CN102557888A - Method for deeply desulfurizing methyl tertiary butyl ether - Google Patents

Method for deeply desulfurizing methyl tertiary butyl ether Download PDF

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Publication number
CN102557888A
CN102557888A CN2011104363689A CN201110436368A CN102557888A CN 102557888 A CN102557888 A CN 102557888A CN 2011104363689 A CN2011104363689 A CN 2011104363689A CN 201110436368 A CN201110436368 A CN 201110436368A CN 102557888 A CN102557888 A CN 102557888A
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mtbe
sulfur
tower
butyl ether
tertiary butyl
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CN2011104363689A
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CN102557888B (en
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柯明
于沛
宋昭峥
蒋庆哲
陈萌
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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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

A kind of method of MTBE deep desulfuration
Technical field
The invention belongs to petrochemical industry, be specifically related to a kind of method of sulfur-containing methyl tertbutyl ether deep desulfuration.
Background technology
MTBE is the important blending component of producing the high-octane rating motor spirit, carries out etherification reaction production, MTBE (MTBE) boiling point＞55 ℃ through iso-butylene in the LPG liquefied petroleum gas (LPG) and methyl alcohol.Because the LPG liquefied petroleum gas total sulfur after refining exceeds standard, particularly catalytic cracking and delayed coking blended LPG liquefied petroleum gas total sulfur are sometimes up to hundreds of μ gg -1, after the isobutylene etherification with methanol reaction sulphur in the LPG liquefied petroleum gas is concentrated in the MTBE in the LPG liquefied petroleum gas of refining back, make total sulfur content in the MTBE up to hundreds of μ gg -1, even thousands of μ gg -1Because the total sulfur content of MTBE is high, can't be used for concocting the motor spirit of producing country IV or state V, how to solve the high problem of MTBE total sulfur content, be the refinery urgent problem.Through to the sulfide analysis in the MTBE, find that sulfide in the MTBE mainly is the higher sulfide of boiling point such as the above thioether of NSC 9370 (109 ℃ of boiling points), methylethyl disulfide (121 ℃ of boiling points), diethylammonium disulfide (152～154 ℃ of boiling points), C5 (boiling point＞100 ℃) and thiophene-based (boiling point＞84 ℃).
Solution MTBE total sulfur exceeds standard two kinds of approach are arranged at present: LPG liquefied petroleum gas refining plant desulfuration efficiency is improved through technological transformation in (1); Concerning the catalytic cracking LPG liquefied petroleum gas, can make the LPG liquefied petroleum gas total sulfur after making with extra care drop to 20 μ gg through technological transformation -1Below, but also be difficult to stably produce total sulfur less than 50 μ gg -1Below MTBE, but the LPG liquefied petroleum gas total sulfur after possibly will making with extra care through technological transformation hardly for the LPG liquefied petroleum gas total sulfur of delayed coking drops to 20 μ gg -1Below; (2) LPG liquefied petroleum gas after refining partly increases by one at gas separation unit and takes off C 5Tower, the sulfide that makes weights such as NSC 9370 is through taking off C 5Tower is removed, and makes C 4The sulphur content of component drops to 20 μ gg -1Below, just might produce total sulfur less than 50 μ gg -1Following MTBE, but the energy consumption increase is more.
Therefore develop a kind of less investment, simple to operate, process cost is low, the MTBE deep desulfuration technology of non-secondary pollution is very necessary.
Chinese patent CN200910018228 discloses the method for a kind of high sulfur content MTBE desulfurization.Be that the high sulfur content MTBE is placed distillation tower, through the reboiler heating, keeping tower still 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 cat head is 1～10.
CN03816238; WO2004007412, US7304188, patents such as JP2005532400 disclose the method for preparing the high-purity methyl tertbutyl ether; Characteristic 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 and be 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
The method that the purpose of this invention is to provide a kind of MTBE deep desulfuration.
The method of a kind of MTBE deep desulfuration of the present invention is characterized in that: in said method, sulfur-containing methyl tertbutyl ether and light oil are mixed together; Mixed mixture gets into rectifying tower, and through the sulphur compound in the rectifying tower rectifying deep removal sulfur-containing methyl tertbutyl ether, the tower still 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: said light oil is boiling point greater than 60 ℃ reformed gasoline; Straight-run spirit after the hydrogenating desulfurization; Coker gasoline boat kerosene or solar oil after the hydrogenating desulfurization, the add-on of light oil is the 1wt%～15wt% of sulfur-containing methyl tertbutyl ether gross weight.
The invention is characterized in: the straight-run spirit after described reformed gasoline, the hydrogenating desulfurization, the coker gasoline sulphur content after the 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 MTBE deep desulfuration of the present invention comprises the steps:
(a) sulfur-containing methyl tertbutyl ether and light oil are mixed together;
(b) mixed mixture gets into rectifying tower, but through the sulphur in the rectifying tower rectifying deep removal sulfur-containing methyl tertbutyl ether;
The sulfur-bearing heavy constituent of (c) being hanged down out by rectifying tower can be gone the hydro-refining unit desulfurization;
Wherein, the sulfur-containing methyl tertbutyl ether is that raw material production is come out with catalytic liquid gasification or catalysis and coking mixed liquefied gas, and the total sulfur content of sulfur-containing methyl tertbutyl ether is at 10 μ gg -1～2000 μ gg -1
In (a) step, light oil is that boiling point is greater than 60 ℃ reformed gasoline or the straight-run spirit after the hydrogenating desulfurization or the coker gasoline after the hydrogenating desulfurization or boat kerosene or solar oil.The amount that light oil adds is the 1wt%～15wt% of sulfur-containing methyl tertbutyl ether gross weight.
Straight-run spirit after described reformed gasoline, the hydrogenating desulfurization, the coker gasoline sulphur content after the 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 go reformed pre-hydrogenated desulfurization, and boat kerosene and solar oil can go the desulfurization of diesel oil hydrofining device.
The method of a kind of MTBE deep desulfuration of the present invention can be with the total sulfur content of MTBE by the gg of μ more than 1000 -1Be reduced to 10 μ gg -1Below, the MTBE after the rectifying satisfies the requirement of the motor spirit be used for concocting producing country IV or state V well.
Description of drawings
Fig. 1 is the schematic flow sheet of MTBE process for deep desulphurization.
1-sulfur-containing methyl tertbutyl ether line; 2-sulfur-containing methyl tertbutyl ether transferpump; 3-light oil line; 4-light oil transferpump; The 5-static mixer; The 6-heat exchanger; The 7-rectifying tower; 8-water cooler A; The 9-return tank; The 10-reflux pump; 11-makes with extra care the MTBE pump, and the refining MTBE of 12-goes out the device line; The 13-reboiler; 14-heating steam; The heavy constituent of 15-sulfur-bearing; 16-water cooler A; The device line is told in the reorganization of 17-sulfur-bearing
Embodiment
Comparative example
Make an experiment raw material at the small-sized rectifier unit of 500ml: MTBE, sulphur content are 864 μ gg -1The rectifying tower operational condition is: tower bottom pressure is 0.025MPa, and tower top pressure 0.02MPa, column bottom temperature are 85 ℃, and 55 ℃ of tower top temperatures, theoretical plate number are 8, and reflux ratio is 6.MTBE sulphur total sulfur content after the rectifying is 145 μ gg -1
Embodiment 1
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 95wt% (sulphur content 864 μ gg -1) with reformed gasoline (the sulphur content 0 μ gg of 5wt% -1) mixture, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 72 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 2.MTBE sulphur total sulfur content after the rectifying is 2 μ gg -1
Embodiment 2
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 95wt% (sulphur content 864 μ gg -1) with reformed gasoline (the sulphur content 0 μ gg of 5wt% -1) mixture, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 72 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 0.5.MTBE sulphur total sulfur content after the rectifying is 9 μ gg -1
Embodiment 3
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 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, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 72 ℃, 54 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 2.MTBE sulphur total sulfur content after the rectifying is 3 μ gg -1
Embodiment 4
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 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, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 72 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 1.MTBE sulphur total sulfur content after the rectifying is 6 μ gg -1
Embodiment 5
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 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, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 95 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 1.MTBE sulphur total sulfur content after the rectifying is 8 μ gg -1
Embodiment 6
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 95wt% (sulphur content 864 μ gg -1) with boat kerosene (the sulphur content 238 μ gg of 5wt% -1) mixture, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 95 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 2.MTBE sulphur total sulfur content after the rectifying is 5 μ gg -1
Embodiment 7
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 95wt% (sulphur content 864 μ gg -1) with solar oil (the sulphur content 289 μ gg of 5wt% -1) mixture, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 100 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 1.MTBE sulphur total sulfur content after the rectifying is 7 μ gg -1
Embodiment 8
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 95wt% (sulphur content 1458 μ gg -1) and 5wt% solar oil (sulphur content 289 μ gg -1) mixture, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 100 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 4.MTBE sulphur total sulfur content after the rectifying is 6 μ gg -1
Embodiment 9
Make an experiment raw material at the small-sized rectifier unit of 500ml: the MTBE of 95wt% (sulphur content 371 μ gg -1) with solar oil (the sulphur content 289 μ gg of 5wt% -1) mixture, the rectifying tower operational condition is: tower bottom pressure is 0.025MPa, tower top pressure 0.02MPa, column bottom temperature are 100 ℃, 55 ℃ of tower top temperatures, theoretical plate number are 8, reflux ratio is 1.MTBE sulphur total sulfur content after the rectifying is 5 μ gg -1

Claims (3)

1. the method for a MTBE deep desulfuration, it is characterized in that: in said method, sulfur-containing methyl tertbutyl ether and light oil are mixed together; Mixed mixture gets into rectifying tower, and through the sulphur compound in the rectifying tower rectifying deep removal sulfur-containing methyl tertbutyl ether, the tower still 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.
2. the method for MTBE deep desulfuration according to claim 1; It is characterized in that: said light oil is boiling point greater than 60 ℃ reformed gasoline; Straight-run spirit after the hydrogenating desulfurization; Coker gasoline after the hydrogenating desulfurization, boat kerosene or solar oil, the add-on of light oil is the 1wt%～15wt% of sulfur-containing methyl tertbutyl ether gross weight.
3. the method for MTBE deep desulfuration according to claim 2 is characterized in that: the straight-run spirit after described reformed gasoline, the hydrogenating desulfurization, the coker gasoline sulphur content after the 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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Cited By (6)

* Cited by examiner, † Cited by third party
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
CN103820149A (en) * 2012-11-16 2014-05-28 中国石油天然气股份有限公司 Method for reducing sulfur content in liquefied gas
CN103880605A (en) * 2012-12-21 2014-06-25 中国石油天然气股份有限公司 Method for removing sulfides with high boiling points in methyl tert-butyl ether
CN105712848A (en) * 2016-03-23 2016-06-29 陆明全 Methyl tertiary butyl ether desulfurizing agent and application method thereof
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
CN108218677A (en) * 2016-12-22 2018-06-29 中国石油天然气股份有限公司 A kind of method and device of methyl tertiary butyl ether(MTBE) desulfurization

Citations (1)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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 (2)

* Cited by examiner, † Cited by third party
Title
CHUNSHAN SONG: "An overview of new approaches to deep desulfurization for ultra-clean gasoline，diesel fuel and jet fuel", 《CATALYSIS TODAY》 *
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》 *

Cited By (9)

* Cited by examiner, † Cited by third party
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
CN103820149A (en) * 2012-11-16 2014-05-28 中国石油天然气股份有限公司 Method for reducing sulfur content in liquefied gas
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
CN103880605A (en) * 2012-12-21 2014-06-25 中国石油天然气股份有限公司 Method for removing sulfides with high boiling points in methyl tert-butyl ether
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)
CN105712848A (en) * 2016-03-23 2016-06-29 陆明全 Methyl tertiary butyl ether desulfurizing agent and application method thereof
CN108218677A (en) * 2016-12-22 2018-06-29 中国石油天然气股份有限公司 A kind of method and device of methyl tertiary butyl ether(MTBE) desulfurization
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

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