CN102617297B - 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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- CN102617297B CN102617297B CN201210065730.0A CN201210065730A CN102617297B CN 102617297 B CN102617297 B CN 102617297B CN 201210065730 A CN201210065730 A CN 201210065730A CN 102617297 B CN102617297 B CN 102617297B
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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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 methyl tertiary butyl ether.
Background technology
In recent years, along with the fast development of national economy, oil refining, chemical industry become the mainstay of the national economy.Methyl tertiary butyl ether (MTBE), as a kind of high octane gasoline component, is good gasoline high-octane rating additive and octane promoter.MTBE and gasoline can dissolve each other and demixing phenomenon not occur by arbitrary proportion, while being in harmonious proportion with gasoline component, have good Blending effect, are in harmonious proportion octane value higher than its clear octane number.Along with the height enterprise of global oil price, energy scarcity is day by day serious, and MTBE can improve the octane value of gasoline, can reduce the discharge of tail gas waste gas, is conducive to protection of the environment, in China, is widely used.
Sulphur in MTBE product mainly be take disulphide as main, and the realization of the de-disulphide technology of MTBE, causes equipment corrosion in the existence of eliminating sulphur, reduces 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 the feed composition of this and upstream also has relation, and this has brought great difficulty virtually to production and the sale of MTBE.The existing desulfurization technology of MTBE is mainly to control feed sulphur content and adopt the directly mode of distillation.
1, by controlling the sulphur content of raw material, particularly controlling the sulphur content in material carbon four, is generally the mode by alkali cleaning, and the mode of alkali cleaning can only remove hydrogen sulfide and mercaptan sulfur, and the sulphur of other forms is more difficult removing.And in alkali washing process, can produce by product disulphide, thereby disulphide can be entrained in alkali lye to be transferred in carbon four raw materials, causes that MTBE total sulfur is higher.So want to control the sulphur content carbon four from source, need a large amount of, change alkali lye frequently, in could interim assurance carbon four compared with low sulfur content, and change in a large number, frequently alkali, cause alkaline residue quantity discharged greatly to increase, environment has been caused to larger pressure, also increased processing cost simultaneously.
2, directly the mode of distillation is directly placed in MTBE distillation tower by MTBE exactly, utilize distillation principle to realize the object that removes disulphide, because the disulphide content in MTBE is less, belong to ppm rank, this just causes after straight run distillation, MTBE earning rate declines, and earning rate only has 40-60%, and economic benefit reduces greatly.
Summary of the invention
The object of this invention is to provide a kind of device and method that removes disulphide in methyl tertiary butyl ether, made up weak point of the prior art.
The object of the invention is to be achieved through the following technical solutions:
A kind of device that removes disulphide in methyl tertiary butyl ether (MTBE), comprise static mixer and the MTBE distillation tower being connected with static mixer, MTBE distillation tower middle and lower part is connected with reboiler by MTBE and diesel fuel mixtures material discharge nozzle with the rear MTBE of heating and diesel fuel mixtures material feed-pipe, MTBE distillation tower top is connected with condenser by gasification MTBE discharge nozzle, condenser by condensation after MTBE discharge nozzle be connected with return tank, return tank is connected with MTBE distillation tower by product MTBE return line, on product MTBE return line, be connected with product MTBE discharge nozzle, MTBE distillation tower bottom is connected with water cooler by reclaiming diesel oil delivery pipe, water cooler is provided with and reclaims diesel oil discharge nozzle, cooling water inlet pipe one and cooling water outlet pipe one.
Described static mixer is provided with MTBE feed-pipe and low-sulfur diesel-oil feed-pipe, and static mixer inside is provided with ripple packing.Described MTBE distillation tower inside is provided with column plate, and the quantity of column plate is 1-70.Described reboiler is provided with steam feed pipe and water of condensation rising pipe one; Described MTBE and diesel fuel mixtures material discharge nozzle are provided with recycle pump, and circulating-pump outlet is connected with reboiler bottom with diesel fuel mixtures material discharge nozzle by MTBE.Described condenser is provided with cooling water inlet pipe two and water of condensation rising pipe two.Described product MTBE return line is provided with reflux pump, and reflux pump import is connected with described return tank bottom by product MTBE return line.
Utilize said apparatus to remove the method for disulphide in methyl tertiary butyl ether (MTBE), comprise the following steps:
First low-sulfur diesel-oil is mixed after static mixer fully mixes by 1:1 with methyl tertiary butyl ether, the disulphide in methyl tertiary butyl ether, due to the similar principle that mixes, is extracted in low-sulfur diesel-oil;
Then be placed in MTBE distillation tower, MTBE distillation tower heats by reboiler, keeps MTBE base product temperature at 100-120 ℃, 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 methyl tertiary butyl ether finished product steams and keeps reflux ratio from MTBE distillation tower top is 1-1.5, and low-sulfur diesel-oil reclaims after water cooler is cooled to below 35 ℃ from MTBE base product.
Beneficial effect of the present invention is: easy to operate, technique is simple, pollution-free, less investment, cost are low, advanced technology; There is wide market outlook and economic benefit, energy-conserving and environment-protective simultaneously; MTBE product earning rate is high, reaches more than 90%, and whole technique preparation flow is safe and reliable, constant product quality.
Accompanying drawing explanation
With reference to the accompanying drawings the present invention is described in further detail below.
Fig. 1 is the apparatus structure schematic diagram that removes disulphide in methyl tertiary butyl ether described in the embodiment of the present invention.
In figure:
1, static mixer; 2, MTBE distillation tower; 3, MTBE and diesel fuel mixtures material discharge nozzle; 4, MTBE and diesel fuel mixtures material feed-pipe after heating; 5, reboiler; 6, gasification MTBE discharge nozzle; 7, condenser; 8, MTBE discharge nozzle after condensation; 9, return tank; 10, product MTBE return line; 11, product MTBE discharge nozzle; 12, reclaim diesel oil delivery pipe; 13, water cooler; 14, reclaim diesel oil discharge nozzle; 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, water of condensation rising pipe one; 23, recycle pump; 24, cooling water inlet pipe two; 25, water of condensation rising pipe two; 26, reflux pump.
Embodiment
As shown in Figure 1, the device that removes disulphide in methyl tertiary butyl ether (MTBE) described in the embodiment of the present invention, comprise static mixer 1 and the MTBE distillation tower 2 being connected with static mixer 1, MTBE distillation tower 2 middle and lower parts are connected with reboiler 5 by MTBE and diesel fuel mixtures material discharge nozzle 3 with the rear MTBE of heating and diesel fuel mixtures material feed-pipe 4, MTBE distillation tower 2 tops are connected with condenser 7 by gasification MTBE discharge nozzle 6, condenser 7 is connected with return tank 9 by MTBE discharge nozzle 8 after condensation, return tank 9 is connected with MTBE distillation tower 2 by product MTBE return line 10, on product MTBE return line 10, be connected with product MTBE discharge nozzle 11, MTBE distillation tower 2 bottoms are connected with water cooler 13 by reclaiming diesel oil delivery pipe 12, water cooler 13 is provided with and reclaims diesel oil discharge nozzle 14, cooling water inlet pipe 1 and cooling water outlet pipe 1.
Described static mixer 1 is provided with MTBE feed-pipe 17 and low-sulfur diesel-oil feed-pipe 18, and static mixer 1 inside is provided with ripple packing 19, can increase contacting of MTBE and low-sulfur diesel-oil, and it is mixed fully.Described MTBE distillation tower 2 inside are provided with column plate 20, and the quantity of column plate 20 is 1-70.Described reboiler 5 is provided with steam feed pipe 21 and water of condensation rising pipe 1; Described MTBE and diesel fuel mixtures material discharge nozzle 3 are provided with recycle pump 23, and recycle pump 23 outlets are connected with reboiler 5 bottoms with diesel fuel mixtures material discharge nozzle 3 by MTBE.Described condenser 7 is provided with cooling water inlet pipe 2 24 and water of condensation rising pipe 2 25.Described product MTBE return line 10 is provided with reflux pump 26, and reflux pump 26 imports are connected with described return tank 9 bottoms by product MTBE return line 10.
During disulphide in removing methyl tertiary butyl ether, first by low-sulfur diesel-oil and methyl tertiary butyl ether in mass ratio 1:1 mix after static mixer 1 fully mixes, disulphide in methyl tertiary butyl ether, due to the similar principle that mixes, is extracted in low-sulfur diesel-oil; Then be placed in MTBE distillation tower 2, MTBE distillation tower 2 heats by reboiler 5, keeps MTBE distillation tower 2 end temperature at 100-120 ℃, 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 methyl tertiary butyl ether 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 MTBE base product.
Application example
Raw material condition: MTBE total sulfur 600ppm, hydrogenated diesel oil total sulfur 900-1300ppm.
Experimental data is 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 that experiment is used is relatively high, and requiring the diesel oil using is low-sulfur diesel-oil, and total sulfur is below 50ppm;
(3) boiling point due to disulphide (Methyl disulfide) is 109 ℃, therefore controls dry point for being not more than 105 ℃, can cause that MTBE earning rate is relatively low.
By lab scale, test, the process program of this project is verified, for construction scale device provides Technology and design considerations.The physical parameter feature of MTBE product, disulphide of take in the present invention is foundation, and with the cut point under differing temps, separated different product of distillation, reaches the refining object of MTBE; The principle that adopts distillation, removes the disulphide in MTBE, by taking off the still-process of the MTBE distillation tower of disulphide, decolouring, obtains the finished product MTBE of low sulfur content.
Claims (6)
1. a method that removes disulphide in methyl tertiary butyl ether (MTBE), it is characterized in that, the device that the method adopts comprises static mixer (1) and the MTBE distillation tower (2) being 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 by MTBE and diesel fuel mixtures material discharge nozzle (3) and heating after MTBE and diesel fuel mixtures material feed-pipe (4) be connected with reboiler (5), MTBE distillation tower (2) top is connected with condenser (7) by gasification MTBE discharge nozzle (6), condenser (7) is connected with return tank (9) by MTBE discharge nozzle (8) after condensation, return tank (9) is connected with MTBE distillation tower (2) by product MTBE return line (10), on product MTBE return line (10), be connected with product MTBE discharge nozzle (11), MTBE distillation tower (2) bottom is connected with water cooler (13) by reclaiming diesel oil delivery pipe (12), water cooler (13) is provided with and reclaims diesel oil discharge nozzle (14), cooling water inlet pipe one (15) and cooling water outlet pipe one (16), described method comprises the following steps:
By low-sulfur diesel-oil and methyl tertiary butyl ether in mass ratio 1:1 mix and after static mixer fully mixes, the disulphide in methyl tertiary butyl ether, due to the similar principle that mixes, is extracted in low-sulfur diesel-oil;
Then said mixture is placed in to MTBE distillation tower, MTBE distillation tower heats by reboiler, keeps MTBE base product temperature at 100-120 ℃, 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; And
Methyl tertiary butyl ether finished product steams from MTBE distillation tower top, and to keep reflux ratio be 1-1.5, and low-sulfur diesel-oil reclaims after water cooler is cooled to below 35 ℃ from MTBE base product.
2. the method that removes disulphide in methyl tertiary butyl ether (MTBE) according to claim 1, it is characterized in that: described static mixer (1) is provided with MTBE feed-pipe (17) and low-sulfur diesel-oil feed-pipe (18), static mixer (1) inside is provided with ripple packing (19).
3. the method that removes disulphide in methyl tertiary butyl ether (MTBE) according to claim 2, is characterized in that: the quantity of described column plate (20) is 1-70.
4. the method that removes disulphide in methyl tertiary butyl ether (MTBE) according to claim 3, is characterized in that: described reboiler (5) is provided with steam feed pipe (21) and water of condensation rising pipe one (22); Described MTBE and diesel fuel mixtures material discharge nozzle (3) are provided with recycle pump (23), and recycle pump (23) outlet is connected with reboiler (5) bottom with diesel fuel mixtures material discharge nozzle (3) by MTBE.
5. the method that removes disulphide in methyl tertiary butyl ether (MTBE) according to claim 4, is characterized in that: described condenser (7) is provided with cooling water inlet pipe two (24) and water of condensation rising pipe two (25).
6. the method that removes disulphide in methyl tertiary butyl ether (MTBE) according to claim 5, it is characterized in that: described product MTBE return line (10) is provided with reflux pump (26), reflux pump (26) import is connected with described return tank (9) bottom by product MTBE return line (10).
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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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| 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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| CN102617297B true CN102617297B (en) | 2014-08-27 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
Citations (3)
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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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0669306A1 (en) * | 1994-02-28 | 1995-08-30 | Texaco Development Corporation | Energy conservation during plural stage distillation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
| Title |
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| JP特开平7-258136A 1995.10.09 |
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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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