CN102617297A - Device and method for removing disulfide from methyl tertiary butyl ether (MTBE) - Google Patents
Device and method for removing disulfide from methyl tertiary butyl ether (MTBE) Download PDFInfo
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- CN102617297A CN102617297A CN2012100657300A CN201210065730A CN102617297A CN 102617297 A CN102617297 A CN 102617297A CN 2012100657300 A CN2012100657300 A CN 2012100657300A CN 201210065730 A CN201210065730 A CN 201210065730A CN 102617297 A CN102617297 A CN 102617297A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a device and method for removing disulfide from methyl tertiary butyl ether (MTBE). The device comprises a static mixer, an MTBE distillation tower, a condenser, a refluxing tank, a cooler and a reboiler. The method comprises the following steps of: fully mixing low-sulfur diesel oil with MTBE in the ratio of 1:1; extracting disulfide from the MTBE into the low-sulfur diesel oil according to the rule of similarity; putting into the MTBE distillation tower; heating the MTBE distillation tower through the reboiler; evaporating finished MTBE from a tower top, and keeping the reflux ratio at 1-1.5; and cooling the low-sulfur diesel oil through the cooler below 35 DEG C for recovering. The device and the method have the beneficial effects of convenience for operating, simple process, no pollution, small investment, low cost, advanced technology, wide market prospect, high economic benefit, energy saving, environmental friendliness, high product yield, safety and reliability in an entire process preparation flow and stable product quality.
Description
Technical field
The present invention relates to a kind of device and method that removes disulphide in the MTBE.
Background technology
In recent years, along with the fast development of national economy, oil refining, chemical industry become the mainstay of the national economy.MTBE (MTBE) is good gasoline high-octane rating additive and octane promoter as a kind of high octane gasoline component.MTBE and gasoline can arbitrary proportion dissolve each other and demixing phenomenon do not take place, and when being in harmonious proportion with gasoline component, good mediation effect are arranged, and the octane value that is in harmonious proportion is higher than its clear octane number.Along with the height enterprise of global oil price, energy scarcity is serious day by day, and MTBE can improve the octane value of gasoline, can reduce the tail gas exhaust gas discharging, helps protecting environment, has obtained using widely in China.
Sulphur in the MTBE product is main with disulphide mainly, and MTBE takes off the realization of disulphide technology, causes equipment corrosion in the existence of eliminating sulphur, reduces the pollution aspect and has development prospect and practical value widely.Because the oil of China is in the majority with high-content sulphur, the product disulphide content of domestic MTBE is generally higher, and this feed composition with the upper reaches also has relation, and this has brought great difficulty to production and the sale of MTBE virtually.The existing desulfurization technology of MTBE mainly is the control feed sulphur content and adopts direct distillatory mode.
1, through control raw material sulphur content, particularly control the sulphur content in the material carbon four, generally be mode through alkali cleaning, the mode of alkali cleaning can only remove hydrogen sulfide and mercaptan sulfur, the sulphur of other forms then difficulty remove.And in alkali washing process, can produce by product disulphide, thereby disulphide then can be entrained in to be transferred in the alkali lye in carbon four raw materials, causes that the MTBE total sulfur is higher.So want the sulphur content from source control carbon four; Need a large amount of, frequent replacing alkali lye, in could interim assurance carbon four than low sulfur content, and a large amount of, the frequent alkali that changes causes the alkaline residue quantity discharged to increase greatly; Environment is caused bigger pressure, also increased processing cost simultaneously.
2, directly the distillatory mode directly places the MTBE distillation tower with MTBE exactly; Utilize the distillation principle to realize removing the purpose of disulphide,, belong to the ppm rank because the disulphide content among the MTBE is less; After this just causes straight run distillation; The MTBE earning rate descends, and earning rate has only 40-60%, and economic benefit reduces greatly.
Summary of the invention
The purpose of this invention is to provide a kind of device and method that removes disulphide in the MTBE, remedied weak point of the prior art.
The objective of the invention is to realize through following technical scheme:
A kind of device that removes disulphide in the MTBE (MTBE); Comprise static mixer and the MTBE distillation tower that is connected with static mixer; MTBE distillation tower middle and lower part is connected with reboiler through MTBE and diesel fuel mixtures material extraction line with heating back MTBE and diesel fuel mixtures material feed-pipe; MTBE distillation tower top is connected with condensing surface through gasification MTBE extraction line; Condensing surface through condensation after the MTBE extraction line be connected with return tank, return tank is connected with the MTBE distillation tower through product MTBE return line, is connected with product MTBE extraction line on the product MTBE return line; MTBE distillation tower bottom is connected with water cooler through reclaiming the diesel oil delivery pipe, and water cooler is provided with and reclaims diesel oil extraction line, cooling water inlet pipe one and cooling water outlet pipe one.
Said static mixer is provided with MTBE feed-pipe and low-sulfur diesel-oil feed-pipe, and static mixer inside is equipped with ripple packing.Said MTBE distillation tower inside is provided with column plate, and the quantity of column plate is 1-70.Said reboiler is provided with steam feed pipe and water of condensation rising pipe one; Said MTBE and diesel fuel mixtures material extraction line are provided with recycle pump, and circulating-pump outlet is connected with the reboiler bottom with diesel fuel mixtures material extraction line through MTBE.Said condensing surface is provided with cooling water inlet pipe two and water of condensation rising pipe two.Said product MTBE return line is provided with reflux pump, and the reflux pump import is connected with said return tank bottom through product MTBE return line.
Utilize said apparatus to remove the method for disulphide in the MTBE (MTBE), may further comprise the steps:
At first low-sulfur diesel-oil is mixed behind the static mixer thorough mixing by 1:1 with MTBE, the disulphide in the MTBE is extracted in the low-sulfur diesel-oil owing to the similar principle that mixes;
Place the MTBE distillation tower then, the MTBE distillation tower keeps MTBE base product temperature at 100-120 ℃ through the reboiler heating, and pressure is 0.1 ± 0.02 Mpa, and MTBE distillation tower top temperature is 40-60 ℃, and pressure is 0.08 ± 0.02 Mpa;
Last MTBE finished product steams and keeps reflux ratio from MTBE distillation cat head is 1-1.5, and low-sulfur diesel-oil reclaims after water cooler is cooled to below 35 ℃ from the MTBE base product.
Beneficial effect of the present invention is: easy to operate, technology is simple, pollution-free, less investment, low, the advanced technology of cost; Have vast market prospect and economic benefit, energy-conserving and environment-protective simultaneously; MTBE product earning rate is high, reaches more than 90%, and whole prepared flow process is safe and reliable, constant product quality.
Description of drawings
According to accompanying drawing the present invention is done further explain below.
Fig. 1 is the described apparatus structure synoptic diagram that removes disulphide in the MTBE of the embodiment of the invention.
Among the figure:
1, static mixer; 2, MTBE distillation tower; 3, MTBE and diesel fuel mixtures material extraction line; 4, heating back MTBE and diesel fuel mixtures material feed-pipe; 5, reboiler; 6, gasification MTBE extraction line; 7, condensing surface; 8, MTBE extraction line after the condensation; 9, return tank; 10, product MTBE return line; 11, product MTBE extraction line; 12, reclaim the diesel oil delivery pipe; 13, water cooler; 14, reclaim the diesel oil extraction line; 15, cooling water inlet pipe one; 16, cooling water outlet pipe one; 17, MTBE feed-pipe; 18, low-sulfur diesel-oil feed-pipe; 19, ripple packing; 20, column plate; 21, steam feed pipe; 22, the water of condensation rising pipe one; 23, recycle pump; 24, cooling water inlet pipe two; 25, the water of condensation rising pipe two; 26, reflux pump.
Embodiment
As shown in Figure 1; The described device that removes disulphide in the MTBE (MTBE) of the embodiment of the invention; Comprise static mixer 1 and the MTBE distillation tower 2 that is connected with static mixer 1; MTBE distillation tower 2 middle and lower parts are connected with reboiler 5 through MTBE and diesel fuel mixtures material extraction line 3 with heating back MTBE and diesel fuel mixtures material feed-pipe 4; MTBE distillation tower 2 tops are connected with condensing surface 7 through gasification MTBE extraction line 6; Condensing surface 7 is connected with return tank 9 through MTBE extraction line 8 after the condensation, and return tank 9 is connected with MTBE distillation tower 2 through product MTBE return line 10, is connected with product MTBE extraction line 11 on the product MTBE return line 10; MTBE distillation tower 2 bottoms are connected with water cooler 13 through reclaiming diesel oil delivery pipe 12, and water cooler 13 is provided with and reclaims diesel oil extraction line 14, cooling water inlet pipe 1 and cooling water outlet pipe 1.
Said static mixer 1 is provided with MTBE feed-pipe 17 and low-sulfur diesel-oil feed-pipe 18, and static mixer 1 inside is equipped with ripple packing 19, can increase contacting of MTBE and low-sulfur diesel-oil, makes its sufficient mixing.Said MTBE distillation tower 2 inside are provided with column plate 20, and the quantity of column plate 20 is 1-70.Said reboiler 5 is provided with steam feed pipe 21 and water of condensation rising pipe 1; Said MTBE and diesel fuel mixtures material extraction line 3 are provided with recycle pump 23, and recycle pump 23 outlets are connected with reboiler 5 bottoms with diesel fuel mixtures material extraction line 3 through MTBE.Said condensing surface 7 is provided with cooling water inlet pipe 2 24 and water of condensation rising pipe 2 25.Said product MTBE return line 10 is provided with reflux pump 26, and reflux pump 26 imports are connected with said return tank 9 bottoms through product MTBE return line 10.
During disulphide in removing MTBE; At first low-sulfur diesel-oil is mixed behind static mixer 1 thorough mixing by mass ratio 1:1 with MTBE; Disulphide in the MTBE is extracted in the low-sulfur diesel-oil owing to the similar principle that mixes; Place MTBE distillation tower 2 then, MTBE distillation tower 2 keeps MTBE distillation tower 2 end temperature at 100-120 ℃ through reboiler 5 heating, and pressure is 0.1 ± 0.02 Mpa, and MTBE distillation tower 2 top temperature are 40-60 ℃, and pressure is 0.08 ± 0.02 Mpa; Last MTBE finished product steams and keeps reflux ratio from MTBE distillation tower 2 tops is 1-1.5, and low-sulfur diesel-oil reclaims after water cooler is cooled to below 35 ℃ from the MTBE base product.
Application example
Raw material condition: MTBE total sulfur 600ppm, hydrogenated diesel oil total sulfur 900-1300ppm.
Experimental data such as table 1:
Four groups of experimental datas of table 1
Experiment conclusion:
(1) optimum volume ratio of MTBE and hydrogenated diesel oil is 1:1;
(2) total sulfur of the hydrogenated diesel oil of experiment use is higher relatively, and the diesel oil that requires to use is low-sulfur diesel-oil, and total sulfur is below 50ppm;
(3) because the boiling point of disulphide (DMDS) is 109 ℃, therefore control dry point, can cause that the MTBE earning rate is relatively low for being not more than 105 ℃.
Through the lab scale test, the process program of this project obtains checking, for the construction scale device provides Technology and design considerations.Physical parameter characteristics with MTBE product, disulphide among the present invention are foundation, with the point of the cut under the differing temps, separate different product of distillation, reach MTBE purified purpose; Adopt the distillatory principle, remove the disulphide among the MTBE, the still-process of the MTBE distillation tower through taking off disulphide, decolouring obtains the finished product MTBE of low sulfur content.
Claims (7)
1. device that removes disulphide in the MTBE (MTBE); Comprise static mixer (1) and the MTBE distillation tower (2) that is connected with static mixer (1); MTBE distillation tower (2) inside is provided with column plate (20); It is characterized in that: MTBE distillation tower (2) middle and lower part is connected with reboiler (5) through MTBE and diesel fuel mixtures material extraction line (3) and heating back MTBE and diesel fuel mixtures material feed-pipe (4); MTBE distillation tower (2) top is connected with condensing surface (7) through gasification MTBE extraction line (6); Condensing surface (7) is connected with return tank (9) through MTBE extraction line (8) after the condensation; Return tank (9) is connected with MTBE distillation tower (2) through product MTBE return line (10); Be connected with product MTBE extraction line (11) on the product MTBE return line (10), MTBE distillation tower (2) bottom is connected with water cooler (13) through reclaiming diesel oil delivery pipe (12), and water cooler (13) is provided with and reclaims diesel oil extraction line (14), cooling water inlet pipe one (15) and cooling water outlet pipe one (16).
2. the device that removes disulphide in the MTBE according to claim 1; It is characterized in that: said static mixer (1) is provided with MTBE feed-pipe (17) and low-sulfur diesel-oil feed-pipe (18), and static mixer (1) inside is equipped with ripple packing (19).
3. the device that removes disulphide in the MTBE according to claim 2 is characterized in that: the quantity of said column plate (20) is 1-70.
4. the device that removes disulphide in the MTBE according to claim 3 is characterized in that: said reboiler (5) is provided with steam feed pipe (21) and water of condensation rising pipe one (22); Said MTBE and diesel fuel mixtures material extraction line (3) are provided with recycle pump (23), and recycle pump (23) outlet is connected with reboiler (5) bottom with diesel fuel mixtures material extraction line (3) through MTBE.
5. the device that removes disulphide in the MTBE according to claim 4 is characterized in that: said condensing surface (7) is provided with cooling water inlet pipe two (24) and water of condensation rising pipe two (25).
6. the device that removes disulphide in the MTBE according to claim 5; It is characterized in that: said product MTBE return line (10) is provided with reflux pump (26), and reflux pump (26) import is connected with said return tank (9) bottom through product MTBE return line (10).
7. a method of utilizing each described device of claim 1-6 to remove disulphide in the MTBE (MTBE) is characterized in that, said method comprising the steps of:
Low-sulfur diesel-oil is mixed by mass ratio 1:1 with MTBE and behind the static mixer thorough mixing, the disulphide in the MTBE since the similar principle that mixes be extracted in the low-sulfur diesel-oil;
Then said mixture is placed the MTBE distillation tower, the MTBE distillation tower keeps MTBE base product temperature at 100-120 ℃ through the reboiler heating, and pressure is 0.1 ± 0.02 Mpa, and MTBE distillation tower top temperature is 40-60 ℃, and pressure is 0.08 ± 0.02 Mpa;
The MTBE finished product steams from MTBE distillation cat head, and to keep reflux ratio be 1-1.5, and low-sulfur diesel-oil reclaims after water cooler is cooled to below 35 ℃ from the MTBE base product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210065730.0A CN102617297B (en) | 2012-01-13 | 2012-01-13 | Device and method for removing disulfide from methyl tertiary butyl ether (MTBE) |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210065730.0A CN102617297B (en) | 2012-01-13 | 2012-01-13 | Device and method for removing disulfide from methyl tertiary butyl ether (MTBE) |
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| CN102617297A true CN102617297A (en) | 2012-08-01 |
| CN102617297B CN102617297B (en) | 2014-08-27 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013727A (en) * | 2012-12-28 | 2013-04-03 | 新疆盛世龟兹葡萄酒有限公司 | Novel waste discharge device |
| CN103045421A (en) * | 2012-12-28 | 2013-04-17 | 新疆盛世龟兹葡萄酒有限公司 | Novel reboiling device |
| CN103553885A (en) * | 2013-11-07 | 2014-02-05 | 黑龙江安瑞佳石油化工有限公司 | Desulfurization method for rectified MTBE (methyl tertiary butyl ethers) |
| CN103922900A (en) * | 2014-04-03 | 2014-07-16 | 西南石油大学 | Method for removing sulfide in methyl tertiary butyl ether through double-solvent extractive distillation |
| CN104262116A (en) * | 2014-06-23 | 2015-01-07 | 贺立明 | MTBE deep desulfurization device and method thereof |
| CN104447223A (en) * | 2014-11-07 | 2015-03-25 | 安徽泰合森能源科技有限责任公司 | High-temperature desulfurization device |
| 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 |
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| US6232509B1 (en) * | 1994-06-06 | 2001-05-15 | Catalytic Distillation Technologies | Etherification process |
| 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 |
| CN202430145U (en) * | 2012-01-13 | 2012-09-12 | 宁波中一石化科技有限公司 | Device for removing disulfides in methyl tert-butyl ether |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07258136A (en) * | 1994-02-28 | 1995-10-09 | Texaco Dev Corp | Conservation of energy in multi-stage distillation |
| US6232509B1 (en) * | 1994-06-06 | 2001-05-15 | Catalytic Distillation Technologies | Etherification process |
| 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 |
| CN202430145U (en) * | 2012-01-13 | 2012-09-12 | 宁波中一石化科技有限公司 | Device for removing disulfides in methyl tert-butyl ether |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013727A (en) * | 2012-12-28 | 2013-04-03 | 新疆盛世龟兹葡萄酒有限公司 | Novel waste discharge device |
| CN103045421A (en) * | 2012-12-28 | 2013-04-17 | 新疆盛世龟兹葡萄酒有限公司 | Novel reboiling device |
| CN103013727B (en) * | 2012-12-28 | 2015-09-02 | 新疆盛世龟兹葡萄酒有限公司 | A kind of Novel waste discharge device |
| CN103553885A (en) * | 2013-11-07 | 2014-02-05 | 黑龙江安瑞佳石油化工有限公司 | Desulfurization method for rectified MTBE (methyl tertiary butyl ethers) |
| CN103922900A (en) * | 2014-04-03 | 2014-07-16 | 西南石油大学 | Method for removing sulfide in methyl tertiary butyl ether through double-solvent extractive distillation |
| CN104262116A (en) * | 2014-06-23 | 2015-01-07 | 贺立明 | MTBE deep desulfurization device and method thereof |
| CN104447223A (en) * | 2014-11-07 | 2015-03-25 | 安徽泰合森能源科技有限责任公司 | High-temperature desulfurization device |
| 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 |
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| CN102617297B (en) | 2014-08-27 |
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Address after: 315040, Zhejiang, Ningbo province National hi tech Zone Lingyun road 1177 Lingyun Industrial Park, building 10, north 2 floor Applicant after: NINGBO ZHONGYI PETROCHEMICAL TECHNOLOGY CO., LTD. Address before: 315040, Zhejiang, Ningbo province National hi tech Zone Lingyun road 1177 Lingyun Industrial Park, building 10, north 2 floor Applicant before: Ningbo Zhongyi Petrochemical Technology Co., Ltd. |
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