation of polymkeric substance, improves tertiary butanol selectivity;
3) tower top of the present invention is without backflow, reduces energy consumption, and because refluxing without iso-butylene, thus decrease the generation of by-product polymer and carbon eight ether, improve selective isobutene;
4) generate iso-butylene by trimethyl carbinol Direct Dehydration in lower concentration tertiary butanol aqueous solution in the present invention, compared with methyl tertiary butyl ether cracking process, the product water of generation is pollution-free, temperature of reaction is low, and by-products content is few, and the later stage is without the need to being separated, technical process is simple, reduces equipment and process cost;
5) catalyst loading of the present invention is simple to operate, and catalyst levels is few, does not need to tie up, and do not need casting, cost is low;
6) trimethyl carbinol transformation efficiency of the present invention is more than 98%, and selectivity is more than 99.90%, and exhaust gas mutually middle iso-butylene content is up to more than 99.99%, is applicable to suitability for industrialized production.
7) distillation tower of the present invention and fixed-bed reactor are directly in conjunction with formation catalytic distillation tower, simplify technical process, reduce equipment and process cost.
Accompanying drawing explanation
Fig. 1 the present invention is prepared the process flow sheet of the method for high-purity isobutylene by lower concentration tertiary butanol aqueous solution.
Embodiment
Carry out clear, complete description below with reference to accompanying drawing to the technical scheme of various embodiments of the present invention, obviously, described embodiment is only a part of embodiment of the present invention, instead of whole embodiments.Based on the embodiment in the present invention, other embodiments all that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belong to the scope that the present invention protects.
As shown in Figure 1, the present invention prepares the method for high-purity isobutylene by lower concentration tertiary butanol aqueous solution, and it comprises the following steps:
(1) more than the catalyst section first in the middle part of catalytic distillation tower loading number of theoretical plate is 5 ~ 40 (preferably 10 ~ 30), and diameter is the θ ring filler of Ф 3; Below catalyst section, load number of theoretical plate is again 10 ~ 60 (preferably 15 ~ 45), and diameter is the θ ring filler of Ф 3; Then with glass filler, catalyzer is divided into 3 ~ 12 sections (preferably 4 ~ 10 sections) again, and according to the standard loading catalyst of every section of loading catalyst quality 5 ~ 50g (preferably 10 ~ 35g);
(2) by tower middle feed fresh feed pump by massfraction be the tertiary butanol aqueous solution of 2% ~ 70% (preferably 4% ~ 50%), be that 0.06 ~ 1.20kg/h passes into catalytic distillation tower according to flow velocity, meanwhile, be 0.00 ~ 0.30kg/h (preferably 0.10 ~ 0.25kg/h) by deionized water according to flow velocity to enter via the top of overhead water fresh feed pump autocatalysis distillation tower, by catalytic distillation tower pressure-controlling at 0.05 ~ 0.7Mpa (preferably 0.1 ~ 0.5Mpa), catalytic distillation tower temperature is controlled at 80 ~ 200 DEG C (preferably 90 ~ 190 DEG C), and by tower reactor reboiler, thermal distillation is added to tertiary butanol aqueous solution, to form tertiary butanol and water azeotrope, catalyst layer in the middle part of tertiary butanol and water azeotrope and catalytic distillation tower is reacted, the trimethyl carbinol in tertiary butanol and water azeotrope is generated iso-butylene by catalyst layer dehydration, the unreacted trimethyl carbinol continues to rise and is absorbed by the deionized water under from tower top in the process risen with gas at epimere θ ring filler layer, arrive catalyst layer and continue dehydration generation iso-butylene,
(3) at the high-purity isobutylene product that overhead extraction gas phase obtains, at tower reactor extraction deionized water.
Wherein, above-mentioned catalyzer lower floor temperature of reaction is 60 ~ 120 DEG C, preferably 75 ~ 115 DEG C; Catalyzer upper strata and lower floor's temperature head are 1 ~ 80 DEG C, preferably 7 ~ 74 DEG C; The air speed of the trimethyl carbinol is 0.05 ~ 0.60h-1, preferably 0.10 ~ 0.45h-1.
Catalyzer is large hole cation exchanger resin, and its diameter is φ 0.45 ~ 1.25, and water content is 40 ~ 50%, functional group >=3.10 [H+], maximum operating temperature 180 DEG C.
Below in conjunction with specific embodiment, the invention will be further described:
Embodiment 1
First below the catalyst section in catalytic distillation tower, load number of theoretical plate 25, diameter is the θ ring filler of Ф 3; More than catalyst section, load number of theoretical plate 12 again, diameter is the θ ring filler of Ф 3; Then divide 5 sections by catalyst section and be respectively charged into 15g catalyzer; And then, be that the tertiary butanol aqueous solution of 5% passes into catalytic distillation tower with flow velocity 0.15kg/h by mass content, meanwhile, deionized water entered catalytic distillation tower with flow velocity 0.12kg/h from tower top, at working pressure 0.2Mpa, at bottom temperature 130 DEG C, add thermal distillation.
Wherein, in the embodiment of the present invention 1, catalyzer lower floor temperature is 98 DEG C, and catalyzer upper strata temperature is 31 DEG C, and trimethyl carbinol transformation efficiency is 98.50%, selectivity 99.93%, and in exhaust gas body, iso-butylene content is 99.73%.
Embodiment 2
First below the catalyst section in catalytic distillation tower, load number of theoretical plate 40, diameter is the θ ring filler of Ф 3; More than catalyst section, load number of theoretical plate 25 again, diameter is the θ ring filler of Ф 3; Then divide 8 sections by catalyst section and be respectively charged into 30g catalyzer; And then by mass content be 45% tertiary butanol aqueous solution pass into catalytic distillation tower with flow velocity 0.85kg/h, meanwhile, deionized water is entered catalytic distillation tower with flow velocity 0.20kg/h from tower top, at working pressure 0.1Mpa, at bottom temperature 100 DEG C, adds thermal distillation.
Wherein, in the embodiment of the present invention 1, catalyzer lower floor temperature is 80 DEG C, and catalyzer upper strata temperature is 73 DEG C, and trimethyl carbinol transformation efficiency is 99.21%, selectivity 99.98%, and in exhaust gas body, iso-butylene content is 99.35%.
Embodiment 3
First below the catalyst section in catalytic distillation tower, load number of theoretical plate 35, diameter is the θ ring filler of Ф 3; More than catalyst section, load number of theoretical plate 20 again, diameter is the θ ring filler of Ф 3; Then divide 7 sections by catalyst section and be respectively charged into 25g catalyzer; And then by mass content be 15% tertiary butanol aqueous solution pass into catalytic distillation tower with flow velocity 0.65kg/h, meanwhile, deionized water is entered catalytic distillation tower with flow velocity 0.23kg/h from tower top, at working pressure 0.3Mpa, at bottom temperature 180 DEG C, adds thermal distillation.
Wherein, in the embodiment of the present invention 1, catalyzer lower floor temperature is 110 DEG C, and catalyzer upper strata temperature is 36 DEG C, and trimethyl carbinol transformation efficiency is 99.58%, selectivity 99.96%, and in exhaust gas body, iso-butylene content is 99.99%.
Embodiment 4
First below the catalyst section in catalytic distillation tower, load number of theoretical plate 35, diameter is the θ ring filler of Ф 3; More than catalyst section, load number of theoretical plate 20 again, diameter is the θ ring filler of Ф 3; Then divide 6 sections by catalyst section and be respectively charged into 25g catalyzer; And then by mass content be 25% tertiary butanol aqueous solution pass into catalytic distillation tower with flow velocity 0.65kg/h, meanwhile, deionized water is entered catalytic distillation tower with flow velocity 0.23kg/h from tower top, at working pressure 0.3Mpa, at bottom temperature 170 DEG C, adds thermal distillation.
Wherein, in the embodiment of the present invention 1, catalyzer lower floor temperature is 110 DEG C, and catalyzer upper strata temperature is 36 DEG C, and trimethyl carbinol transformation efficiency is 99.82%, selectivity 99.90%, and in exhaust gas body, iso-butylene content is 99.95%.
Embodiment 5
First below the catalyst section in catalytic distillation tower, load number of theoretical plate 40, diameter is the θ ring filler of Ф 3; More than catalyst section, load number of theoretical plate 25 again, diameter is the θ ring filler of Ф 3; Then divide 8 sections by catalyst section and be respectively charged into 30g catalyzer; And then by mass content be 15% tertiary butanol aqueous solution pass into catalytic distillation tower with flow velocity 0.85kg/h, meanwhile, deionized water is entered catalytic distillation tower with flow velocity 0.20kg/h from tower top, at working pressure 0.2Mpa, at bottom temperature 130 DEG C, adds thermal distillation.
Wherein, in the embodiment of the present invention 1, catalyzer lower floor temperature is 98 DEG C, and catalyzer upper strata temperature is 32 DEG C, and trimethyl carbinol transformation efficiency is 99.52%, selectivity 99.95%, and in exhaust gas body, iso-butylene content is 99.56%.
The method operating process that the present invention prepares high-purity isobutylene by lower concentration tertiary butanol aqueous solution is simple, convenient, and cost is low, and raw material tertiary butanol aqueous solution enters from catalyzer orlop in the middle part of tower, decreases the generation of by product, improves tertiary butanol selectivity; Tower top directly passes into deionized water in order to absorb the trimethyl carbinol in residual gas, improves trimethyl carbinol transformation efficiency, and contributes to the distribution of catalyst layer homogeneous temperature, decrease the generation of polymkeric substance, improve tertiary butanol selectivity, recovered water at the bottom of tower, tower top can the highly purified iso-butylene of extraction.
The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, the any simple modification done above embodiment according to technical spirit of the present invention, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.
Claims (10)
1. prepared a method for high-purity isobutylene by lower concentration tertiary butanol aqueous solution, it is characterized in that, comprise following concrete steps:
(1) first respectively to more than the catalyst section in the middle part of catalytic distillation tower and following filling θ ring filler; Then again with glass filler by catalyst segments and to loading catalyst in every section of catalyst section;
(2) tertiary butanol aqueous solution is passed into catalytic distillation tower by tower middle feed fresh feed pump, and the top of deionized water via overhead water fresh feed pump autocatalysis distillation tower is entered; By tower reactor reboiler, thermal distillation is added to tertiary butanol aqueous solution, to form tertiary butanol and water azeotrope, catalyst layer in the middle part of tertiary butanol and water azeotrope and catalytic distillation tower is reacted, the trimethyl carbinol in tertiary butanol and water azeotrope is generated iso-butylene by catalyst layer dehydration, the unreacted trimethyl carbinol continues to rise and is absorbed by deionized water in the process risen with gas at epimere θ ring filler layer, arrives catalyst layer and continues dehydration generation iso-butylene;
(3) at the high-purity isobutylene product that overhead extraction gas phase obtains, at tower reactor extraction deionized water.
2. the method for claim 1, it is characterized in that: described in described step (1), catalyzer is large hole cation exchanger resin, its diameter is φ 0.45 ~ 1.25, and water content is 40 ~ 50%, functional group >=3.10 [H+], maximum operating temperature is 180 DEG C.
3. the method for claim 1, is characterized in that: more than catalyst section described in described step (1) loading number of theoretical plate is 5 ~ 40, and diameter is the θ ring filler of φ 3; Loading number of theoretical plate below described catalyst section is 10 ~ 60, and diameter is the θ ring filler of φ 3; Described catalyzer is divided into 3 ~ 12 sections and according to the standard loading catalyst of every section of loading catalyst quality 5 ~ 50g.
4. the method for claim 1, is characterized in that: described in described step (2), the massfraction of tertiary butanol aqueous solution is 2% ~ 70%.
5. the method for claim 1, is characterized in that: tertiary butanol aqueous solution described in described step (2) is that 0.06 ~ 1.20kg/h passes into described catalytic distillation tower according to flow velocity.
6. the method for claim 1, is characterized in that: the described deionized water in described step (2) is that 0.00 ~ 0.30kg/h passes into described catalytic distillation tower according to flow velocity.
7. the method for claim 1, is characterized in that: described in described step (2), the pressure-controlling of catalytic distillation tower is at 0.05 ~ 0.7Mpa, and temperature controls at 80 ~ 200 DEG C, and it is assembled by distillation tower and fixed-bed reactor.
8. the method for claim 1, is characterized in that: in described step (2), catalyzer lower floor temperature of reaction is 60 ~ 120 DEG C.
9. the method for claim 1, is characterized in that: in described step (2), catalyzer upper strata and lower floor's temperature head are 1 ~ 80 DEG C.
10. method as claimed in claim 6, it is characterized in that, the method being prepared high-purity isobutylene by lower concentration tertiary butanol aqueous solution as claimed in claim 1, is characterized in that: described in described step (2), the air speed of the trimethyl carbinol is 0.05 ~ 0.60h-1.
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Cited By (6)
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| CN104971665A (en) * | 2015-07-21 | 2015-10-14 | 宁波金海晨光化学股份有限公司 | Synthesizer for 4,4-dimethyl-1,3-dioxane |
| CN106631713A (en) * | 2017-01-10 | 2017-05-10 | 北京恩泽福莱科技有限公司 | Method for preparing MTBE by etherification of tert-butyl alcohol and methanol |
| CN108774100A (en) * | 2018-04-28 | 2018-11-09 | 信汇科技有限公司 | A kind of tert-butyl alcohol and methanol prepare the integrated processes of methyl tertiary butyl ether(MTBE) and isobutene |
| CN109096026A (en) * | 2018-08-28 | 2018-12-28 | 宁波昊德化学工业股份有限公司 | A kind of production method of isobutene |
| CN109689597A (en) * | 2016-09-06 | 2019-04-26 | 三菱化学株式会社 | The isolation and purification method of isobutene and the manufacturing method of isobutene |
| 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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| CN104971665A (en) * | 2015-07-21 | 2015-10-14 | 宁波金海晨光化学股份有限公司 | Synthesizer for 4,4-dimethyl-1,3-dioxane |
| CN109689597A (en) * | 2016-09-06 | 2019-04-26 | 三菱化学株式会社 | The isolation and purification method of isobutene and the manufacturing method of isobutene |
| CN109689597B (en) * | 2016-09-06 | 2021-11-12 | 三菱化学株式会社 | Method for separating and purifying isobutylene and method for producing isobutylene |
| CN106631713A (en) * | 2017-01-10 | 2017-05-10 | 北京恩泽福莱科技有限公司 | Method for preparing MTBE by etherification of tert-butyl alcohol and methanol |
| CN108774100A (en) * | 2018-04-28 | 2018-11-09 | 信汇科技有限公司 | A kind of tert-butyl alcohol and methanol prepare the integrated processes of methyl tertiary butyl ether(MTBE) and isobutene |
| WO2019206324A1 (en) * | 2018-04-28 | 2019-10-31 | 信汇科技有限公司 | Combined method for preparing methyl tert-butyl ether and isobutylene from tert-butyl alcohol and methanol |
| 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 |
| CN109096026A (en) * | 2018-08-28 | 2018-12-28 | 宁波昊德化学工业股份有限公司 | A kind of production method of isobutene |
| CN109096026B (en) * | 2018-08-28 | 2021-07-06 | 宁波昊德化学工业股份有限公司 | Production method of isobutene |
| 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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