CN103739454A - Process for preparing MTBE (Methyl Tert Butyl Ether) from C4 fraction in etherified liquefied gas - Google Patents
Process for preparing MTBE (Methyl Tert Butyl Ether) from C4 fraction in etherified liquefied gas Download PDFInfo
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- CN103739454A CN103739454A CN201310721122.5A CN201310721122A CN103739454A CN 103739454 A CN103739454 A CN 103739454A CN 201310721122 A CN201310721122 A CN 201310721122A CN 103739454 A CN103739454 A CN 103739454A
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 117
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 13
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 238000006266 etherification reaction Methods 0.000 claims abstract description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 68
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 10
- 238000010533 azeotropic distillation Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 6
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001768 cations Chemical group 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 5
- 230000003068 static effect Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 2
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000003808 methanol extraction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 230000036632 reaction speed Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MRMOZBOQVYRSEM-UHFFFAOYSA-N tetraethyllead Chemical compound CC[Pb](CC)(CC)CC MRMOZBOQVYRSEM-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- FVNIMHIOIXPIQT-UHFFFAOYSA-N 2-methoxybutane Chemical compound CCC(C)OC FVNIMHIOIXPIQT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iso-butylene forms carbonium ion Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical techniques, and in particular relates to a process for preparing MTBE (Methyl Tert Butyl Ether) from C4 fraction in an etherified liquefied gas. The process for preparing MTBE (Methyl Tert Butyl Ether) from the C4 fraction in the etherified liquefied gas is characterized in that in an MTBE synthesis device, raw materials C4 and methanol are fed into a reactor, on the presence of a catalyst, isobutene in C4 and methanol are subjected to etherification reaction so as to generate MTBE; the reaction material comprising surplus methanol, etherified C4, the product MTBE, a byproduct dimethyl ether and C8 tertiary butanol is fed into an azeotrope tower; a crude MTBE product flows out from the bottom of the azeotrope tower. By adopting the process for producing MTBE from the C4 fraction in the etherified liquefied gas as the raw material by using the method provided by the invention, the yield of MTBE can be 96%.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to that a kind of to take the C 4 fraction in liquefied gas after ether be raw material production MTBE(methyl tertiary butyl ether) technique.
Background technology
?iso-butylene in C4 and methyl alcohol generation etherification reaction generate MTBE(methyl tertiary butyl ether).Product MTBE is for the production of high-purity isobutylene, or as carrying high-octane additive in high-grade gasoline production, methyl alcohol superfluous in etherification reaction is recovered use.Hybrid C 4 after etherification reaction is called as C4 after ether, and its main ingredient is Trimethylmethane, normal butane, n-butene, cis-2-butene, Trans-2-butene and a small amount of divinyl.After ether, carbon four can be regarded civil liquefied gas, but its price is more expensive compared with normal domestic Qi Lai lecture, and pure burning result of use is also not as domestic gas.
Along with the promotion and application of white gasoline, as the demand of the methyl tertiary butyl ether (MTBE) of gasoline high-quality blend component, day by day increase, for effectively utilizing the iso-butylene in C4 fraction to produce highly purified MTBE product.
Methyl tertiary butyl ether is a kind of additive, and colourless liquid, has ethereal odor, is slightly soluble in water, can be used as gasoline dope and replaces tetraethyllead, and excellent property is efficient, good market prospects, and production technique is simple, synthetic under certain temperature and pressure.
MTBE synthesizer flow process and present situation introduction, in MTBE synthesizer, raw material C4 and methyl alcohol enter reactor, under the effect of macropore strong acid cation resin catalyst, iso-butylene in C4 and methyl alcohol generation etherification reaction, generate MTBE, reacted material comprises superfluous methyl alcohol, C4 after ether, product MTBE, by product dme, C8, MSBE(methyl sec-butyl ether), the trimethyl carbinol etc., being sent to azeotropic distillation column divides, at component distillation tower bottom, flowing out purity is the more than 98% thick product of MTBE, it is further separated that thick MTBE sends into MTBE rectifying tower, can obtain the MTBE essence product of high purity.Methanol extraction tower is discharged and be sent to the azeotrope that after methyl alcohol and ether, C4 forms in azeotropic distillation column from tower top, in methanol extraction tower, take water as extraction agent, by the methanol extraction in C4 after ether, send the methanol aqueous solution of formation to methanol distillation column and carry out Methanol Recovery, water at the bottom of methanol distillation column returns to methanol extraction tower, as extraction water, recycles.After ether, C4 is from methanol extraction overhead extraction, and is sent to refinery, as the raw materials for production of alkyl plant.
Under selected processing condition, iso-butylene in raw material C4 and industrial methanol mix by beds reaction generation MTBE, iso-butylene and methyl alcohol are under the effect of strong acidic ion resin catalyzer, and iso-butylene forms carbonium ion in tertiary carbon position, have higher reactive behavior.Methyl alcohol generates MTBE owing to belonging to the addition reaction that polar molecule carries out with it.This reaction is thermopositive reaction, temperature of reaction is 40-80 ℃, the restriction that the building-up reactions of MTBE is subject to thermodynamic(al)equilibrium at low temperatures, to the orienting response that generates MTBE, simultaneously, from reaction power, at higher temperature, accelerate anti-speed degree, but side reaction is accelerated, in production operation, to make empty suitable temperature of reaction for this reason, under the condition of reaction, moisture and isobutene reaction contained in raw material generate the trimethyl carbinol, iso-butylene autohemagglutination generates dipolymer methyl alcohol and is condensed into dme, the byproduct trimethyl carbinol and dipolymer also have higher octane value, can call in gasoline in company with MTBE.The reaction preference of synthetic MTBE is very high, and 98-99% adopts reaction distillation Shengji postoperative, and isobutene conversion is more than or equal to 99%, and byproduct generates seldom, and other C4 component in C 4 fraction except iso-butylene is considered as inert substance under reaction conditions.
Summary of the invention
In order to solve above-mentioned technical problem, the invention provides the C 4 fraction in liquefied gas after ether of utilizing that a kind of yield is high and prepare the technique of MTBE.
The technique that C 4 fraction of take after ether of the present invention is raw material production MTBE is to solve above technical problem by following technical scheme:
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, the step of this technique is as follows:
In the synthesizer of MTBE, raw material C4 and methyl alcohol enter reactor, under the effect of catalyzer, iso-butylene in C4 and methyl alcohol generation etherification reaction, generate MTBE, described reaction mass comprises that C4, product MTBE after superfluous methyl alcohol, ether, by product dme, the C8 trimethyl carbinol are admitted to azeotropic distillation column separation, flow out MTBE crude product at component distillation tower bottom.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, the parameter of this technique is as follows:
Raw material C4 comprises that following component iso-butylene content is 14.9%, and propylene is 0.01%, and Trimethylmethane is 45.25%; Normal butane is 19.1%, and butylene is 4.1%, and cis-n-butene is 9.3%, trans-n-butene 6.4%, amylene 0.75%.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, in raw material C4, iso-butylene content is 8%～30%.
Preferably, in above-mentioned raw material C4, iso-butylene content is 10%～25%.
In above-mentioned raw material C4, iso-butylene content is 20%.
Above-mentioned alfin ratio is 1.2.
Produce the suitable condition of MTBE, reactor bed material is in gas-liquid mixed material, each bed temperature is poor little, if the easy autohemagglutination of iso-butylene in excess Temperature C4, make in product oligomer too high, temperature is controlled too low meeting makes reaction not exclusively, so the optimum temperature of reaction of reactor is controlled between the temperature setting in the present invention.
The reaction pressure of reaction pressure: MTBE is an important influence factor, pressure is low, the interior vaporization rate of reactor is high, bed tempertaure is low, isobutene conversion is low, pressure is high, and bed is almost adiabatic reaction, and each section of temperature difference is large, etherification procedure easily produces by product, production practice prove, the optimum pressure of reactor should be between 0.7-0.75Mpa, very favourable for synthetic MTBE reaction.
Alfin ratio: alfin ratio is the key parameter of synthetic MTBE reaction, in reaction feed, methyl alcohol compares with the acid of iso-butylene the selection ratio that generates MTBE, and the impact such as the transformation efficiency of the generation iso-butylene of the by products such as the trimethyl carbinol and oligopolymer is significantly.When alfin ratio is greater than or equal to 1 time, its initial reaction speed is faster, and reaction is beneficial to MTBE direction and generates, more than MTBE purity to 99%.When alfin ratio is less than 1, initial reaction speed and iso-butylene starting point concentration are irrelevant, now depend on the starting point concentration of methyl alcohol, methanol concentration is lower, and initial reaction speed is slower, is unfavorable for that MTBE generates, be conducive to the generation of by product, so sour alkene is the most suitable than being just controlled at 1.05-1.10.
Beneficial effect of the present invention is, adopts method of the present invention to take the technique that the C 4 fraction in liquefied gas is raw material production MTBE after ether, and the yield of MTBE can reach 96%.
Embodiment
Below in conjunction with embodiment, the present invention is further described, so that those skilled in the art more understands the present invention, but with this, does not limit the present invention.
Embodiment 1
In the synthesizer of MTBE, raw material C4 and methyl alcohol enter reactor, under the effect of catalyzer, iso-butylene in C4 and methyl alcohol generation etherification reaction, generate MTBE, described reaction mass comprises that C4, product MTBE after superfluous methyl alcohol, ether, by product dme, the C8 trimethyl carbinol are admitted to azeotropic distillation column separation, flow out MTBE crude product at component distillation tower bottom.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, the parameter of this technique is as follows:
The temperature of preheater is: 40～55 ℃;
Static mixer is reticulated structure, its aperture DN50; Alfin ratio 1.2 wherein;
Catalyzer is cation resin catalyzing agent;
Pressure 1.0MPa ± 0.1 of reactor;
40～45 ℃ of tower top temperatures;
Medium temperature is 65 ℃;
Column bottom temperature is 54～55 ℃;
Azeotrope column and pressure 0.7Mpa;
65 ℃ of tower tops;
At the bottom of tower 120～140 ℃.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, raw material C4 comprises that following component iso-butylene content is 14.9%, and propylene is 0.01%, and Trimethylmethane is 45.25%; Normal butane is 19.1%, and butylene is 4.1%, and cis-n-butene is 9.3%, trans-n-butene 6.4%, amylene 0.75%.
It is further separated that crude product MTBE sends into rectifying tower, can obtain highly purified MTBE, methanol extraction tower is discharged and be sent to the azeotrope that after methyl alcohol and ether, C4 forms in azeotropic distillation column from tower top, in methanol extraction tower, take water as extraction agent, by the methanol extraction in C4 after ether, send the methanol aqueous solution of formation to Methanol Recovery, water at the bottom of methanol distillation column returns to methanol extraction tower, as extraction water, recycle, and C4, from methanol extraction overhead extraction, and is sent to refinery after ether, as the raw materials for production of alkyl plant.
Embodiment 2
In the synthesizer of MTBE, raw material C4 and methyl alcohol enter reactor, under the effect of catalyzer, iso-butylene in C4 and methyl alcohol generation etherification reaction, generate MTBE, described reaction mass comprises that C4, product MTBE after superfluous methyl alcohol, ether, by product dme, the C8 trimethyl carbinol are admitted to azeotropic distillation column separation, flow out MTBE crude product at component distillation tower bottom.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, the parameter of this technique is as follows:
The temperature of preheater is: 40～55 ℃;
Static mixer is reticulated structure, its aperture DN50; Alfin ratio 1.15 wherein;
Catalyzer is cation resin catalyzing agent;
Pressure 1.0MPa ± 0.1 of reactor;
40～45 ℃ of tower top temperatures;
Medium temperature is 65 ℃;
Column bottom temperature is 54～55 ℃;
Azeotrope column and pressure 0.7Mpa;
65 ℃ of tower tops;
At the bottom of tower 120～140 ℃.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, raw material C4 comprises that following component iso-butylene content is 10%, and propylene is 0.01%, and Trimethylmethane is 45.25%; Normal butane is 19.1%, and butylene is 4.1%, and cis-n-butene is 9.3%, trans-n-butene 6.4%, amylene 0.75%.
Embodiment 3
In the synthesizer of MTBE, raw material C4 and methyl alcohol enter reactor, under the effect of catalyzer, iso-butylene in C4 and methyl alcohol generation etherification reaction, generate MTBE, described reaction mass comprises that C4, product MTBE after superfluous methyl alcohol, ether, by product dme, the C8 trimethyl carbinol are admitted to azeotropic distillation column separation, flow out MTBE crude product at component distillation tower bottom.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, the parameter of this technique is as follows:
The temperature of preheater is: 40～55 ℃;
Static mixer is reticulated structure, its aperture DN50; Alfin ratio 1.3 wherein;
Catalyzer is cation resin catalyzing agent;
Pressure 1.0MPa ± 0.1 of reactor;
40～45 ℃ of tower top temperatures;
Medium temperature is 65 ℃;
Column bottom temperature is 54～55 ℃;
Azeotrope column and pressure 0.7Mpa;
65 ℃ of tower tops;
At the bottom of tower 120～140 ℃.
Utilize the C 4 fraction in liquefied gas after ether to prepare the technique of MTBE, raw material C4 comprises that following component iso-butylene content is 30%, and propylene is 0.01%, and Trimethylmethane is 25.25%; Normal butane is 19.1%, and butylene is 4.1%, and cis-n-butene is 9.3%, trans-n-butene 6.4%, amylene 0.75%.
Claims (6)
1. a technique of utilizing the C 4 fraction in liquefied gas after ether to prepare MTBE, it is characterized in that, in the synthesizer of MTBE, raw material C4 and methyl alcohol enter reactor, under the effect of catalyzer, the iso-butylene in C4 and methyl alcohol generation etherification reaction, generate MTBE, described reaction mass comprises that C4, product MTBE after superfluous methyl alcohol, ether, by product dme, the C8 trimethyl carbinol are admitted to azeotropic distillation column separation, flow out MTBE crude product at component distillation tower bottom.
2. a kind of technique of utilizing the C 4 fraction in liquefied gas after ether to prepare MTBE as claimed in claim 1, is characterized in that,
The temperature of preheater is: 40～55 ℃;
Static mixer is reticulated structure, its aperture DN50; Alfin ratio 1.15～1.3 wherein;
Catalyzer is cation resin catalyzing agent;
Pressure 1.0MPa ± 0.1 of reactor;
40～45 ℃ of tower top temperatures;
Medium temperature is 65 ℃;
Column bottom temperature is 54～55 ℃;
Azeotrope column and pressure 0.7Mpa;
65 ℃ of tower tops;
At the bottom of tower 120～140 ℃.
3. a kind of technique of utilizing the C 4 fraction in liquefied gas after ether to prepare MTBE as claimed in claim 1, is characterized in that, in described raw material C4, iso-butylene content is 8%～30%.
4. a kind of technique of utilizing the C 4 fraction in liquefied gas after ether to prepare MTBE as claimed in claim 1, is characterized in that, in described raw material C4, iso-butylene content is 10%～25%.
5. a kind of technique of utilizing the C 4 fraction in liquefied gas after ether to prepare MTBE as claimed in claim 1, is characterized in that, described raw material C4 comprises that following component iso-butylene content is 14.9%, and propylene is 0.01%, and Trimethylmethane is 45.25%; Normal butane is 19.1%, and butylene is 4.1%, and cis-n-butene is 9.3%, trans-n-butene 6.4%, amylene 0.75%.
6. a kind of technique of utilizing the C 4 fraction in liquefied gas after ether to prepare MTBE as claimed in claim 1, is characterized in that, described alfin ratio is 1.2.
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Cited By (5)
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| CN108047002A (en) * | 2017-11-27 | 2018-05-18 | 滨州市裕祥化工有限公司 | It is a kind of to produce obtained MTBE components and liquefied gas and preparation method thereof using carbon after ether four |
| CN108834410A (en) * | 2017-01-06 | 2018-11-16 | 株式会社Lg化学 | The preparation method of methyl tert-butyl ether |
| CN110437868A (en) * | 2018-05-03 | 2019-11-12 | 中国石油天然气股份有限公司 | Method for producing high value-added product by using mixed C4 |
| CN110437867A (en) * | 2018-05-03 | 2019-11-12 | 中国石油天然气股份有限公司 | Method for producing high value-added product by using liquefied gas |
| CN113943213A (en) * | 2021-11-15 | 2022-01-18 | 丹东明珠特种树脂有限公司 | High-purity MTBE (methyl tert-butyl ether) process method for efficiently removing isobutene and preparation system thereof |
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| CN108047002A (en) * | 2017-11-27 | 2018-05-18 | 滨州市裕祥化工有限公司 | It is a kind of to produce obtained MTBE components and liquefied gas and preparation method thereof using carbon after ether four |
| CN110437868A (en) * | 2018-05-03 | 2019-11-12 | 中国石油天然气股份有限公司 | Method for producing high value-added product by using mixed C4 |
| CN110437867A (en) * | 2018-05-03 | 2019-11-12 | 中国石油天然气股份有限公司 | Method for producing high value-added product by using liquefied gas |
| CN110437867B (en) * | 2018-05-03 | 2021-09-28 | 中国石油天然气股份有限公司 | Method for producing high value-added product by using liquefied gas |
| CN110437868B (en) * | 2018-05-03 | 2021-09-28 | 中国石油天然气股份有限公司 | Method for producing high value-added product by using mixed C4 |
| CN113943213A (en) * | 2021-11-15 | 2022-01-18 | 丹东明珠特种树脂有限公司 | High-purity MTBE (methyl tert-butyl ether) process method for efficiently removing isobutene and preparation system thereof |
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