CN103333042B - A kind of preparation method of amylene - Google Patents
A kind of preparation method of amylene Download PDFInfo
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- CN103333042B CN103333042B CN201310314884.3A CN201310314884A CN103333042B CN 103333042 B CN103333042 B CN 103333042B CN 201310314884 A CN201310314884 A CN 201310314884A CN 103333042 B CN103333042 B CN 103333042B
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- amylene
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Abstract
The present invention relates to a kind of preparation method of amylene, comprise the following steps: enter a fixed-bed catalytic hydrogenator after 1) being mixed with hydrogen by the C 5 fraction being rich in m-pentadiene and carry out selective hydrogenation, catalyzer is Pd/Al
2o
3; In hydrogen and material, the molar feed ratio of diolefin is 1 ~ 3 ﹕ 1, mass space velocity 1 ~ 8hr
-1, reaction pressure is 10 ~ 20bar, and temperature of reaction is 30 ~ 90 DEG C; By hydrogenation, m-pentadiene contained in material is converted into 1-amylene and 2-amylene; 2) utilize the boiling-point difference of each component in hydrogenation material, separated by 1-amylene in the rectifying tower that a theoretical plate number is 80 ~ 100, bottom temperature is 55 ~ 80 DEG C, and tower top temperature is 40 ~ 60 DEG C, and reflux ratio is 10 ~ 30, and tower working pressure is 2 ~ 5bar; 3) above-mentioned tower bottoms is sent into again a theoretical plate number be 80 ~ 100 rectifying tower in 2-amylene is separated, bottom temperature is 62 ~ 87 DEG C, and tower top temperature is 47 ~ 67 DEG C, and reflux ratio is 10 ~ 30, and tower working pressure is 2 ~ 5bar.Advantage of the present invention is by 1-amylene more than 98.5% of the method production purity easily of hydrogenation and rectifying and 2-amylene product.
Description
Technical field
The present invention relates to a kind of preparation method of amylene, after particularly being mixed with hydrogen by the C 5 fraction being rich in m-pentadiene, pass through Pd/Al
2o
3beds, makes m-pentadiene selec-tive hydrogenation be converted into 1-amylene and 2-pentene mixture, then obtains the method for 1-amylene and 2-amylene product respectively by rectifying separation.
Background technology
1-amylene is the intermediate of the comparatively narrow fine chemical product of a kind of Application Areas, and it produces 1,2-pentanediol through epoxidation, and then produce the raw material of sterilant Wocosin 50TK.Wocosin 50TK is good and minimum to the environmental influence green organic pesticide of a kind of development prospect of alternative organophosphorus pesticide; 2-amylene is then a kind of important Organic Chemicals, can be used as raw material and the polymerization retarder of producing 2-amylalcohol and 3-amylalcohol through hydration reaction.
The process by-product of usual naphtha steam cracking ethene goes out a considerable amount of C5 fraction, and its amount is about 10% of ethylene yield.The comprehensive utilization of current C5 fraction is mainly separated C5 fraction and obtains being worth diolefin and the isopentene products such as higher m-pentadiene, isoprene and dicyclopentadiene, after being separated diolefin and isopentene, remaining carbon five material is called raffinate carbon-5, accounts for 10 ~ 15% of C5 fraction raw material.About containing the 1-amylene of about 10% and the 2-amylene of about 20% in raffinate carbon-5.More and each component boiling point of carbon five component contained by raffinate carbon-5 closely, therefore although the mode of employing precise distillation produces 1-amylene and 2-amylene, but institute's product purity that obtains is lower, the 1-amylene of content more than 98.5% and 2-amylene product cannot be obtained.
Summary of the invention
The invention provides a kind of preparation method of amylene, after being mixed with hydrogen by the C 5 fraction being rich in m-pentadiene, pass through Pd/Al
2o
3beds, makes m-pentadiene selec-tive hydrogenation be converted into positive amylene and 2-pentene mixture, 1-amylene and 2-pentene mixture, then the method being obtained 1-amylene and 2-amylene product by rectifying separation respectively.
Below the concrete technical scheme of the present invention:
A preparation method for amylene, comprises the following steps:
1) enter a fixed-bed catalytic hydrogenator after being mixed with hydrogen by the C 5 fraction being rich in m-pentadiene and carry out selective hydrogenation, catalyzer is Pd/Al
2o
3.In hydrogen and material, the molar feed ratio of diolefin is 1 ~ 3 ﹕ 1, fresh feed mass space velocity 1 ~ 8hr
-1, reaction pressure is 10 ~ 20bar, and temperature of reaction is 30 ~ 90 DEG C.By hydrogenation, m-pentadiene contained in material is converted into 1-amylene and 2-amylene substantially.
2) utilize the boiling-point difference of each component in hydrogenation material, in the rectifying tower that a theoretical plate number is 80 ~ 100,1-amylene is separated.Bottom temperature is 55 ~ 80 DEG C, and tower top temperature is 40 ~ 60 DEG C, and reflux ratio is 10 ~ 30, and tower working pressure is 2 ~ 5bar.
3) above-mentioned tower bottoms is sent into again a theoretical plate number be 80 ~ 100 rectifying tower in 2-amylene is separated.Bottom temperature is 62 ~ 87 DEG C, and tower top temperature is 47 ~ 67 DEG C, and reflux ratio is 10 ~ 30, and tower working pressure is 2 ~ 5bar.
Above-mentioned steps 1) described in the catalyzer of selective hydrogenation be generally Pd/Al
2o
3, palladium is active ingredient, Al
2o
3for carrier, palladium metal charge capacity is preferably 0.25 ~ 0.30% of catalyzer total mass; In hydrogen and material, the mol ratio of diolefin is preferably 1.1 ~ 2.5 ﹕ 1; Mass space velocity is preferably 4 ~ 6hr
-1; Reaction pressure is preferably 12 ~ 16bar, and temperature of reaction is preferably 35 ~ 70 DEG C.
Above-mentioned steps 2) described in the bottom temperature of rectifying tower be preferably 60 ~ 70 DEG C; Tower top temperature is preferably 45 ~ 55 DEG C; Reflux ratio is preferably 15 ~ 25; Tower working pressure is preferably 2.5 ~ 3.5bar.
Above-mentioned steps 3) described in the bottom temperature of rectifying tower be preferably 67 ~ 77 DEG C; Tower top temperature is preferably 52 ~ 62 DEG C; Reflux ratio is preferably 15 ~ 25; Tower working pressure is preferably 2.5 ~ 3.5bar.
Present invention employs ripe selective hydrogenation Pd/Al in step 1
2o
3catalyzer, this catalyzer can the hydrogenation of m-pentadiene in fcc raw material under suitable hydroconversion condition, makes it change into the lower 1-amylene of boiling point and 2-amylene.In the hydrogenation process of m-pentadiene, due to thermodynamic (al) cause, hysomer can be there is and change into 2-amylene in the 1-amylene having part to generate, and be the mol ratio of diolefin in hydrogen and material to the processing parameter that it has the greatest impact, suitable trim point need be found at m-pentadiene hydrogenation conversion and 1-amylene.During this external selective hydrogenation, the selectivity of special concern hydrogenation, reduce the repeated hydrogenation of monoolefine as far as possible, improve the yield of reaction.
Compared with prior art, advantage of the present invention is by adopting the method for hydrogenation and rectifying to produce 1-amylene and 2-amylene product.Because the boiling point of component each in hydrogenation products differs comparatively obvious with 1-amylene and 2-amylene, therefore rectifying can be passed easily through come the 1-amylene of production purity more than 98.5% and 2-amylene product.
Below by embodiment, details of the present invention is further described.
Embodiment
Embodiment
One, selective hydrogenation
Hydrogenator one ruler cun is the stainless steel tubular reactor of φ 25mm × 1000mm, and load 100ml catalyzer in reaction tubes, catalyzer take Pd as active constituent, Al
2o
3for carrier, Pd content is the 0.30wt% of catalyzer total mass.Reactor bottom filling inert ceramic balls.Live catalyst needed to activate with hydrogen before charging.
After the hydrogenation products being rich in C 5 fraction 30 times of quality of cyclopentenes is diluted, send into hydrogenator by the bottom of reactor after mixing with the hydrogen measured by mass flowmeter with the speed of setting with pump after preheating and carry out hydrogenation reaction.Hydrogenation material enters a gas-liquid separator by hydrogenator top, and liquid phase material enters product storage tank.The unreacting hydrogen separated by gas-liquid separator is emptying enter wet gas meter metering after variable valve decompression after, or Returning reacting system after compression.System pressure is by governor valve control.In hydrogen and material, the molar feed ratio of diolefin is 1 ~ 3 ﹕ 1, mass space velocity 1 ~ 8hr
-1, reaction pressure is 10 ~ 20bar, and temperature of reaction is 30 ~ 90 DEG C.Be rich in the composition of the C 5 fraction of cyclopentenes in table 1.The composition of typical hydrogenation products is in table 2.Hydrogenation products is analyzed by gas-chromatography; Gas chromatograph used is 5890 chromatographic instruments that Agilent company of the U.S. produces.
Table 1.
| Component | Content (wt%) |
| 1-amylene | 0.0000 |
| Skellysolve A | 0.0000 |
| Isoprene | 0.0025 |
| Trans amylene-2 | 0.0000 |
| Cis amylene-2 | 0.0000 |
| 2-methyl butene-2 | 0.0025 |
| Anti-form-1,3-pentadiene | 17.2197 |
| Cyclopentadiene | 0.0025 |
| Cis-1,3-pentadiene | 38.8162 |
| Cyclopentenes | 28.1759 |
| 2,2-dimethylbutane | 0.0012 |
| Pentamethylene | 10.6726 |
| Other | 5.1069 |
Table 2.
| Component | Content (wt%) |
| 1-amylene | 17.0520 |
| Skellysolve A | 0.0003 |
| Isoprene | 0.0000 |
| Trans amylene-2 | 25.8988 |
| Cis amylene-2 | 13.0838 |
| 2-methyl butene-2 | 0.0050 |
| Anti-form-1,3-pentadiene | 0.0005 |
| Cyclopentadiene | 0.0000 |
| Cis-1,3-pentadiene | 0.0005 |
| Cyclopentenes | 28.1759 |
| 2,2-dimethylbutane | 0.0012 |
| Pentamethylene | 10.6751 |
| Other | 5.1069 |
Two, 1-amylene product rectifying
The hydrogenation reaction solution obtained shown in table 2 is sent into rectifying tower and carries out rectifying.Rectifying tower is packing tower, and the theoretical plate number of rectifying tower is 80 ~ 100.Bottom temperature is 55 ~ 80 DEG C, and tower top temperature is 40 ~ 60 DEG C, and reflux ratio is 10 ~ 30, and tower working pressure is 2 ~ 5bar.Obtain 1-amylene from rectifying tower tower top, purity is more than 98.5%.Table 3 is compositions of typical 1-amylene product.
Table 3.
| Component | Content (wt%) |
| 1-amylene | 99.59 |
| Skellysolve A | 0.12 |
| Trans-2-butene-2 | 0.18 |
| Cis-butene-2 | 0.11 |
Three, 2-amylene product rectifying
The hydrogenation reaction solution obtained shown in table 2 is sent into rectifying tower and carries out rectifying.Rectifying tower is packing tower, and the theoretical plate number of rectifying tower is 80 ~ 100.Bottom temperature is 62 ~ 87 DEG C, and tower top temperature is 47 ~ 67 DEG C, and reflux ratio is 10 ~ 30, and tower working pressure is 2 ~ 5bar.Obtain 2-amylene from rectifying tower tower top, purity is more than 98.5%.Table 4 is compositions of typical 2-amylene product.
Table 4.
| Component | Content (wt%) |
| 2-amylene | 99.51 |
| Skellysolve A | 0.32 |
| 2-methyl butene-2 | 0.17 |
Claims (1)
1. a preparation method for amylene, comprises the following steps:
1) enter a fixed-bed catalytic hydrogenator after being mixed with hydrogen by the C 5 fraction being rich in m-pentadiene and carry out selective hydrogenation, catalyzer is Pd/Al
2o
3; In hydrogen and material, the molar feed ratio of diolefin is 1.1 ~ 2.5 ﹕ 1, mass space velocity 4 ~ 6hr
-1, reaction pressure is 12 ~ 16bar, and temperature of reaction is 35 ~ 70 DEG C; By hydrogenation, m-pentadiene contained in material is converted into 1-amylene and 2-amylene substantially;
2) boiling-point difference of each component in hydrogenation material is utilized, separated by 1-amylene in the rectifying tower that a theoretical plate number is 80 ~ 100, bottom temperature is 60 ~ 70 DEG C, and tower top temperature is 45 ~ 55 DEG C, reflux ratio is 15 ~ 25, and tower working pressure is 2.5 ~ 3.5bar;
3) above-mentioned tower bottoms is sent into again a theoretical plate number be 80 ~ 100 rectifying tower in 2-amylene is separated, bottom temperature is 67 ~ 77 DEG C, and tower top temperature is 52 ~ 62 DEG C, and reflux ratio is 15 ~ 25, and tower working pressure is 2.5 ~ 3.5bar;
Step 1) described in catalyst P d/Al
2o
3in Pd content be 0.25 ~ 0.30% of catalyzer total mass.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104557410B (en) * | 2013-10-11 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method of the amylene of high-purity 1 |
| CN108083961A (en) * | 2017-12-15 | 2018-05-29 | 派尔科化工材料（启东）有限公司 | A kind of method of 2- amylalcohols dehydration production n-pentene |
| CN108117473B (en) * | 2017-12-15 | 2021-02-09 | 派尔科化工材料（启东）有限公司 | Method for producing amylene by dehydrating 2-pentanol |
| CN110759802B (en) * | 2018-07-27 | 2023-04-11 | 中国石油化工股份有限公司 | Simultaneous production process of 2-methyl-butene-1 and 2-methyl-butene-2 |
Citations (6)
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|---|---|---|---|---|
| EP0155551A1 (en) * | 1984-03-06 | 1985-09-25 | Mitsubishi Kasei Corporation | Method for the partial hydrogenation of conjugated dienes |
| CN1796340A (en) * | 2004-12-24 | 2006-07-05 | 中国石化上海石油化工股份有限公司 | Separation method for refining coarse piperyene |
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| CN101289361A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 2-amylene by separating C5 distillate of petroleum |
| CN101289360A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 2-amylene by separating C5 distillate of petroleum |
| CN101289362A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0155551A1 (en) * | 1984-03-06 | 1985-09-25 | Mitsubishi Kasei Corporation | Method for the partial hydrogenation of conjugated dienes |
| CN1796340A (en) * | 2004-12-24 | 2006-07-05 | 中国石化上海石油化工股份有限公司 | Separation method for refining coarse piperyene |
| CN101289363A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 1-amylene by separating C5 distillate of petroleum |
| CN101289361A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 2-amylene by separating C5 distillate of petroleum |
| CN101289360A (en) * | 2007-04-19 | 2008-10-22 | 中国石化上海石油化工股份有限公司 | Process for preparing 2-amylene by separating C5 distillate of petroleum |
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