CN102701917A - Method for synthesizing MTBE (methyl tert-butyl ether) by reaction of mixed C4 with low isobutene content and methanol - Google Patents
Method for synthesizing MTBE (methyl tert-butyl ether) by reaction of mixed C4 with low isobutene content and methanol Download PDFInfo
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- CN102701917A CN102701917A CN2012101833386A CN201210183338A CN102701917A CN 102701917 A CN102701917 A CN 102701917A CN 2012101833386 A CN2012101833386 A CN 2012101833386A CN 201210183338 A CN201210183338 A CN 201210183338A CN 102701917 A CN102701917 A CN 102701917A
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Abstract
The invention relates to a method for synthesizing MTBE (methyl tert-butyl ether) by the reaction of mixed C4 with a low isobutene content and methanol, which comprises the following steps: 1, pre-etherification reaction: the mixed C4 containing 10-15wt% of isobutene and the methanol are fully mixed by a static mixer according to the molecular ratio of isobutene to methanol of (1:1)-(1:1.1), and then the mixture enters a pre-etherification reactor provided with a fixed bed catalyst bed layer for pre-etherification; 2, etherification reaction: material coming out of the pre-etherification reactor enters an etherification reactor provided with a fixed bed catalyst bed layer for etherification, wherein the conversion rate of the isobutene at an outlet of the etherification reactor is larger than or equal to 90%; and 3, product separation and purification: material coming out of the etherification reactor enters a catalytic distillation tower for further reaction and separation, the upper part of the catalytic distillation tower is provided with a catalyst bed layer, and an MTBE product is produced at the lower part of the catalytic distillation tower. Compared with the prior art, the method disclosed by the invention has the characteristics that a weight separation tower is eliminated, the loss of the isobutene in weight separation is avoided, and the yield of the MTBE product is improved.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to the method for the synthetic MTBE of a kind of low in isobutene content mixed c 4 and methyl alcohol reaction.
Background technology
MTBE (MTBE) has the characteristics that octane value is high, steam forces down that are in harmonious proportion; And be the carrier of oxygen; There is lower atmosphere active; Can significantly reduce the discharging of CO and unburn hydro carbons, be ideal processed oil blend component, is that raw material production MTBE is present industrial main method with iso-butylene and methyl alcohol in the carbon four.
At present low in isobutene content mixed c 4 is produced the main method of MTBE (MTBE) and is: the mixed c 4 that contains iso-butylene separates back and methyl alcohol through the static mixer thorough mixing through weight; Mixing raw material gets into after the feed heater preheating in the cleaner of dress with cation exchange resin catalyst; Remove wherein alkali and alkalimetal ion; After the feed cooler cooling, get into reactor drum then and carry out etherification reaction; Separate through catalytic fractionator limit coronite at last, obtain the process mode of product MTBE.
See that from technical process what low in isobutene content mixed c 4 was produced MTBE mainly comprises following step:
1. the raw material weight separates: through the weight knockout tower iso-butylene content in the raw materials mix carbon four is brought up to greater than 18w%.2. raw materials pretreatment: get into behind mixed c 4 that the weight separation is later and the methyl alcohol process static mixer thorough mixing and be equipped with in the cleaner of cation exchange resin catalyst, remove wherein alkali and alkalimetal ion.3. react and product separation: the material that cleaner comes out gets into reactor drum through behind the steam heater; In reactor drum under the effect of cation exchange resin catalyst; Preparatory etherification reaction takes place generate MTBE, reacted material gets into catalytic distillation tower with vapour-liquid blended form to be continued etherification reaction to take place and carry out product separation, and methyl alcohol and unreacted carbon four distillate from cat head with the form of azeotrope; Overhead product gets into return tank after the overhead condenser condensation; Wherein a part of backflow as tower, reflux ratio is 0.9-1.2, another part is as the charging of extraction tower.The material that comes out at the bottom of the catalytic distillation Tata becomes the MTBE product after overcooling.
Can find out that from above this flow process is not enough below also existing in the design: 1. weight separates energy consumption and the investment that increases device, and inevitably can cause the loss of part iso-butylene.2. the effect of cleaner has no idea to control, in case the effect of cleaner guarantees to increase the unitary load of downstream process, makes device isobutene conversion and MTBE purity have no idea to reach requirement.
Summary of the invention
The objective of the invention is to be to provide a kind of good in economic efficiency and a kind of low in isobutene content mixed c 4 of ability assurance device long-term operation and the method for the synthetic MTBE of methyl alcohol reaction.
The technical process that the present invention adopts may further comprise the steps: 1. etherification reaction in advance: the mixed c 4 that contains iso-butylene 10-15wt% and methyl alcohol by iso-butylene and methanol molecules than 1:1-1:1.1 through the static mixer thorough mixing after through the reaction feed heater heats to 30-50 ℃; Get into preparatory methyltertiarvbutyl ether reactor and carry out preparatory etherificate, methyltertiarvbutyl ether reactor is provided with layer 2-3 fixed bed catalyst bed in advance.2. etherification reaction: the material that comes out from preparatory methyltertiarvbutyl ether reactor gets into methyltertiarvbutyl ether reactor and carries out preparatory etherificate after side cooler is cooled to 30-50 ℃, and methyltertiarvbutyl ether reactor is provided with layer 2-3 fixed bed catalyst bed, methyltertiarvbutyl ether reactor outlet isobutene conversion >=90 %.3. product separation is purified: the material that comes out from methyltertiarvbutyl ether reactor gets into catalytic distillation tower and further reacts and separate; Catalytic fractionator top is provided with 3-12 layer beds; Catalytic distillation tower outlet isobutene conversion >=99.5 %, the MTBE of catalytic distillation tower bottom obtains the MTBE product after cooling.
The reaction conditions that the present invention is more excellent: preparatory methyltertiarvbutyl ether reactor air speed 2-4h
-1(amount to mixed c 4 and methyl alcohol, be designated hereinafter simply as wet basis), temperature in 30-50 ℃, methyltertiarvbutyl ether reactor air speed 1-1.5h
-1(wet basis), temperature in 30-50 ℃, the equilibrium temperature of methyltertiarvbutyl ether reactor and methyltertiarvbutyl ether reactor is controlled at about 70-90 ℃ in advance, and iso-butylene and methyl alcohol are by molecular ratio 1:1-1:1.1 in the charging mixed c 4, and reflux ratio is 0.9-1.2 when catalytic distillation.
The present invention uses catalyzer when preparatory etherification reaction, etherification reaction and catalytic distillation be large-scale Zeo-karb, like the D006 catalyzer.
Effective effect of the present invention is: change original cleaner into preparatory methyltertiarvbutyl ether reactor, methyltertiarvbutyl ether reactor is provided with layer 2-3 fixed bed catalyst bed in advance, in advance methyltertiarvbutyl ether reactor air speed 3-4h
-1(wet basis), temperature in are controlled at 30-50 ℃.Through such change; Assisted reaction function with original cleaner; Become the present preparatory methyltertiarvbutyl ether reactor and the composite reaction of methyltertiarvbutyl ether reactor, made the load of methyltertiarvbutyl ether reactor become littler, the temperature rise through each bed of control simultaneously makes reaction more gentle; Guaranteed to be reflected at and also can obtain qualified MTBE product under the low in isobutene content, and prolonged the on-stream time of life of catalyst and device greatly through the combination of preparatory methyltertiarvbutyl ether reactor and methyltertiarvbutyl ether reactor.Compare with existing technology after the cancellation weight knockout tower, avoided the loss of iso-butylene when weight separates, improved the yield of MTBE product.The invention provides low in isobutene content mixed c 4 and the methyl alcohol that a kind of transformation efficiency is high, cost is low and react the method for synthesizing MTBE.
Description of drawings
Fig. 1 is preparatory etherification technology schema;
Identify among the figure: 1-low in isobutene content mixed c 4,2-methyl alcohol, 3-carbon four-methanol mixed device, 4-reaction feed interchanger; The preparatory methyltertiarvbutyl ether reactor of 5-, 6-reacts side cooler, 7-methyltertiarvbutyl ether reactor, 8-MTBE product interchanger; The 9-catalytic distillation tower, 10-catalytic distillation cat head water cooler, 11-catalytic distillation tower return tank; 12-catalytic distillation tower reflux pump is established reboiler at the bottom of the 13-catalytic distillation Tata, the 14-MTBE reactor product cooler; The 15-MTBE product pump, 16-carbon four-methanol azeotrope, 17-MTBE product.
Fig. 2 is carbon four weight separation process scheme figure;
Identify among the figure: 1-low in isobutene content mixed c 4,2-methyl alcohol, heavy carbon four at the bottom of the 3-tower, 4-carbon four weight knockout towers; 5-carbon four-methanol mixed device, 6-reaction feed interchanger, the 7-cleaner, 8-reacts side cooler; The 9-methyltertiarvbutyl ether reactor, 10-catalytic distillation tower charging-MTBE product interchanger, 11-catalytic distillation tower, 12-catalytic distillation cat head water cooler; 13-catalytic distillation tower return tank, 14-catalytic distillation tower reflux pump is established reboiler at the bottom of the 15-catalytic distillation Tata, the 16-MTBE reactor product cooler; The 17-MTBE product pump, 18-carbon four-methanol azeotrope, 19-MTBE product.
Embodiment
Below come for the present invention is described further through practical implementation instance and accompanying drawing, but be not to further qualification of the present invention.
Embodiment 1
By 27.42t/h with low in isobutene content be 10.64wt% mixed c 4 (1) with 1.67t/h methyl alcohol (2) through carbon four-methanol mixed device (3) fill mix after; Be heated to 30-50 ℃ through reaction feed interchanger (4); Get into preparatory methyltertiarvbutyl ether reactor (5) from top; Methyltertiarvbutyl ether reactor D006 loaded catalyst is 12.26t in advance, and layer 2-3 fixed bed catalyst bed is set, and air speed is 2.23h
-1Remove wherein alkali and alkalimetal ion, after reaction side cooler (6) is cooled to 30-50 ℃, get into methyltertiarvbutyl ether reactor (7) then, methyltertiarvbutyl ether reactor D006 loaded catalyst is 26.5t; Methyltertiarvbutyl ether reactor is provided with layer 2-3 fixed bed catalyst bed, and air speed is 1.03 h
-1After the reacted reaction product of methyltertiarvbutyl ether reactor (7) and MTBE product process catalytic distillation tower charging-MTBE product interchanger (8) heat exchange, get into catalytic distillation tower (9); Top is provided with 3-12 layer beds; Establish reboiler (13) at the bottom of the catalytic distillation Tata; The residue carbon four-methanol azeotrope (16) of catalytic distillation cat head gets into catalytic distillation tower return tank (11) through catalytic distillation cat head water cooler (10) cooling back; Return catalytic distillation tower (9) through catalytic distillation tower reflux pump (a 12) part through backflow again; Reflux ratio is 0.9-1.2, and a part of residue carbon four-methanol azeotrope separates to extraction tower, the MTBE product (17) at the bottom of the catalytic distillation Tata through catalytic distillation tower charging-MTBE product interchanger (8) heat exchange and MTBE reactor product cooler (14) after MTBE product pump (15) is delivered to the tank field as product.
In advance conversion for isobutene is 89.29% during etherification reaction, and isobutene conversion is 92.2% during methyltertiarvbutyl ether reactor, and total isobutene conversion is 99.91%, and MTBE purity is 99.24%, produces MTBE product 4.62t/h.
Embodiment 2
By 34.47t/h with low in isobutene content be 15.08wt% mixed c 4 (1) with 2.97t/h methyl alcohol (2) through carbon four-methanol mixed device (3) fill mix after; Be heated to 30-50 ℃ through reaction feed interchanger (4); Get into preparatory methyltertiarvbutyl ether reactor (5) from top; Methyltertiarvbutyl ether reactor D006 loaded catalyst is 12.26t in advance, and layer 2-3 fixed bed catalyst bed is set, and air speed is 2.81 h
-1Remove wherein alkali and alkalimetal ion, after reaction side cooler (6) is cooled to 30-50 ℃, get into methyltertiarvbutyl ether reactor (7) then, methyltertiarvbutyl ether reactor D006 loaded catalyst is 26.5t; Methyltertiarvbutyl ether reactor is provided with layer 2-3 fixed bed catalyst bed, and air speed is 1.30 h
-1After the reacted reaction product of methyltertiarvbutyl ether reactor (7) and MTBE product process catalytic distillation tower charging-MTBE product interchanger (8) heat exchange, get into catalytic distillation tower (9); Top is provided with 3-12 layer beds; Establish reboiler (13) at the bottom of the catalytic distillation Tata; The residue carbon four-methanol azeotrope (16) of catalytic distillation cat head gets into catalytic distillation tower return tank (11) through catalytic distillation cat head water cooler (10) cooling back; Return catalytic distillation tower (9) through catalytic distillation tower reflux pump (a 12) part through backflow again; Reflux ratio is 0.9-1.2, and a part of residue carbon four-methanol azeotrope separates to extraction tower, the MTBE product (17) at the bottom of the catalytic distillation Tata through catalytic distillation tower charging-MTBE product interchanger (8) heat exchange and MTBE reactor product cooler (14) after MTBE product pump (15) is delivered to the tank field as product.
In advance conversion for isobutene is 88.29% during etherification reaction, and isobutene conversion is 90.2% during etherification reaction, and total isobutene conversion is 99.88%, and MTBE purity is 99.37%, produces MTBE product 8.21t/h.
Comparative Examples
Is that 15.08wt% mixed c 4 (1) gets into separation in the carbon four weight knockout towers (4) by 34.47t/h with low in isobutene content; Heavy carbon four (3) retrieval systems at the bottom of the tower; Light carbon four of cat head and 3.2t/h methyl alcohol (2) are behind carbon four-methanol mixed device (5) thorough mixing; Be heated to 30-50 ℃ through reaction feed interchanger (6); Get into cleaner (7) from top; Remove wherein alkali and alkalimetal ion, after reaction side cooler (8) is cooled to 30-50 ℃, get into methyltertiarvbutyl ether reactor (9) then, after the reacted reaction product of methyltertiarvbutyl ether reactor (9) and MTBE product process catalytic distillation tower charging-MTBE product interchanger (10) heat exchange, get into catalytic distillation tower (11); Establish reboiler (15) at the bottom of the catalytic distillation Tata; The residue carbon four-methanol azeotrope (18) of catalytic distillation cat head gets into catalytic distillation tower return tank (13) through catalytic distillation cat head water cooler (12) cooling back, returns catalytic distillation tower (11) through catalytic distillation tower reflux pump (a 14) part through backflow again, and reflux ratio is 0.9-1.2; A part of residue carbon four-methanol azeotrope (18) to extraction tower separates, the MTBE product (19) at the bottom of the catalytic distillation Tata through catalytic distillation tower charging-MTBE product interchanger (10) heat exchange and MTBE reactor product cooler (16) after MTBE product pump (17) is delivered to the tank field as product.
Behind the weight knockout tower, light carbon four amounts are 25.87t/h, and iso-butylene content is 19.74wt%; Discharge heavy carbon four amounts and be 8.6t/h, wherein iso-butylene content is 1.06wt%; Isobutene conversion is 90.2% during etherification reaction, and total isobutene conversion is 99.67%, and MTBE purity is 99.32%, produces MTBE product 8.05t/h.
Embodiment of the present invention only is the description that preferred implementation of the present invention is carried out; Be not that design of the present invention and scope are limited; Under the prerequisite that does not break away from design philosophy of the present invention, engineering technical personnel make technical scheme of the present invention in this area various modification and improvement all should fall into protection scope of the present invention; The technology contents that the present invention asks for protection all is documented in claims.
Claims (5)
1. the method for the synthetic MTBE of low in isobutene content mixed c 4 and methyl alcohol reaction is used large-scale Zeo-karb, it is characterized in that may further comprise the steps:
1) preparatory etherification reaction: the mixed c 4 that contains iso-butylene 10-15wt% and methyl alcohol by iso-butylene and methanol molecules than for 1:1-1:1.1 at the static mixer thorough mixing after the reaction feed heater heats to 30-50 ℃; Get into preparatory methyltertiarvbutyl ether reactor and carry out preparatory etherificate, methyltertiarvbutyl ether reactor is provided with layer 2-3 fixed bed catalyst bed in advance;
2) etherification reaction: the material that comes out from preparatory methyltertiarvbutyl ether reactor gets into methyltertiarvbutyl ether reactor and carries out etherificate after side cooler is cooled to 30-50 ℃, and methyltertiarvbutyl ether reactor is provided with layer 2-3 fixed bed catalyst bed, methyltertiarvbutyl ether reactor outlet isobutene conversion >=90 %;
3) product separation is purified: the material that comes out from methyltertiarvbutyl ether reactor gets into catalytic distillation tower and further reacts and separate; Catalytic fractionator top is provided with 3-12 layer beds; Catalytic distillation tower outlet isobutene conversion >=99.5 %, catalytic distillation tower bottom extraction MTBE product.
2. according to the method for the synthetic MTBE of claim 1, it is characterized in that large-scale Zeo-karb is D006.
3. according to claim 1, the method for 2 synthetic MTBE is characterized in that preparatory methyltertiarvbutyl ether reactor air speed 2-4h
-1, temperature in 30-50 ℃, the etherification reaction actuator temperature is controlled at 70-90 ℃ in advance.
4. according to claim 1, the method for 2 synthetic MTBE is characterized in that methyltertiarvbutyl ether reactor air speed 1-1.5h
-1, temperature in 30-50 ℃, the equilibrium temperature of methyltertiarvbutyl ether reactor is controlled at 70-90 ℃.
5. according to the method for the synthetic MTBE of claim 1, reflux ratio is 0.9-1.2 when it is characterized in that catalytic distillation.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739454A (en) * | 2013-12-24 | 2014-04-23 | 山东滨州裕华化工厂有限公司 | Process for preparing MTBE (Methyl Tert Butyl Ether) from C4 fraction in etherified liquefied gas |
| CN104250204A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Mixing etherification technology |
| CN105175209A (en) * | 2015-08-17 | 2015-12-23 | 山东成泰化工有限公司 | Method for preparing isobutene from methyl tert-butyl ether |
| CN105218325A (en) * | 2014-06-11 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of preparation technology of low-sulfur methyl tertiary butyl ether |
| CN106866385A (en) * | 2017-02-28 | 2017-06-20 | 山东京博石油化工有限公司 | A kind of method for producing high-purity methyl tertiary butyl ether(MTBE) |
| 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 |
| CN113943213A (en) * | 2021-11-15 | 2022-01-18 | 丹东明珠特种树脂有限公司 | High-purity MTBE (methyl tert-butyl ether) process method for efficiently removing isobutene and preparation system thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250204A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Mixing etherification technology |
| CN104250204B (en) * | 2013-06-25 | 2016-06-15 | 中国石油化工股份有限公司 | A kind of complex etherified technique |
| CN103739454A (en) * | 2013-12-24 | 2014-04-23 | 山东滨州裕华化工厂有限公司 | Process for preparing MTBE (Methyl Tert Butyl Ether) from C4 fraction in etherified liquefied gas |
| 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 |
| CN105218325A (en) * | 2014-06-11 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of preparation technology of low-sulfur methyl tertiary butyl ether |
| CN105218325B (en) * | 2014-06-11 | 2021-04-13 | 中国石油化工股份有限公司 | Preparation process of low-sulfur methyl tert-butyl ether |
| CN105175209A (en) * | 2015-08-17 | 2015-12-23 | 山东成泰化工有限公司 | Method for preparing isobutene from methyl tert-butyl ether |
| CN106866385A (en) * | 2017-02-28 | 2017-06-20 | 山东京博石油化工有限公司 | A kind of method for producing high-purity methyl tertiary butyl ether(MTBE) |
| CN106866385B (en) * | 2017-02-28 | 2020-04-17 | 山东京博石油化工有限公司 | Method for producing high-purity methyl tert-butyl 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 |
| CN113943213A (en) * | 2021-11-15 | 2022-01-18 | 丹东明珠特种树脂有限公司 | High-purity MTBE (methyl tert-butyl ether) process method for efficiently removing isobutene and preparation system thereof |
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Application publication date: 20121003 |