CN103193603A - Regeneration method of MTBE (methyl tert-butyl ether) adsorbent desulfurization solvent - Google Patents
Regeneration method of MTBE (methyl tert-butyl ether) adsorbent desulfurization solvent Download PDFInfo
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- CN103193603A CN103193603A CN2013101433299A CN201310143329A CN103193603A CN 103193603 A CN103193603 A CN 103193603A CN 2013101433299 A CN2013101433299 A CN 2013101433299A CN 201310143329 A CN201310143329 A CN 201310143329A CN 103193603 A CN103193603 A CN 103193603A
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Abstract
The invention provides a method for regenerating an MTBE (methyl tert-butyl ether) adsorbent desulfurization solvent and recycling MTBE. The method specifically comprises the following steps of: during vacuum regeneration of the MTBE adsorbent desulfurization solvent, dissolving a mixture including the MTBE and sulfide which are subjected to vacuum extraction in methanol recycle-water of an MTBE device, dissolving the MTBE in the methanol recycle-water, recycling the MTBE through a methanol recycling system of the MTBE device, and recycling the sulfide by using a methanol water absorption tank because the sulfide is insoluble in water to realize the recycling of the MTBE and the regeneration of an adsorbent solvent.
Description
Technical field
The invention belongs to the petrochemical technology field.Relate to the sulfide technology among the MTBE that removes, specifically provide the renovation process that a kind of adsorptive distillation removes sulfide solvent among the MTBE.
Background technology
The MTBE(methyl tertiary butyl ether) is iso-butylene and methyl alcohol addition reaction product in the liquefied petroleum gas (LPG) (C-4-fraction).MTBE is high-octane rating clean gasoline blending component, also is the raw material that high-purity iso-butylene is produced in cracking, is a kind of important petrochemical materials and product.
Along with crude oil heaviness, poor qualityization development and requirement that comprehensive utilization of resources is constantly deepened, sulphur content raises gradually in catalytic cracking and the coking C-4-fraction.In C-4-fraction and methyl alcohol addition reaction production MTBE, sulfocompound and butene reaction generation macromole sulfide such as the mercaptan in the C-4-fraction.Because the sulfide of MTBE has than hydro carbons and has higher solvability, when MTBE separates with carbon four behind the ether, the sulfide that the reaction of sulfocompound and C 4 olefin generates in the carbon four and the sulfide in the C-4-fraction are almost all by the enrichment of product MTBE institute, cause sulfide content height in the MTBE product, not only can not meet the clean gasoline standard, and influence the follow-up chemical utilization of MTBE.Removing sulfide among the MTBE, is the difficult problem that refining of petroleum and petrochemical enterprise are badly in need of solution.
Remove at present that sulfide mainly adopts alkali washing process such as diethanolamine in the liquefied petroleum gas (LPG), but owing to the development trend along with crude oil heaviness, poor qualityization, sulfide molecules increases in the liquefied petroleum gas (LPG), is difficult to realize that by prior art wherein sulfide is removed to standard-required; Remove the sulfide of hydrocarbon raw materials such as gasoline, diesel oil, generally adopt the hydrofining technology at present, but MTBE is oxygenatedchemicals, because the carbon-sulfur bond bond energy is far above the carbon-oxygen bond bond energy, in hydrodesulfurization process, carbon-oxygen bond hydrogenation deoxidation at first generates corresponding alkane among the MTBE, and causes a large amount of MTBE losses.Therefore, must develop MTBE and remove technology at sulfide among the unsettled MTBE of molecular structure.
The contriver discloses the technology that a kind of adsorptive distillation removes sulfide among the MTBE in the CN102898286A patent.Be higher than MTBE with boiling point, the material that thioether, mercaptan and disulphide and thiophene is had strong adsorption selectivity is sorbent material, under certain temperature and processing condition, with sulfide selective adsorption among the MTBE in sorbent material; Contain sulfur absorbent simultaneously and adopt the method reprocessing cycle of vacuum distilling to use, and reclaim sulfide, realize sulfide among the MTBE is removed and recycles.But also adsorb a small amount of MTBE in the time of solvent adsorption sulfide, adopt vacuum distilling to remove and when reclaiming sulfide, can cause the MTBE loss, and have a small amount of MTBE to enter atmosphere with vacuum system, cause topsoil.
Summary of the invention
According to background technology, the MTBE adsorptive distillation removes in the sulfide process: MTBE and solvent have certain mutual solubility, when adopting vacuum distilling to remove in the adsorption solvent sulfide, can cause the MTBE loss and to topsoil; Find that simultaneously the sulfide among the MTBE mainly exists with thioether, alkyl disulfide and alkyl trisulphide form, and thioether, alkyl disulfide, alkyl trisulphide are water insoluble substantially, MTBE has certain solubleness in water.According to the characteristic of MTBE and sulfide, the invention provides a kind of regeneration of MTBE adsorption desulfurize solvent and the method that MTBE reclaims.
Be exactly specifically: when MTBE adsorption desulfurize solvent vacuum regeneration, the MTBE that vacuum is extracted out and the mixture of sulfide are dissolved in the methanol recycled water of MTBE device, MTBE is dissolved in methanol recycled water, reclaim MTBE by MTBE device methanol recovery system, because sulfide is water insoluble, sulfide is reclaimed by the methanol-water tourie, realizes that MTBE reclaims and adsorption solvent regeneration.
The regeneration of MTBE adsorption desulfurize solvent realizes in the following way: the rich solvent that absorbs sulfide among the MTBE, extract the rich solvent that is rich in sulphur and MTBE out by MTBE absorption distillation thionizer tower reactor and send into solvent vacuum regeneration tower, MTBE and the sulfide that will be dissolved under certain temperature and vacuum tightness in the solvent are extracted out, the MTBE that extracts out and mixture of sulfides are sent into carbon four washing methanol aqueous solution storage tanks in the MTBE device are housed, MTBE and mixture of sulfides are with after methanol-water contacts, MTBE is dissolved in the methanol aqueous solution, deliver to the methanol distillation column of MTBE device, reclaim methyl alcohol and MTBE; Sulfide is insoluble to methanol-water, extracts sulfide out by the upper strata of methanol aqueous solution storage tank.
The present invention has following advantage:
1, eliminated the loss of lyosorption regeneration MTBE and to air environmental pollution;
2, utilize the methanol recovery system that has now in the MTBE device, reclaim MTBE, flow process is simple, and process cost is low.
Embodiment
The invention will be further described by the following examples, but the present invention is not subjected to the restriction of embodiment.
Embodiment all the test all in Sinopec Jiujiang the neat prosperous chemical industry MTBE of company limited adsorptive distillation desulfurization commerical test device finish.
Embodiment 1
Sulfur-bearing 5%(massfraction) and contain the 15%(massfraction) to send into diameter with the speed of 300Kg/h be that 800 millimeters, height are 1000 millimeters vacuum absorption solvent reclamation jar by absorbing the distillation tower tower reactor for the rich lyosorption of MTBE, the control of the temperature of solvent vacuum regeneration jar is 50KPa at 85 ℃, vacuum tightness, and it is 25m that the vacuum extractum is delivered to volume
3The Methanol Recovery storage tank, the dissolving MTBE after methanol aqueous solution loop back methanol distillation column.Analyze vacuum extractum composition, methanol aqueous solution composition, methanol aqueous solution jar upper strata sulfide composition, regeneration back solvent composition, and add up the MTBE plant yield.Analysis and statistics see Table 1.
Embodiment 2
Sulfur-bearing 3%(massfraction) and contain the 10%(massfraction) to send into diameter with the speed of 400Kg/h be that 800 millimeters, height are 1000 millimeters vacuum absorption solvent reclamation jar by absorbing the distillation tower tower reactor for the rich lyosorption of MTBE, the control of the temperature of solvent vacuum regeneration jar is 30KPa at 75 ℃, vacuum tightness, and it is 25m that the vacuum extractum is delivered to volume
3The Methanol Recovery storage tank, the dissolving MTBE after methanol aqueous solution loop back methanol distillation column.Analyze vacuum extractum composition, methanol aqueous solution composition, methanol aqueous solution jar upper strata sulfide composition, regeneration back solvent composition, and add up the MTBE plant yield.Analysis and statistics see Table 1.
Embodiment 3
Sulfur-bearing 15%(massfraction) and contain the 15%(massfraction) to send into diameter with the speed of 500Kg/h be that 800 millimeters, height are 1000 millimeters vacuum absorption solvent reclamation jar by absorbing the distillation tower tower reactor for the rich lyosorption of MTBE, the control of the temperature of solvent vacuum regeneration jar is 40KPa at 80 ℃, vacuum tightness, and it is 25m that the vacuum extractum is delivered to volume
3The Methanol Recovery storage tank, the dissolving MTBE after methanol aqueous solution loop back methanol distillation column.Analyze vacuum extractum composition, methanol aqueous solution composition, methanol aqueous solution jar upper strata sulfide composition, regeneration back solvent composition, and add up the MTBE plant yield.Analysis and statistics see Table 1.
Embodiment 4
Sulfur-bearing 10%(massfraction) and contain the 20%(massfraction) to send into diameter with the speed of 300Kg/h be that 800 millimeters, height are 1000 millimeters vacuum absorption solvent reclamation jar by absorbing the distillation tower tower reactor for the rich lyosorption of MTBE, the control of the temperature of solvent vacuum regeneration jar is 50KPa at 85 ℃, vacuum tightness, and it is 25m that the vacuum extractum is delivered to volume
3The Methanol Recovery storage tank, the dissolving MTBE after methanol aqueous solution loop back methanol distillation column.Analyze vacuum extractum composition, methanol aqueous solution composition, methanol aqueous solution jar upper strata sulfide composition, regeneration back solvent composition, and add up the MTBE plant yield.Analysis and statistics see Table 1.
Table 1:MTBE catalyzed oxidation distillation test result
Claims (3)
1. the method that reclaims of the regeneration of a MTBE adsorption desulfurize solvent and MTBE, it is characterized in that: MTBE and the sulfide that will be dissolved under certain temperature and vacuum tightness in the solvent are extracted out, the MTBE that extracts out and mixture of sulfides are sent into the Methanol Recovery aqueous solution storage tank in the MTBE device, MTBE and mixture of sulfides are with after methanol aqueous solution contacts, MTBE is dissolved in the methanol aqueous solution, deliver to the methanol distillation column in the MTBE device, reclaim methyl alcohol and MTBE; Sulfide is insoluble to methanol-water, extracts sulfide out by the upper strata of methanol aqueous solution storage tank.
2. the method that reclaims of the regeneration of MTBE adsorption desulfurize solvent according to claim 1 and MTBE, it is characterized in that: the vacuum regeneration temperature of adsorption desulfurize solvent is 75-85 ℃.
3. the method that reclaims of the regeneration of MTBE adsorption desulfurize solvent according to claim 2 and MTBE, it is characterized in that: adsorption desulfurize solvent vacuum regeneration vacuum tightness is 30-50KPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310143329.9A CN103193603B (en) | 2013-04-24 | 2013-04-24 | MTBE adsorbs the renovation process of desulfurization solvent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310143329.9A CN103193603B (en) | 2013-04-24 | 2013-04-24 | MTBE adsorbs the renovation process of desulfurization solvent |
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| CN103193603A true CN103193603A (en) | 2013-07-10 |
| CN103193603B CN103193603B (en) | 2017-07-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112007483A (en) * | 2020-10-22 | 2020-12-01 | 山东神驰石化有限公司 | Recovery unit for methyl tert butyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0600632B1 (en) * | 1992-11-19 | 1998-08-19 | Huntsman Specialty Chemicals Corporation | Method for the manufacture and recovery of methyl tertiary butyl ether |
| CN102381945A (en) * | 2011-09-05 | 2012-03-21 | 西南石油大学 | Method and device for removing organic sulfur in methyl tertiary butyl ether (MTBE) |
| CN102898286A (en) * | 2012-08-21 | 2013-01-30 | 九江齐鑫化工有限公司 | Method for removing sulfides in MTBE by adsorptive distillation |
-
2013
- 2013-04-24 CN CN201310143329.9A patent/CN103193603B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0600632B1 (en) * | 1992-11-19 | 1998-08-19 | Huntsman Specialty Chemicals Corporation | Method for the manufacture and recovery of methyl tertiary butyl ether |
| CN102381945A (en) * | 2011-09-05 | 2012-03-21 | 西南石油大学 | Method and device for removing organic sulfur in methyl tertiary butyl ether (MTBE) |
| CN102898286A (en) * | 2012-08-21 | 2013-01-30 | 九江齐鑫化工有限公司 | Method for removing sulfides in MTBE by adsorptive distillation |
Non-Patent Citations (1)
| Title |
|---|
| 李华伟等: "吸附法处理甲基叔丁基醚污染物的研究进展", 《环境科学与技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112007483A (en) * | 2020-10-22 | 2020-12-01 | 山东神驰石化有限公司 | Recovery unit for methyl tert butyl ether |
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