CN102557888B - Method for deeply desulfurizing methyl tertiary butyl ether - Google Patents
Method for deeply desulfurizing methyl tertiary butyl ether Download PDFInfo
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- CN102557888B CN102557888B CN201110436368.9A CN201110436368A CN102557888B CN 102557888 B CN102557888 B CN 102557888B CN 201110436368 A CN201110436368 A CN 201110436368A CN 102557888 B CN102557888 B CN 102557888B
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- tertiary butyl
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Abstract
The invention provides a method for deeply desulfurizing methyl tertiary butyl ether. The method is characterized in that the sulfur-containing methyl tertiary butyl ether is mixed with light oil to form a mixture; the mixture enters a distillation column for distillation, so as to remove sulfur compounds in the sulfur-containing methyl tertiary butyl ether; and the column reactor temperature of the distillation column is 70 DEG C to 120 DEG C, the column top temperature is 50 DEG C to 60 DEG C, the pressure is 0.01 MPa to 0.15 MPa, the theoretical column plate number is 3 to 20 and the reflux ratio is 0.25 to 10. By adopting the method, the total sulfur content of the methyl tertiary butyl ether can be reduced from more than 1000 Mug*g-1 to less than 1000 Mug*g-1, and the distilled methyl tertiary butyl ether can well satisfy the requirement of mixing automotive gasoline of a production country IV or a production country V.
Description
Technical field
The invention belongs to petrochemical industry, be specifically related to a kind of method of sulfur methyl tertiary butyl ether deep desulfuration.
Background technology
Methyl tertiary butyl ether is the important blending component of producing High-octane mogas, by iso-butylene in liquefied petroleum gas (LPG) (LPG) and methyl alcohol, carries out etherification reaction production, 55 ℃ of methyl tertiary butyl ether (MTBE) boiling point >.Because the liquefied petroleum gas (LPG) total sulfur after refining exceeds standard, the liquefied petroleum gas (LPG) total sulfur that particularly catalytic cracking and delayed coking mix is sometimes up to hundreds of μ gg
-1, after isobutylene etherification with methanol reaction, can make the sulphur in liquefied petroleum gas (LPG) be concentrated in methyl tertiary butyl ether in liquefied petroleum gas (LPG) after refining, make total sulfur content in methyl tertiary butyl ether up to hundreds of μ gg
-1, even thousands of μ gg
-1.Because the total sulfur content of methyl tertiary butyl ether is high, cannot be used for concocting the motor spirit of producing country IVHuo state V, how to solve the problem that methyl tertiary butyl ether total sulfur content is high, be refinery urgent problem.By the sulfide analysis in methyl tertiary butyl ether, find that the sulfide in methyl tertiary butyl ether is mainly the higher sulfide of boiling point such as dimethyl disulfide (109 ℃ of boiling points), methylethyl disulfide (121 ℃ of boiling points), diethyl disulfide (152～154 ℃ of boiling points), thioether more than C5 (100 ℃ of boiling point >) and thiophene-based (84 ℃ of boiling point >).
Solution methyl tertiary butyl ether total sulfur exceeds standard and has two kinds of approach at present: (1) improves liquefied petroleum gas (LPG) refining plant desulfuration efficiency by technological transformation, concerning catalytic cracking liquefied petroleum gas (LPG), by technological transformation, can make the liquefied petroleum gas (LPG) total sulfur after refining drop to 20 μ gg
-1below, but be also difficult to stably to produce total sulfur and be less than 50 μ gg
-1following methyl tertiary butyl ether, but may the liquefied petroleum gas (LPG) total sulfur after refining be dropped to 20 μ gg by technological transformation hardly for the liquefied petroleum gas (LPG) total sulfur of delayed coking
-1below; (2) liquefied petroleum gas (LPG) after refining partly increases a de-C at gas separation unit
5tower, makes the heavy de-C of sulfide warp such as dimethyl disulfide
5tower is removed, and makes C
4the sulphur content of component drops to 20 μ gg
-1below, just likely produce total sulfur and be less than 50 μ gg
-1following methyl tertiary butyl ether, but energy consumption increase is more.
Therefore develop a kind of less investment, simple to operate, process cost is low, the methyl tertiary butyl ether deep desulfuration technique of non-secondary pollution is very necessary.
Chinese patent CN200910018228 discloses the method for a kind of high sulfur content MTBE desulfurization.Be that high sulfur content methyl tertiary butyl ether is placed in to distillation tower, by reboiler, heat, keeping tower reactor temperature is 90～120 ℃, pressure is 0.08 ± 0.02MPa, tower top temperature is 69～75 ℃, and pressure is 0.06 ± 0.02MPa, and making finished product steam and keep reflux ratio from tower top is 1～10.
CN03816238, WO2004007412, US7304188, the patents such as JP2005532400 disclose the method for preparing high-purity methyl tertbutyl ether, feature is that industrial MTBE is separated into the cut that has lower boiling and comprise MTBE, first alcohol and water, have mean boiling point and comprise purity higher than the cut of 99.7% MTBE, and have high boiling point and comprise TBA and the cut of butene low polymers, fractionation is carried out at least two towers and at least one partition-wall column.
Summary of the invention
A kind of method that the object of this invention is to provide methyl tertiary butyl ether deep desulfuration.
The method of a kind of methyl tertiary butyl ether deep desulfuration of the present invention, it is characterized in that: in described method, sulfur methyl tertiary butyl ether and light oil are mixed together, mixed mixture enters rectifying tower, and by the sulphur compound in rectifying tower rectifying deep removal sulfur methyl tertiary butyl ether, the tower reactor temperature of rectifying tower is 70 ℃～120 ℃, tower top temperature is 50 ℃～60 ℃, pressure is 0.01MPa～0.15MPa, and theoretical plate number is 3～20, and reflux ratio is 0.25～10.
The invention is characterized in: described light oil is the reformed gasoline that boiling point is greater than 60 ℃, straight-run spirit after hydrogenating desulfurization, coker gasoline boat kerosene or solar oil after hydrogenating desulfurization, the add-on of light oil is the 1wt%～15wt% of sulfur methyl tertiary butyl ether gross weight.
The invention is characterized in: described reformed gasoline, the straight-run spirit after hydrogenating desulfurization, the coker gasoline sulphur content after hydrogenating desulfurization are at 10 μ gg
-1below, boat kerosene or solar oil sulphur content are at 300 μ gg
-1below.
The method of a kind of methyl tertiary butyl ether deep desulfuration of the present invention, comprises the steps:
(a) sulfur methyl tertiary butyl ether and light oil are mixed together;
(b) mixed mixture enters rectifying tower, the sulphur by rectifying tower rectifying in can deep removal sulfur methyl tertiary butyl ether;
(c) by the low sulfur-bearing heavy constituent out of rectifying tower, can go hydro-refining unit desulfurization;
Wherein, sulfur methyl tertiary butyl ether take catalytic liquefaction gas or catalysis and coking mixed liquefied gas as raw material production out, the total sulfur content of sulfur methyl tertiary butyl ether is at 10 μ gg
-1～2000 μ gg
-1.
In (a) step, light oil is that boiling point is greater than the reformed gasoline of 60 ℃ or the straight-run spirit after hydrogenating desulfurization or the coker gasoline after hydrogenating desulfurization or boat kerosene or solar oil.The amount that light oil adds is the 1wt%～15wt% of sulfur methyl tertiary butyl ether gross weight.
Described reformed gasoline, the straight-run spirit after hydrogenating desulfurization, the coker gasoline sulphur content after hydrogenating desulfurization are at 10 μ gg
-1below, boat kerosene or solar oil sulphur content are at 300 μ gg
-1below.
In the sulfur-bearing heavy constituent described in (c) step, gasoline can the whole pre-hydrogenating desulfurization of duplicate removal, and boat kerosene and solar oil can go Diesel Oil Hydrofining Unit desulfurization.
The method of a kind of methyl tertiary butyl ether deep desulfuration of the present invention can be by the total sulfur content of methyl tertiary butyl ether by the gg of μ more than 1000
-1be reduced to 10 μ gg
-1below, the methyl tertiary butyl ether after rectifying meets the requirement of the motor spirit be used for concocting producing country IVHuo state V well.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of methyl tertiary butyl ether process for deep desulphurization.
1-sulfur methyl tertiary butyl ether line; 2-sulfur methyl tertiary butyl ether transferpump; 3-light oil line; 4-light oil transferpump; 5-static mixer; 6-heat exchanger; 7-rectifying tower; 8-water cooler A; 9-return tank; 10-reflux pump; 11-refines methyl tertiary butyl ether pump, and the refining methyl tertiary butyl ether of 12-goes out device line; 13-reboiler; 14-heating steam; 15-sulfur-bearing heavy constituent; 16-water cooler A; The restructuring of 17-sulfur-bearing separates device line
Embodiment
Comparative example
At the small-sized rectifier unit of 500ml, test raw material: methyl tertiary butyl ether, sulphur content is 864 μ gg
-1.Rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, and column bottom temperature is 85 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 6.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 145 μ gg
-1.
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 95wt% (sulphur content 864 μ gg
-1) with reformed gasoline (the sulphur content 0 μ gg of 5wt%
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 72 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 2.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 2 μ gg
-1.
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 95wt% (sulphur content 864 μ gg
-1) with reformed gasoline (the sulphur content 0 μ gg of 5wt%
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 72 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 0.5.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 9 μ gg
-1.
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 97wt% (sulphur content 864 μ gg
-1) with 60 ℃～90 ℃ hydrogenating desulfurizations of 3wt% after straight-run spirit (sulphur content 2 μ gg
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 72 ℃, 54 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 2.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 3 μ gg
-1.
Embodiment 4
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 92wt% (sulphur content 864 μ gg
-1) with 60 ℃～90 ℃ hydrogenating desulfurizations of 8wt% after straight-run spirit (sulphur content 0 μ gg
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 72 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 1.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 6 μ gg
-1.
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 95wt% (sulphur content 864 μ gg
-1) with 90 ℃～120 ℃ hydrogenating desulfurizations of 5wt% after straight-run spirit (sulphur content 0 μ gg
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 95 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 1.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 8 μ gg
-1.
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 95wt% (sulphur content 864 μ gg
-1) with boat kerosene (the sulphur content 238 μ gg of 5wt%
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 95 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 2.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 5 μ gg
-1.
Embodiment 7
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 95wt% (sulphur content 864 μ gg
-1) with solar oil (the sulphur content 289 μ gg of 5wt%
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 100 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 1.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 7 μ gg
-1.
Embodiment 8
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 95wt% (sulphur content 1458 μ gg
-1) and 5wt% solar oil (sulphur content 289 μ gg
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 100 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 4.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 6 μ gg
-1.
Embodiment 9
At the small-sized rectifier unit of 500ml, test the methyl tertiary butyl ether of raw material: 95wt% (sulphur content 371 μ gg
-1) with solar oil (the sulphur content 289 μ gg of 5wt%
-1) mixture, rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature is 100 ℃, 55 ℃ of tower top temperatures, theoretical plate number is 8, reflux ratio is 1.Methyl tertiary butyl ether sulphur total sulfur content after rectifying is 5 μ gg
-1.
Claims (1)
1. the method for a methyl tertiary butyl ether deep desulfuration, it is characterized in that: in described method, sulfur methyl tertiary butyl ether and light oil are mixed together, and mixed mixture enters rectifying tower, by the sulphur compound in rectifying tower rectifying deep removal sulfur methyl tertiary butyl ether, the tower reactor temperature of rectifying tower is 70 ℃～120 ℃, tower top temperature is 50 ℃～60 ℃, and pressure is 0.01MPa～0.15MPa, and theoretical plate number is 3～20, reflux ratio is 0.25～10
Described light oil is the reformed gasoline that boiling point is greater than 60 ℃, the straight-run spirit after hydrogenating desulfurization, and the coker gasoline after hydrogenating desulfurization, boat kerosene or solar oil, the add-on of light oil is the 1wt%～15wt% of sulfur methyl tertiary butyl ether gross weight,
Described reformed gasoline, the straight-run spirit after hydrogenating desulfurization, the coker gasoline sulphur content after hydrogenating desulfurization are at 10 μ gg
-1below, boat kerosene or solar oil sulphur content are at 300 μ gg
-1below.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103820149B (en) * | 2012-11-16 | 2015-10-28 | 中国石油天然气股份有限公司 | A kind of method reducing sulphur content in liquefied gas |
| CN103880605B (en) * | 2012-12-21 | 2016-08-10 | 中国石油天然气股份有限公司 | A kind of remove the method for higher boiling sulfur compound in methyl tertiary butyl ether(MTBE) |
| CN105712848B (en) * | 2016-03-23 | 2018-02-02 | 陆明全 | A kind of methyl tertiary butyl ether(MTBE) desulfurizing agent and its application method |
| CN108218677B (en) * | 2016-12-22 | 2021-08-31 | 中国石油天然气股份有限公司 | Method and device for desulfurizing methyl tert-butyl ether |
| CN107721830A (en) * | 2017-08-25 | 2018-02-23 | 中国石油化工股份有限公司 | The mixed fragrant MTBE extractions antigum inhibitor of one kind |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643392A (en) * | 2009-08-31 | 2010-02-10 | 山东玉皇化工有限公司 | Method for desulphurizing methyl tertiary butyl ether with high sulphur content |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643392A (en) * | 2009-08-31 | 2010-02-10 | 山东玉皇化工有限公司 | Method for desulphurizing methyl tertiary butyl ether with high sulphur content |
Non-Patent Citations (3)
| Title |
|---|
| Chunshan Song.An overview of new approaches to deep desulfurization for ultra-clean gasoline，diesel fuel and jet fuel.《CATALYSIS TODAY》.2003,第86卷第211-263页. * |
| 王豪等.直硫柴油催化氧化脱硫萃取剂研究.《石油与天然气化工》.2004,第33卷(第6期),第416-419页. |
| 直硫柴油催化氧化脱硫萃取剂研究;王豪等;《石油与天然气化工》;20041231;第33卷(第6期);第416-419页 * |
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