CN103382146B - Recovery method for isobutene in cracking process of methyl tert-butyl ether - Google Patents
Recovery method for isobutene in cracking process of methyl tert-butyl ether Download PDFInfo
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- CN103382146B CN103382146B CN201210135851.8A CN201210135851A CN103382146B CN 103382146 B CN103382146 B CN 103382146B CN 201210135851 A CN201210135851 A CN 201210135851A CN 103382146 B CN103382146 B CN 103382146B
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Abstract
The invention discloses a recovery method for isobutene in the cracking process of methyl tert-butyl ether for preparation of isobutene. The method comprises the following steps: step 1) mixing light components obtained at the top of a light component-removing tower and containing dimethyl ether and isobutene with reacted materials and water; step 2) introducing a mixed material obtained in the step 1) into a first water scrubber to obtain a water phase at the bottom of the water scrubber and an oil phase at the top of the water scrubber; step 3) introducing the water phase obtained in the step 2) into a methanol recovery tower to recover methanol and to obtain a material flow containing dimethyl ether at the top of the recovery tower; step 4) introducing the oil phase obtained in the step 2) into a rectifying tower and allowing components at the top of the rectifying tower to enter into a second water scrubber so as to obtain a water phase at the bottom of the second water scrubber and an oil phase at the top of the second water scrubber; and step 5) introducing the oil phase obtained in the step 4) into the light component-removing tower so as to obtain pure isobutene at the bottom of the light component-removing tower and returning light components containing dimethyl ether and isobutene obtained at the top of the light component-removing tower to the step 1). The method provided by the invention has the advantages of simple process flow, easy operation, capacity of complete recovery of isobutene, reduction of production cost and substantial improvement of economic benefits of an apparatus.
Description
Technical field
The present invention relates to the method reclaiming iso-butylene, be specifically related to the method for Separation and Recovery iso-butylene in methyl tert-butyl ether cracking iso-butylene technique.
Background technology
The technique of the high-purity iso-butylene of methyl tertiary butyl ether (MTBE) cracking adopts the flow process of five towers separation, i.e. the first water wash column, methanol distillation column, iso-butylene rectifying tower (weight-removing column), the second water wash column and iso-butylene treating tower (lightness-removing column) usually.Wherein the effect of weight-removing column removes unreacted MTBE in product, carbon five and isobutene dimer, and the effect of lightness-removing column is the light constituent dme removed in product iso-butylene, and the effect of first, second water wash column washes away the methyl alcohol in anti-rear material.
In existing MTBE cracking technology, water wash column comprises atmospheric operation and low voltage operated two kinds.During atmospheric operation, in water wash column, water does not almost have receptivity to dme, and by the restriction of water wash column mass-transfer efficiency time low voltage operated, the effect absorbing dme is not good equally, still containing more dme in last lightness-removing column charging.And lightness-removing column is last one separation circuit in the technique of the high-purity iso-butylene of methyl tertiary butyl ether (MTBE) cracking, containing dme about 20 ~ 25% in the lightness-removing column tower top light constituent finally obtained, and the content of iso-butylene is 75 ~ 80%, this strand of material uses as liquefied gas substantially at present.Lightness-removing column top light constituent at present containing a large amount of iso-butylene does not still have other effective Application way.Wherein Application way is that lightness-removing column top light constituent is returned a MTBE synthesizer, then dme will with unreacted carbon four logistics separating device.But because carbon four logistics of this part separating device as raw material for alkylation, will have strict demand to dme content wherein, therefore return the problem that this route of synthesizer also faces separation of dimethyl ether from C_4 hydrocarbon class.
Lightness-removing column top light constituent there is no industrial utility value, can only do fuel and use, cause the very large wasting of resources.Therefore, need to find a kind of simple technique, from the light constituent of lightness-removing column top, fully can recycle iso-butylene, improve the utilization ratio of resource.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention is in conjunction with the existing processing condition of the high-purity iso-butylene of MTBE cracking, provide a kind of method of Separation and Recovery iso-butylene from cracking isobutene by methyl-tert-butyl ether device, utilize simple technique just can iso-butylene fully in the light constituent of Separation and Recovery lightness-removing column top, under the prerequisite ensureing iso-butylene purity at the bottom of lightness-removing column, improve the output of iso-butylene, reduce production cost, improve economic benefit.
The invention provides a kind of method of Separation and Recovery iso-butylene from cracking isobutene by methyl-tert-butyl ether device, comprise following steps:
Step 1) mixes containing the lightness-removing column top light constituent of dme and iso-butylene, anti-rear material and water;
Step 2) mixture obtained in step 1) is passed into the first water wash column, obtain aqueous phase at the bottom of tower and tower top oil phase;
Step 3) is by step 2) in aqueous phase pass into methanol distillation column, reclaim methyl alcohol, and obtain at tower top the logistics comprising dme;
Step 4) is by step 2) in oil phase pass into rectifying tower, the component of rectifying tower tower top enters the second water wash column, obtains aqueous phase at the bottom of tower and tower top oil phase;
Oil phase in step 4) is passed into lightness-removing column by step 5), obtains high-purity isobutylene at the bottom of tower, and the light constituent containing dme and iso-butylene that tower top obtains returns step 1).
In aforesaid method, in described step 1), when lightness-removing column top is mixed containing dme and the light constituent of iso-butylene, anti-rear material and water, carry out contact mass transfer with water, made the dme of water absorption portion.In a specific embodiment, the temperature 0 ~ 40 DEG C during described mixing, working pressure 0.5 ~ 0.7MPa, with this understanding, can make water absorb dme in more polyhybrid material.
In a specific embodiment of aforesaid method, being blended in static mixer in described step 1) is carried out.Described static mixer can be the suitable type of any design, as SV type, SK type, SX type, SH type and SL type etc.Described static mixer is preferably SV type static mixer.
In aforesaid method, described step 2) in, in described first water wash column, add wash water to contact with mixture is reverse, as the mixture obtained in step 1) is entered the first water wash column at the bottom of tower, contact with another part wash water added from tower top is reverse in water wash column, carry out mass transfer further, thus absorb the dme contained in light constituent further.Remaining dme enters tower top oil phase together with iso-butylene, and dme is then only absorbed by the water and enters aqueous phase at the bottom of tower.
In a specific embodiment of aforesaid method, described mixing tank is placed in the bottom of the first water wash column.Light constituent lightness-removing column top being contained dme, iso-butylene and a small amount of water passes into the static mixer at the bottom of the first water wash column, carries out contact mass transfer, absorption portion dme together with material after anti-with wash water.For strengthening assimilation effect, the wash water consumption at the bottom of the first water wash column suitably can increase during compared with normal operation, because in whole technique, wash water recycles, increases the material consumption that wash water consumption can't increase device.Then this strand of material enters the first water wash column at the bottom of tower, contacts, carry out mass transfer further in water wash column with another part wash water added from tower top is reverse, thus absorbs the most of dme contained in light constituent.Residue dme enters tower top oil phase together with iso-butylene, and dme is then only absorbed by the water and enters aqueous phase at the bottom of tower.
In aforesaid method, in described step 3), the dme being absorbed into aqueous phase enters methanol distillation column with aqueous phase at the bottom of the first water wash column tower, methyl alcohol is from the column plate side take-off near tower top, containing the dme of a certain amount of methyl alcohol then from the regular extraction of return tank of top of the tower, after a static mixer washing, remove liquid petroleum gas system.The dme that such reaction produces can emptying separating device separately.
In aforesaid method, in described step 4), described step 2) in the tower top oil phase comprising residue dme and iso-butylene enter rectifying tower, remove the heavy constituent in oil phase.Described heavy constituent comprises unreacted MTBE, carbon five and isobutene dimer.What obtain at the bottom of rectifying tower is heavy constituent, the overhead components comprising dme and iso-butylene of rectifying tower top enters the second water wash column, after washing away Trace Methanol and a small amount of dme, dme and Trace Methanol enter in aqueous phase at the bottom of tower, and part dme and iso-butylene enter tower top oil phase.
In aforesaid method, in described step 5), enter lightness-removing column (or claiming iso-butylene treating tower), obtain highly purified iso-butylene at the bottom of tower from the second water wash column tower top oil phase out, the light constituent that what tower top obtained comprise dme and iso-butylene is back to step 1).In a specific embodiment, highly purified iso-butylene refers to the iso-butylene that purity is greater than 99.9%.
In the present invention, described anti-rear material refers to the material in methyl tert-butyl ether cracking iso-butylene technique after scission reaction, comprises uncracked methyl tertiary butyl ether, dme, methyl alcohol, iso-butylene, water and Diisobutylene.
According to method provided by the invention, technical process is simple, easy to operate, and the light constituent Separation and Recovery iso-butylene that can obtain from lightness-removing column top, avoids the waste of iso-butylene in light constituent, the iso-butylene that cracking is obtained substantially can Separation and Recovery fully, reduces production cost; Simultaneously, due to the emptying of iso-butylene in most tower top light constituent can be reduced, the dme that emptying economic worth is relatively much lower in liquefied gas, and can also be separated further as required and obtains highly purified dme, thus greatly improves the economic benefit of device; Improve resource utilization.
Accompanying drawing explanation
Fig. 1 is process flow sheet according to an embodiment of the invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is further detailed, but this does not form any limitation of the invention.
Fig. 1 is process flow sheet according to an embodiment of the invention.From the mixture 12 of the tower top of lightness-removing column 11 iso-butylene out and dme after condenser 14 cools, with wash water 10 and anti-after enter at the bottom of the first water wash column 3 tower static mixer 6 together with material 2, cold water and recirculated water 1 join the top of the first water wash column.The parallel filler being distributed with multilayer column plate or certain altitude of first water wash column 3 inner transverse, the absorption agent water joining tower top can absorb anti-after part dme in methyl alcohol, a small amount of dme and light constituent in material, make it enter into aqueous phase 4 at the bottom of tower.Aqueous phase 4 enters methanol distillation column 7 subsequently, carry out being separated of methyl alcohol and water here, water 10 at the bottom of tower returns the first water wash column and recycles, tower top contains the dme of a certain amount of methyl alcohol and part wash water and washes away after methyl alcohol through static mixer 15 and enter liquid petroleum gas system, and methyl alcohol 8 is extracted out from certain the block column plate near tower top.The oil phase 5 of the first water wash column 3 tower top removes heavy constituent through iso-butylene rectifying tower, second water wash column enters lightness-removing column 11 after washing away Trace Methanol and a small amount of dme, extraction high-purity isobutylene 13 at the bottom of tower, tower top is after condenser 14 condensation, again throw static mixer 6 at the bottom of the first water wash column containing the light constituent 12 of dme about 20 ~ 25% into.
Comparative example 1
MTBE cracking iso-butylene industrial scale is 100,000 tons/year, and MTBE cracking transformation efficiency is 93%, and dimethyl ether selectivity is 2%, and lightness-removing column tower top pressure is about 0.7 ~ 0.9MPa.Anti-rear material is passed into the bottom of the first water wash column, wash water enters the first water wash column from tower top.First water wash column is sieve-tray tower, and the pressure of tower is 0.6MPa.In the first water wash column, the material entered at the bottom of tower mixes with the wash water passed into from tower top, mass transfer, fully absorbs methyl alcohol wherein and most of dme.Absorb aqueous phase at the bottom of the first water wash column tower of methyl alcohol and dme and enter methanol distillation column Separation and Recovery methyl alcohol, tower top obtains the logistics comprising dme, and the wash water at the bottom of tower is back to the first water wash column and recycles.The tower top oil phase of the first water wash column removes after the heavy constituent such as MTBE, Diisobutylene through iso-butylene rectifying tower and enters the second water wash column.After the second water wash column washes away Trace Methanol, the oil phase that tower top comprises dme and iso-butylene enters iso-butylene treating tower, and tower top obtains the logistics comprising dme and iso-butylene, then obtains highly purified iso-butylene at the bottom of tower.Carried out material balance when reaction reaches balance, data are in table 1 and table 3.
Embodiment 1
With comparative example 1, difference is to be provided with static mixer at the bottom of the first water wash column tower, the logistics comprising dme and iso-butylene of post-decompression lightness-removing column tower top is fully mixed with anti-rear material and water in static mixer, and then passes into the first water wash column.Data are in table 2 and table 3.
Comparative example 2
MTBE cracking iso-butylene industrial scale is 100,000 tons/year, and MTBE cracking transformation efficiency is 96%, and dimethyl ether selectivity is 3%.Carried out material balance when reaction reaches balance, data are in table 4 and table 3.
Embodiment 2
With comparative example 2, difference is to be provided with static mixer at the bottom of the first water wash column tower, the logistics comprising dme and iso-butylene of post-decompression lightness-removing column tower top is fully mixed with anti-rear material and water in static mixer, and then passes into the first water wash column.Data are in table 5 and table 3.
Table 3
From table, data can be learnt, according to method Separation and Recovery iso-butylene provided by the invention, under ensureing that obtaining purity at the bottom of lightness-removing column is greater than the prerequisite of the iso-butylene of 99.9%, improve the output of iso-butylene, improve economic benefit.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (5)
1. the method for Separation and Recovery iso-butylene from cracking isobutene by methyl-tert-butyl ether device, comprises following steps:
Step 1), by containing dme and iso-butylene lightness-removing column top light constituent, anti-after material and water mix, the temperature 0 ~ 40 DEG C during described mixing, working pressure 0.5 ~ 0.7MPa;
Step 2), by step 1) in the mixture that obtains pass into the first water wash column, obtain aqueous phase at the bottom of tower and tower top oil phase;
Step 3), by step 2) in aqueous phase pass into methanol distillation column, reclaim methyl alcohol, and obtain at tower top the logistics comprising dme;
Step 4), by step 2) in oil phase pass into rectifying tower, the component of rectifying tower tower top enters the second water wash column, obtains aqueous phase at the bottom of tower and tower top oil phase;
Step 5), by step 4) in oil phase pass into lightness-removing column, obtain high-purity isobutylene at the bottom of tower, described high-purity isobutylene refers to that the light constituent containing dme and iso-butylene that the iso-butylene that purity is greater than 99.9%, tower top obtain returns step 1).
2. method according to claim 1, is characterized in that, described step 1) in be blended in static mixer and carry out.
3. method according to claim 2, is characterized in that, described static mixer is SV type static mixer.
4. method according to claim 3, is characterized in that, described static mixer is placed in the bottom of the first water wash column.
5. method according to claim 1, is characterized in that, in described first water wash column, adds wash water and contacts with mixture is reverse.
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| CN201210135851.8A CN103382146B (en) | 2012-05-03 | 2012-05-03 | Recovery method for isobutene in cracking process of methyl tert-butyl ether |
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| CN107805184B (en) * | 2016-09-08 | 2020-12-18 | 中国石油化工股份有限公司 | Light gasoline etherification and methyl tert-butyl ether cracking combined system and application thereof |
| CN108083968B (en) * | 2017-12-29 | 2020-10-23 | 黄河三角洲京博化工研究院有限公司 | Method for strengthening separation of dimethyl ether in crude isobutene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100438A (en) * | 1997-02-21 | 2000-08-08 | Institut Francais Du Petrole | Process for producing a tertiary olefin by decomposing a tertiary alkyl ether |
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| US7060865B2 (en) * | 2002-11-12 | 2006-06-13 | Exxonmobil Chemical Patents Inc. | Recovery of C4 olefins from a product stream comprising C4 olefins, dimethyl ether and C5+ hydrocarbons |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6100438A (en) * | 1997-02-21 | 2000-08-08 | Institut Francais Du Petrole | Process for producing a tertiary olefin by decomposing a tertiary alkyl ether |
Non-Patent Citations (2)
| Title |
|---|
| MTBE裂解制异丁烯生产工艺及催化研究概述;程引贵等;《甘肃科技》;20070630;第23卷(第6期);第74-76页 * |
| 异丁烯制备工艺脱甲醇分离流程的优化;周继东等;《石油化工设计》;20021231;第19卷(第4期);第18-20页 * |
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