CN101402553B - Method for producing high purity MTBE with C4 and methanol - Google Patents
Method for producing high purity MTBE with C4 and methanol Download PDFInfo
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- CN101402553B CN101402553B CN2008101436563A CN200810143656A CN101402553B CN 101402553 B CN101402553 B CN 101402553B CN 2008101436563 A CN2008101436563 A CN 2008101436563A CN 200810143656 A CN200810143656 A CN 200810143656A CN 101402553 B CN101402553 B CN 101402553B
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Abstract
The invention discloses a method for producing high-purity MTBE by carbon four and methanol. The method is characterized in that the method comprises the following steps: 1. reaction part: the carbon four containing isobutene and the methanol with an alfin mol ratio of (1.20 to 1.25):1 have an etherification reaction with the process condition of the reaction temperature of between 56 and 60 DEG C; 2. product separation: the mixed material coming out of a reactor enters a catalysis distillation tower for continuous etherification reaction with a gas-liquid mixed phase; after the etherification reaction, the carbon four and the redundant methanol are distilled out of the top of the tower in the form of an azeotrope; and the distillate enters a reflux accumulator after being condensed by a condenser on the top of the tower; and one part of the distillate is taken as the reflux of the tower and the other part of the distillate is taken as the feedstock of an extraction tower; and 3. carbon five separation: a crude product of MTBE coming out of the bottom of the catalysis distillation tower enters a carbon five separation tower; the carbon five and small amount of methanol are distilled out of the top of the tower; one part of the carbon five and methanol is taken as the reflux of the tower, and the other part of the carbon five and methanol is taken as a carbon five product sent to a tank farm for storage; and the MTBE product is obtained on the bottom of the tower. The method can effectively reduce the byproducts in the MTBE product and improve the quality of the MTBE product. The method has the advantages of short flow, little equipment investment, low energy consumption, low production cost, and the like.
Description
Technical field
The present invention relates to a kind of is raw material with the carbon four and the methyl alcohol that contain iso-butylene, produces the method for MTBE through etherification reaction.
Background technology
The technology of domestic production methyl tertiary butyl ether (MTBE) mainly contains two types at present, and a kind of is oil refining type MTBE production technique, and its product purity is not high, can only be used as gasoline dope, improves gasoline octane rating; Another kind is a chemical industry type MTBE production technique, and this technology can be produced highly purified MTBE product, mainly as cracking stock, to produce high-purity isobutylene, as the chemical industry monomer.From technical process, produce high purity MTBE product and mainly comprise following step: 1. carbon five separate parts: the heavy carbon four-way of carbon containing five is crossed carbon five knockout towers carbon five is removed; 2. reactive moieties: the carbon that contains iso-butylene four, the methyl alcohol that remove behind the carbon five through the pump pressurization, carry out etherification reaction by entering reactor behind the static mixer thorough mixing respectively; 3. product separation part: the material that comes out from reactor enters azeotropic distillation column and carries out separating of carbon four behind thick MTBE and the ether, obtains the lower thick MTBE of purity; 4. product purification part: the thick MTBE that comes from the azeotropic distillation column still is sent to the finished product treating tower, from the higher smart MTBE finished product of the side line extraction purity for the treatment of tower; The mixture that comes out from the component distillation top of tower enters catalytic distillation tower continuation generation etherification reaction, and the thick MTBE that obtains at the bottom of the tower is as gasoline dope, and carbon four is used as civil liquefied gas behind the ether that cat head comes out after recovery system is handled.But also there is deficiency in this production method, and it shows that mainly facility investment is big, and work flow is long, energy consumption height, production cost height.
Technical scheme
The object of the present invention is to provide the method that a kind of flow process is short, facility investment is few, energy consumption is low, production cost is low by carbon four and methanol production high purity MTBE.
The technical solution used in the present invention is as follows: a kind of by carbon four method with methanol production high purity MTBE, its feature: include following steps: 1. reactive moieties: the carbon four, the methyl alcohol that contain iso-butylene are (1.20～1.25) in the alfin mol ratio: 1 and temperature of reaction be under 56～60 ℃ the processing condition etherification reaction to take place; 2. product separation: the mixture that comes out from reactor enters catalytic distillation tower with the gas-liquid mixed phase and continues to take place etherification reaction, carbon four distillates from cat head with the azeotrope form with the methyl alcohol of surplus behind the ether, overhead product enters return tank after the overhead condenser condensation, wherein a part is as the backflow of tower, reflux ratio is (0.9～1.2): 1, and another part is as the charging of extraction tower; 3. carbon five separates: the thick product MTBE that comes out from the catalytic distillation tower bottom enters decarburization five knockout towers, carbon five and a spot of methyl alcohol distillate from cat head, a part is returned in the tower as refluxing, reflux ratio is (10～20): 1, another part is delivered to the tank field as carbon five products and is stored, the tower still obtains the MTBE product, decarburization five knockout tower roof pressure: 0.30～0.35MPa; Tower top temperature: 67～75 ℃; Tower still temperature: 97～115 ℃.
Under the effect of etherificate resin catalyst, carry out when etherification reaction generates product MTBE with the carbon four that contains iso-butylene and methyl alcohol, always inevitably to generate methyl sec-butyl ether MSBE, iso-butylene autopolymer DIB, MSBE is the product of n-butene in the mixed c 4 component and methanol etherification reaction, and DIB is the product of iso-butylene generation self-polymeric reaction in the mixed c 4 component.After progressively strengthening, alfin ratio helps suppressing the generation of MSBE and DIB, when alfin ratio greatly regularly to one, MSBE growing amount that it is corresponding and DIB growing amount descend not clearly, and further strengthen alfin ratio and can produce considerable influence, easily cause the tower still to carry methyl alcohol and influence the quality product of MTBE the quiet run of catalytic distillation tower.
The generation of MTBE and MSBE belongs to parallel reaction in the etherification reaction process simultaneously.The former be subjected to thermodynamics then the person be subjected to kinetic control, reduce the growing amount of MSBE, just must avoid the MTBE reaction to be under the excess catalyst effect, promptly to satisfy the corresponding relation of certain temperature and air speed, select appropriate processing condition, just can reduce the speed of response of MSBE, thereby effectively control the growing amount of by product MSBE.When reactor batch temperature was adjusted downward to 59 ℃ of left and right sides by 70 ℃, the growing amount of MSBE progressively dropped to below 0.1% by about 1.0%, has reached the quality index requirement of industrial chemicals.
The present invention has suppressed the generation of impurity such as by product MSBE and DIB by the operational condition of optimizing reactive system, makes its content reach the quality index requirement of industrial chemicals; Simultaneously, adopted the processing method that from product MTBE, removes carbon five, the MTBE product purity is stabilized in more than 99.0%, reached as the specification of quality of industrial chemicals to MTBE purity; Compare with the device of other production high purity MTBE, the present invention has very remarkable advantages: 1. adopt lower temperature of reaction, effectively reduce the sulphur speed of taking off of catalyzer, prolonged the work-ing life of catalyzer greatly; 2. save two tower systems of azeotropic distillation column and finished product treating tower, saved nearly ten million plant construction investment; 3. adopt the technology of from product MTBE, separating carbon five, can realize the heat integration of carbon five knockout towers and catalytic distillation tower, greatly reduce plant energy consumption.Simultaneously, because equipment size is little, pressure rating is low, and MTBE carbon five knockout tower system, device costs are than low nearly 2,000,000 yuan of carbon four carbon five knockout tower system, device costs; 4. significantly reduced running cost.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Further the present invention will be described below by way of embodiments and drawings:
Embodiment 1:
The carbon four, methyl alcohol that contains iso-butylene is that 1.20:1 and temperature of reaction are to carry out etherification reaction by the technical process of accompanying drawing 1 under 56 ℃ the processing condition to generate product MTBE in the alfin mol ratio, and its experimental data sees Table 1:
Embodiment 2:
The carbon four, methyl alcohol that contains iso-butylene is that 1.21:1 and temperature of reaction are to carry out etherification reaction by the technical process of accompanying drawing 1 under 57 ℃ the processing condition to generate product MTBE in the alfin mol ratio, and its experimental data sees Table 1:
Embodiment 3:
The carbon four, methyl alcohol that contains iso-butylene is that 1.22:1 and temperature of reaction are to carry out etherification reaction by the technical process of accompanying drawing 1 under 58 ℃ the processing condition to generate product MTBE in the alfin mol ratio, and its experimental data sees Table 1:
Embodiment 4:
The carbon four, methyl alcohol that contains iso-butylene is that 1.23:1 and temperature of reaction are to carry out etherification reaction by the technical process of accompanying drawing 1 under 59 ℃ the processing condition to generate product MTBE in the alfin mol ratio, and its experimental data sees Table 1:
Embodiment 5:
The carbon four, methyl alcohol that contains iso-butylene is that 1.25:1 and temperature of reaction are to carry out etherification reaction by the technical process of accompanying drawing 1 under 60 ℃ the processing condition to generate product MTBE in the alfin mol ratio, and its experimental data sees Table 1:
Table-1 MTBE purity and the corresponding relation of operating operating mode
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Alfin ratio | 1.20 | 1.21 | 1.22 | 1.23 | 1.25 |
| The reactor bed temperature (℃) | 60 | 59 | 58 | 57 | 56 |
| MSBE content (%) | 0.05～0.09 | 0.06～0.09 | 0.07～0.10 | 0.08～0.10 | 0.09～0.10 |
| DIB content (%) | 0.01～0.03 | 0.03～0.08 | 0.07～0.10 | 0.07～0.10 | 0.08～0.10 |
| Carbon five content (%) in the material carbon four | 0.41～0.78 | 0.40～0.31 | 0.30～0.21 | 0.15～0.20 | ≤0.14 |
| Carbon five content (%) among the thick MTBE | 1.20～2.12 | 0.80～1.32 | 0.65～1.03 | 0.35～0.65 | ≤0.40 |
| Decarburization five cats head pressure (MPa, G) | 0.35 | 0.34 | 0.33 | 0.32 | 0.30 |
| Decarburization five cat head temperature (℃) | 75 | 73 | 71 | 69 | 67 |
| Temperature at the bottom of decarburization five towers (℃) | 115 | 112 | 110 | 105 | 97 |
| Decarburization five tower reflux ratios | 10：1 | 12：1 | 14：1 | 18：1 | 20：1 |
| Product MTBE purity (%) | 99.08～99.49 | 99.22～99.56 | 99.34～99.52 | 99.40～99.55 | ≥99.70 |
As can be seen from the above table, adopt the higher when lower temperature of reaction of charging alfin, can control the generation of by product MSBE, DIB simultaneously, its content all can reach the quality index requirement of industrial chemicals.By further separation carbon five, the MTBE product purity can be stabilized in more than 99.0%, thereby reach as the requirement of industrial chemicals to MTBE purity.
Claims (1)
1. one kind by carbon four method with methanol production high purity MTBE, its feature: include following steps: 1. reactive moieties: the carbon four, the methyl alcohol that contain iso-butylene are (1.20～1.25) in the alfin mol ratio: 1 and temperature of reaction be under 56～60 ℃ the processing condition etherification reaction to take place; 2. product separation: the mixture that comes out from reactor enters catalytic distillation tower with the gas-liquid mixed phase and continues to take place etherification reaction, carbon four distillates from cat head with the azeotrope form with the methyl alcohol of surplus behind the ether, overhead product enters return tank after the overhead condenser condensation, wherein a part is as the backflow of tower, reflux ratio is (0.9～1.2): 1, and another part is as the charging of extraction tower; 3. carbon five separates: the thick product MTBE that comes out from the catalytic distillation tower bottom enters decarburization five knockout towers, carbon five and a spot of methyl alcohol distillate from cat head, a part is returned in the tower as refluxing, reflux ratio is (10～20): 1, another part is delivered to the tank field as carbon five products and is stored, the tower still obtains the MTBE product, decarburization five knockout tower roof pressure: 0.30～0.35MPa; Tower top temperature: 67～75 ℃; Tower still temperature: 97～115 ℃.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928195B (en) * | 2009-09-17 | 2013-01-30 | 山东齐鲁石化工程有限公司 | Method for preparing butane-1 from CPP C4 |
| CN103641693B (en) * | 2013-12-05 | 2015-02-18 | 河北海特伟业石化有限公司 | Low-energy-consumption MTBE (methyl tert-butyl ether) production method |
| CN103739454B (en) * | 2013-12-24 | 2016-06-08 | 山东滨州裕华化工厂有限公司 | The technique that after utilizing ether, the C 4 fraction in liquefied gas prepares MTBE |
| CN103933752B (en) * | 2014-05-07 | 2016-02-10 | 大庆中蓝石化有限公司 | Carbon four separator C5 mixture piece-rate system |
| CN107382681A (en) * | 2017-08-01 | 2017-11-24 | 山东滨庆新能源开发有限公司 | After the washing of MTBE devices methanol after ether carbon four into azeotropy rectification column reflux technique |
| CN108047002B (en) * | 2017-11-27 | 2019-02-15 | 滨州市裕祥化工有限公司 | It is a kind of to produce obtained MTBE component and liquefied gas and preparation method thereof using carbon four after ether |
| CN113058283A (en) * | 2021-03-01 | 2021-07-02 | 中国石油化工股份有限公司 | Methanol recovery system and process of MTBE (methyl tert-butyl ether) device |
| CN113952904B (en) * | 2021-09-29 | 2023-03-03 | 陕西延长石油（集团）有限责任公司 | Transformation and driving method of MTBE (methyl tert-butyl ether) production system |
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| CN1055913C (en) * | 1995-12-26 | 2000-08-30 | 北京燕山石油化工公司合成橡胶厂 | Process for preparing chemical industry type methyl t-butyl ether |
| CN201037131Y (en) * | 2007-04-11 | 2008-03-19 | 河北凯瑞化工有限责任公司 | Modified device for producing methyl t-butyl ether |
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| CN1055913C (en) * | 1995-12-26 | 2000-08-30 | 北京燕山石油化工公司合成橡胶厂 | Process for preparing chemical industry type methyl t-butyl ether |
| CN201037131Y (en) * | 2007-04-11 | 2008-03-19 | 河北凯瑞化工有限责任公司 | Modified device for producing methyl t-butyl ether |
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Effective date of registration: 20210409 Address after: 414014 room 625, science and technology entrepreneurship service center, Hunan Yueyang Green Chemical Industrial Park, Yunxi District, Yueyang City, Hunan Province Patentee after: Sinopec Baling Petrochemical Co.,Ltd. Address before: 414014 Yunxi District, Hunan City, Yueyang province Yueyang branch Birch Chemical Co., Ltd. Patentee before: YUEYANG HUAKE CHEMICAL Co.,Ltd. |
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Address after: 414014 room 625, science and technology entrepreneurship service center, Hunan Yueyang Green Chemical Industrial Park, Yunxi District, Yueyang City, Hunan Province Patentee after: Sinopec Hunan Petrochemical Co.,Ltd. Address before: 414014 room 625, science and technology entrepreneurship service center, Hunan Yueyang Green Chemical Industrial Park, Yunxi District, Yueyang City, Hunan Province Patentee before: Sinopec Baling Petrochemical Co.,Ltd. |
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