CN103193603B - MTBE adsorbs the renovation process of desulfurization solvent - Google Patents
MTBE adsorbs the renovation process of desulfurization solvent Download PDFInfo
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- CN103193603B CN103193603B CN201310143329.9A CN201310143329A CN103193603B CN 103193603 B CN103193603 B CN 103193603B CN 201310143329 A CN201310143329 A CN 201310143329A CN 103193603 B CN103193603 B CN 103193603B
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- mtbe
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Abstract
The present invention provides the method that a kind of regeneration of MTBE absorption desulfurization solvent and MTBE are reclaimed.It is exactly specifically：When MTBE adsorbs desulfurization solvent vacuum regeneration, the MTBE that vacuum is extracted out is dissolved in the methanol recycled water of MTBE devices with the mixture of sulfide, MTBE is dissolved in methanol recycled water, MTBE is reclaimed by MTBE devices methanol recovery system, because sulfide is water insoluble, sulfide is reclaimed by methanol-water tourie, realizes that MTBE is reclaimed and adsorption solvent regeneration.
Description
Technical field
The invention belongs to technical field of petrochemical industry.It is related to sulfide technology in removing MTBE, is specifically to provide a kind of suction
The renovation process of sulfide solvent in attached distillation removing MTBE.
Background technology
MTBE（Methyl tertiary butyl ether(MTBE)）It is liquefied petroleum gas（C-4-fraction）Middle isobutene and methyl alcohol addition reaction product.
MTBE is both clean gasoline with high octane blending component, is also the raw material of the cracking high-purity isobutene of production, is a kind of important stone
Oily industrial chemicals and product.
As crude oil heaviness, in poor quality develop, and the requirement to the continuous intensification of comprehensive utilization of resources, catalytic cracking and Jiao
Sulfur content gradually rises in changing C-4-fraction.While C-4-fraction and methyl alcohol addition reaction produce MTBE, in C-4-fraction
The sulfur-containing compound such as mercaptan generate macromolecular sulfide with butene reaction.Because MTBE has than hydro carbons with higher to sulfide
Dissolubility, when MTBE is separated with carbon after ether four, in carbon four sulfide of sulfur-containing compound and C 4 olefin reaction generation and
Sulfide almost all in C-4-fraction is enriched with by product MTBE, and sulfide content is high in causing MTBE products, not only not
Clean gasoline standard can be met, and influence the follow-up chemical utilization of MTBE.Sulfide in removing MTBE, is petroleum refining and stone
Oily chemical enterprise urgent need to solve the problem.
Sulfide mainly uses the alkali washing process such as diethanol amine in removing liquefied petroleum gas at present, but due to crude oil weight
Matter, the development trend of in poor quality, sulfide molecules increase, is difficult to wherein sulphur by prior art in liquefied petroleum gas
Compound is removed to standard requirement；The sulfide of the hydrocarbon raw materials such as removing gasoline, diesel oil, generally uses Hydrofining Technology at present,
But MTBE is oxygenatedchemicals, because carbon-sulfur bond bond energy is far above carbon-oxygen bond bond energy, in hydrodesulfurization, carbon oxygen in MTBE
Key hydrogenation deoxidation first, generates corresponding alkane, and causes a large amount of MTBE to lose.Therefore, it is necessary to develop MTBE for molecule knot
Sulfide removing sulfuldioxide in the unstable MTBE of structure.
Inventor discloses a kind of technology of sulfide in adsorptive distillation removing MTBE in CN102898286A patents.With
Boiling point is higher than MTBE, and it is adsorbent to have the material of stronger adsorptive selectivity to thioether, mercaptan and disulphide and thiophene,
Under uniform temperature and process conditions, by sulfide selective absorption in MTBE in adsorbent；Simultaneously containing sulfur absorbent using true
The method regeneration cycle of sky distillation is used, and reclaims sulfide, and sulfide in MTBE is removed and recycled by realization.But solvent
A small amount of MTBE is also adsorbed while absorption sulfide, while using vacuum distillation removing and recovery sulfide, MTBE can be caused
Loss, and there is a small amount of MTBE to enter air with vacuum system, cause atmosphere pollution.
The content of the invention
According to background technology, during MTBE adsorptive distillations removing sulfide：MTBE and solvent have certain mutual
Dissolubility, when sulfide in using vacuum distillation removing adsorption solvent, can cause MTBE to lose and to atmosphere pollution；Find simultaneously
Sulfide in MTBE is main with the presence of thioether, alkyl disulfide and alkyl trisulfide form, and thioether, alkyl curing
Thing, alkyl trisulfide are substantially insoluble in water, and MTBE has certain solubility in water.According to MTBE and the spy of sulfide
Property, the present invention provides the method that a kind of regeneration of MTBE absorption desulfurization solvent and MTBE are reclaimed.
It is exactly specifically：When MTBE adsorbs desulfurization solvent vacuum regeneration, by the MTBE of vacuum extraction and sulfide
Mixture is dissolved in the methanol recycled water of MTBE devices, and MTBE is dissolved in methanol recycled water, is returned by MTBE devices methanol recovery system
MTBE is received, because sulfide is water insoluble, sulfide is reclaimed by methanol-water tourie, realize that MTBE is reclaimed with adsorption solvent again
It is raw.
The regeneration of MTBE absorption desulfurization solvents is realized in the following way：The rich solvent of sulfide in MTBE is absorbed, by
MTBE absorbs distillation desulfurizing tower tower reactor and extracts the rich solvent feeding solvent in vacuo regenerator rich in sulphur and MTBE out, in uniform temperature and
The MTBE and sulfide that will be dissolved under vacuum in solvent are extracted out, and MTBE and the mixture of sulfides feeding of extraction are equipped with MTBE
The washing of carbon four methanol aqueous solution storage tank in device, after MTBE is contacted with mixture of sulfides with methanol-water, MTBE is dissolved in methyl alcohol
In the aqueous solution, the methanol distillation column of MTBE devices is delivered to, reclaim methyl alcohol and MTBE；Sulfide does not dissolve in methanol-water, by methanol-water
Extract sulfide out in the upper strata of solution reservoir.
The present invention has the advantage that：
1st, the loss of lyosoption regeneration MTBE is eliminated and to air environmental pollution；
2nd, using the methanol recovery system in existing MTBE devices, MTBE is reclaimed, flow is simple, and operating cost is low.
Specific embodiment
The invention will be further described by the following examples, but the present invention should not be limited by the examples.
The all experiments of embodiment are in the Qi Xin Chemical Co., Ltd.s MTBE adsorptive distillations desulfurization industry examination of Sinopec Jiujiang
Completed on experiment device.
Embodiment 1
Sulfur-bearing 5%（Mass fraction）With containing 15%（Mass fraction）The rich lyosoption of MTBE by absorption destilling tower tower reactor with
The speed of 300Kg/h sends into a diameter of 800 millimeters, a height of 1000 millimeters of vacuum absorption solvent reclamation tank, solvent in vacuo regeneration
The temperature control of tank is 50KPa in 85 DEG C, vacuum, and vacuum extract delivers to volume for 25m3Methanol Recovery storage tank, dissolving
Methanol aqueous solution loops back methanol distillation column after MTBE.Analysis vacuum extract composition, methanol aqueous solution composition, methanol aqueous solution
Solvent composition after tank upper strata sulfide composition, regeneration, and count MTBE plant yields.Analysis and statistics are shown in Table 1.
Embodiment 2
Sulfur-bearing 3%（Mass fraction）With containing 10%（Mass fraction）The rich lyosoption of MTBE by absorption destilling tower tower reactor with
The speed of 400Kg/h sends into a diameter of 800 millimeters, a height of 1000 millimeters of vacuum absorption solvent reclamation tank, solvent in vacuo regeneration
The temperature control of tank is 30KPa in 75 DEG C, vacuum, and vacuum extract delivers to volume for 25m3Methanol Recovery storage tank, dissolving
Methanol aqueous solution loops back methanol distillation column after MTBE.Analysis vacuum extract composition, methanol aqueous solution composition, methanol aqueous solution
Solvent composition after tank upper strata sulfide composition, regeneration, and count MTBE plant yields.Analysis and statistics are shown in Table 1.
Embodiment 3
Sulfur-bearing 15%（Mass fraction）With containing 15%（Mass fraction）The rich lyosoption of MTBE by absorption destilling tower tower reactor with
The speed of 500Kg/h sends into a diameter of 800 millimeters, a height of 1000 millimeters of vacuum absorption solvent reclamation tank, solvent in vacuo regeneration
The temperature control of tank is 40KPa in 80 DEG C, vacuum, and vacuum extract delivers to volume for 25m3Methanol Recovery storage tank, dissolving
Methanol aqueous solution loops back methanol distillation column after MTBE.Analysis vacuum extract composition, methanol aqueous solution composition, methanol aqueous solution
Solvent composition after tank upper strata sulfide composition, regeneration, and count MTBE plant yields.Analysis and statistics are shown in Table 1.
Embodiment 4
Sulfur-bearing 10%（Mass fraction）With containing 20%（Mass fraction）The rich lyosoption of MTBE by absorption destilling tower tower reactor with
The speed of 300Kg/h sends into a diameter of 800 millimeters, a height of 1000 millimeters of vacuum absorption solvent reclamation tank, solvent in vacuo regeneration
The temperature control of tank is 50KPa in 85 DEG C, vacuum, and vacuum extract delivers to volume for 25m3Methanol Recovery storage tank, dissolving
Methanol aqueous solution loops back methanol distillation column after MTBE.Analysis vacuum extract composition, methanol aqueous solution composition, methanol aqueous solution
Solvent composition after tank upper strata sulfide composition, regeneration, and count MTBE plant yields.Analysis and statistics are shown in Table 1.
Table 1：MTBE catalysis oxidation distillation test results
Claims (3)
1. the method that a kind of regeneration of MTBE absorption desulfurization solvent and MTBE are reclaimed, it is characterised in that：Distillation is absorbed by MTBE de-
Sulphur tower tower reactor extracts the rich solvent feeding solvent in vacuo regenerator rich in sulphur and MTBE out, will dissolving under uniform temperature and vacuum
MTBE and sulfide in solvent are extracted out, and MTBE and the mixture of sulfides of extraction send into the methanol recycled water in MTBE devices
Solution reservoir, after MTBE is contacted with mixture of sulfides with methanol aqueous solution, MTBE is dissolved in methanol aqueous solution, delivers to MTBE
Methanol distillation column in device, reclaims methyl alcohol and MTBE；Sulfide does not dissolve in methanol-water, is taken out by the upper strata of methanol aqueous solution storage tank
Go out sulfide.
2. the method that the regeneration of MTBE absorption desulfurization solvent according to claim 1 and MTBE are reclaimed, it is characterised in that：Inhale
The vacuum regeneration temperature of attached desulfurization solvent is 75-85 DEG C.
3. the method that the regeneration of MTBE absorption desulfurization solvent according to claim 2 and MTBE are reclaimed, it is characterised in that：Inhale
Attached desulfurization solvent vacuum regeneration vacuum is 30-50 KPa.
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 CN103193603A (en) | 2013-07-10 |
| CN103193603B true CN103193603B (en) | 2017-07-04 |
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| CN112007483B (en) * | 2020-10-22 | 2021-01-26 | 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 |
|---|
| 吸附法处理甲基叔丁基醚污染物的研究进展;李华伟等;《环境科学与技术》;20060628;第29卷(第03期);第101-104页 * |
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