CN1116126A - Producing method of high purity butylene-1 - Google Patents
Producing method of high purity butylene-1 Download PDFInfo
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- CN1116126A CN1116126A CN 94110735 CN94110735A CN1116126A CN 1116126 A CN1116126 A CN 1116126A CN 94110735 CN94110735 CN 94110735 CN 94110735 A CN94110735 A CN 94110735A CN 1116126 A CN1116126 A CN 1116126A
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- butene
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Abstract
The present invention relates to a new technology for producing high purity butylene-1. The characteristic is that by utilizing the difference of volatility between impurity compound and carbon-4 component and the azeotropy, through the fractional column while removing the isbutane, the trace sulfide, oxy-compounds, carbon-3 di-olefins and alkyne hydrocarbon are also removed to make the feed-stock enter directly to the selective hydrogenation reaction chamber and make the butadiene by single-olefinified, so as to separate further and have no need of purifying, thus the process is simplified, the energy cost is lowered, meanwhile the pantial pressure of hydrogen in the selective hydrogenation course is lowered, the side reaction is decreased and the yield of butylene-1 is increased.
Description
The present invention relates to the preparation method of butene-1.
Mixed c 4 is produced in paying of refinery catalytic cracking unit and ethene steam cracking device, it is the cheap raw material of producing butene-1, particularly (isobutene and methyl alcohol reaction generate methyl tertiary butyl ether(MTBE) to this mixed c 4 through etherification reaction, as Chinese patent 88109705.5,89105325.5 etc.), removed with the very approaching isobutene of butene-1 boiling point after, producing high-purity butylene-1s by its residue carbon four is process routes of economical rationality the most.Remove in the residue carbon four after the etherificate and contain butene-1, iso-butane, normal butane beyond anti-butene-2 and small amount of carbon three hydrocarbon, also contains the 1.3-butadiene equal altitudes unsaturated hydrocarbons about 1% (M/M).Need remove the 1.3-butadiene very approaching owing to produce high-purity butylene-1 with the butene-1 boiling point.The method of prior art has two kinds, a kind of is degree of depth extract and separate butadiene, as Japan Patent 58-126820, but this method can only make the butadiene content in carbon four logistics reduce to 60-80PPM, when the content of the butene-1 in the carbon four is lower than 50% such as catalytically cracked C four, the concentration of butadiene will can not satisfy polymer grade butene-1 quality requirement greater than 120PPM in the product butene-1, and the investment cost of this method is also higher.Another kind method is to utilize to select the method for hydrogenation to remove butadiene, and on general palladium catalyst, but the butene-1 isomery turns to butene-2, and the butene-1 yield is descended.But German patent DE 3.426.349 thinks behind butene-1 isomerization rate and the hydrogenation that the butadiene residual volume is relevant in the logistics, and the butadiene residual volume is more little, and the butene-1 isomerization rate is high more.Therefore before hydrogenation earlier through twice separated, make butene-1 be concentrated to 85%～90% after, select the hydrogenation and removing butadiene again, can improve butadiene residual volume in the logistics behind hydrogenation like this, take this to improve the butene-1 yield.But in fact, butene-1 concentration improves the isomerization speed that also can increase butene-1, the trace sulfide that is contained in the methyl alcohol that the isobutene etherification technology is produced, dimethyl ether, water and the catalytically cracked C four is all to the hydrogenation reaction of butadiene inhibitory action to some extent, do not turn to butene-2 but do not influence the butene-1 isomery, therefore can not significantly improve the butene-1 yield; Material repeatedly passes through separated, and energy consumption is big.Domestic imported technology will be adsorbed earlier, purified treatment such as drying, Merox desulfurization before hydrogenation, long flow path, energy consumption height.
The objective of the invention is to utilize the characteristic of system itself, when separating the iso-butane bigger first than butene-1 volatility, remove above-mentioned objectionable impurities, make and select hydrogenation process than under to carry out at lower temperature and hydrogen/diolefin, reduce the butene-1 isomerization rate as far as possible, improve the butene-1 yield, technical process is simplified, energy consumption and cost descend.
The objective of the invention is to realize by following design:
In technology of the present invention, at first in a precision fractionation tower, separate the bigger iso-butane of volatility, main is simultaneously by the control operation condition, reach following purpose: 1. utilize azeotropic properties or volatility difference to remove minor amount of water in the carbon four, methyl alcohol, sulfide, dimethyl ether etc. to selecting the harmful impurity of hydrogenation catalyst, make the content of these impurity both satisfy the purity requirement of polymer grade butene-1, do not influence the activity and stability of selecting hydrogenation catalyst again.②。Remove carbon three diolefins and alkynes, thereby reduce the density of hydrogen in the hydrogenation process, reduce the butene-1 isomery and turn to, improve the yield of butene-1 along pair reactions such as anti-butene-2 and butene-1 deep hydrogenation generation normal butanes.
The material that separates after the said components directly enters the selective hydrogenation reaction device, make 1.3-butadiene equal altitudes hydrogenation of unsaturated hydrocarbons generate corresponding monoolefine, separate normal butane and suitable anti-butene-2 through a precision fractionation tower at last, thereby obtain polymer grade height butene-1.
Accompanying drawing is a process flow diagram.The mixed c 4 raw material that comes from ether-based device enters fractionating column [2] after preheater [1] is preheated to 40 ℃～80 ℃, the cat head vapor phase product partly or entirely enters return tank [4] after the condensation through condenser [3], partial condensation liquid is back to tower [2] top through reflux pump [5], rest materials goes out device through pipeline [6], and the water-phase product of separating out in the return tank [4] is discharged by pipeline [7].Tower still material part is returned tower [2] bottom after reboiler [8] is heated, it is to reduce to through cooler [9] that uniform temperature is laggard goes into to select hydrogenation reactor [10], enters fractionating column [11] after making diolefin and alkynes be converted into monoolefine with hydrogen reaction under the effect of catalyst.Vapor-phase material enters return tank [13] after condenser 12 whole condensations, partial condensation liquid is back to tower [11] top through reflux pump [14], and all the other go out device as product through pipeline [15].Tower still material part is returned tower [11] bottom through reboiler [16], and all the other go out device through pipeline [17].
The operating pressure of fractionating column [2] is 0.6-2.0MPa, and operating temperature 40-90 ℃, reflux ratio is 10-200, and number of theoretical plate is the 60-200 piece.
0.6-2.0MPa is pressed in the operation of selective hydrogenation reaction device [10], and operating temperature 40-80 ℃, hydrogen feeding amount is 1.0-2.0 a times of stoichiometry desirable value, and liquid hourly space velocity (LHSV) is 2.-50h
-1The activity of such catalysts component is a palladium, and carrier is Al
2O
3General selection hydrogenation catalyst.
The operating pressure 0.4-1.0MPa of fractionating column [11], operating temperature 40-100 ℃, reflux ratio 2-60, number of theoretical plate 60-200 piece.
Effect of the present invention has reached the purpose of foregoing invention, utilize the character of impurity compound and carbon four systems, when separating the light component iso-butane, remove selecting harmful impurity of hydrogenation catalyst and carbon three height unsaturated hydrocarbons, make hydrogenation catalyst keep high selection hydrogenation activity; Course of reaction is carried out under the condition that more relaxes, thereby suppressed the isomerization reaction of butene-1, improved the butene-1 yield, owing to need before hydrogenation, butene-1 be concentrated through twice separated, need before hydrogenation, not adsorb drying, purified treatment such as desulfurization earlier yet, therefore simplified technology, reduce investment, reduced cost and energy consumption, and improved the yield of butene-1, reach 85-92%, and prior art butene-1 yield is 80-84%.(Deutsche Bundespatent 3426349)
Further specify the present invention with embodiment below:
Embodiment 1.Raw materials usedly be cracking c_4 through the residue C-4-fraction behind the etherification technology, operating condition sees attached list 1, and the composition of raw material compositions, fractionating column [2] tower still material, selective hydrogenation reaction device [10] outlet material and product is listed in during subordinate list 2 shows.The butene-1 yield is 96.1% in the tower [2], selects hydrogenation process butene-1 yield 98.7%, butene-1 yield 96.7% in the tower [11], and the butene-1 total recovery is 91.7%.
Subordinate list 1.The operating parameter of embodiment 1
The composition (M/M%) of each material among subordinate list 2. embodiment 1
| Tower 2 | Reactor 10 | Tower 11 | |
| Operating pressure MPa | ??0.56 | ??????1.0 | ???0.52 |
| Cat head or reactor inlet temperature ℃ | ??47 | ??????45 | ???48 |
| Tower still or reactor outlet temperature ℃ | ??60 | ??????63 | ???60 |
| Reflux ratio | ??130 | ??????/ | ???35 |
| Liquid hourly space velocity (LHSV) h -1 | ???/ | ??????20 | ????/ |
| Hydrogen and diolefin mol ratio | ???/ | ??????1.3 | ????/ |
| Raw material | Tower 2 tower still things | Material behind the hydrogenation | Product | |
| Propane+propylene M/M% | ??0.11 | ????/ | ????/ | ????/ |
| Iso-butane M/M% | ??2.32 | ???0.09 | ???0.09 | ???0.10 |
| Normal butane M/M% | ??6.55 | ???7.46 | ???7.87 | ???0.23 |
| Isobutene M/M% | ??0.10 | ???0.14 | ???0.14 | ???0.29 |
| Butene-1 M/M% | ??66.22 | ???64.62 | ???63.72 | ???99.17 |
| Butene-2 M/M% | ??23.21 | ???26.58 | ???28.18 | ???0.21 |
| 1.3-butadiene PPM | ?12000 | ???11.300 | ???＜20 | ???＜20 |
| C4 alkynes PPM | ???300 | ????80 | ???＜5 | ???＜5 |
| C3 diolefin+alkynes PPM | ???150 | ???＜150 | ???＜2 | ???＜2 |
| Dimethyl ether PPM | ??2100 | ???＜5 | ???＜5 | ???＜5 |
| Methyl alcohol PPM | ???185 | ???＜5 | ???＜5 | ???＜5 |
| Water PPM | ???345 | ???＜20 | ???＜20 | ???＜20 |
| Sulphur PPM | ???＜2 | ???＜1 | ???＜1 | ???＜1 |
Embodiment 2. is raw materials used to be the residue cut of catalytically cracked C four behind etherification technology, the composition of operating condition and each material is listed in the subordinate list 3.4, tower [2] butene-1 yield 89%, select hydrogenation process butene-1 yield 98.2%, tower [11] butene-1 yield 96.4%, butene-1 total recovery 84.5%.And the butene-1 yield only is the operating condition of 80.07%. subordinate list 3. embodiment 2 in the Deutsche Bundespatent 3426349
The composition of each material among subordinate list 4. embodiment 2
| Tower 2 | Reactor [10] | Tower 11 | |
| Operating pressure, MPa | ??0.65 | ?????1.0 | ???0.60 |
| Cat head or reactor inlet temperature, ℃ | ??49 | ?????45 | ???56 |
| Tower still or reactor outlet temperature, ℃ | ??62 | ?????59 | ???67 |
| Reflux ratio | ??45 | ?????/ | ???28 |
| Liquid hourly space velocity (LHSV), h -1 | ???/ | ?????25 | ???/ |
| Hydrogen and diolefin mol ratio | ???/ | ?????1.2 | ???/ |
| Raw material | Tower 2 tower still things | Material behind the hydrogenation | Product | |
| Propane+propylene M/M% | ??4.62 | ??????/ | ?????/ | ????/ |
| Iso-butane M/M% | ??36.73 | ????0.01 | ???0.01 | ??0.02 |
| Normal butane M/M% | ??10.17 | ????17.53 | ???18.20 | ??0.27 |
| Isobutene M/M% | ??0.08 | ????0.14 | ???0.14 | ??0.32 |
| Butene-1 M/M% | ??30.82 | ????51.09 | ???50.17 | ??99.14 |
| Butene-2 M/M% | ??17.15 | ????29.57 | ???31.48 | ??0.25 |
| 1.3-butadiene PPm | ??9360 | ????161.00 | ???25 | ??52 |
| C4 alkynes PPm | ??273 | ????471 | ???＜5 | ??＜5 |
| C3 diene+alkynes PPM | ??714 | ????＜2 | ???＜2 | ??＜2 |
| Dimethyl ether PPm | ??1920 | ????＜5 | ???＜5 | ??＜5 |
| Methyl alcohol PPM | ??69 | ????＜5 | ???＜5 | ??＜5 |
| Water PPm | ??301 | ????＜20 | ???＜20 | ??＜20 |
| Sulphur PPm | ??29 | ????2.5 | ???2.5 | ??＜1 |
Claims (4)
1. new technology of producing high-purity butylene-1 by etherification technology residue C-4-fraction comprises the selection hydrogenation of butadiene and removes. and the separation of other carbon four components beyond the butene-1, it is characterized in that:
A. at first in the fractionating column [2] that separates light component, separate in the iso-butane, remove the material to selecting hydrogenation catalyst to be harmful to such as oxycompound, sulfur-containing compound and carbon three diolefin alkynes,
B. directly enter the selective hydrogenation reaction device from separating the next material of light component fractionating column [2], remove butadiene and the C4 alkynes very approaching with the butene-1 boiling point; Reacting rear material can obtain the polymer grade high-purity butylene-1 through separated tower [11] again,
C. the operating pressure 0.6-2.0MPa of light component knockout tower [2], operating temperature 40-90 ℃, reflux ratio 10-200.
2. by the described method of claim 1, it is characterized in that the number of theoretical plate 60-200 piece of tower [2].
3. by the described method of claim 1, it is characterized in that the operating pressure 0.6-2.0MPa of selective hydrogenation reaction device [11], operating temperature 40-80 ℃, hydrogen feeding amount is 1.0-2.0 a times of stoichiometry desirable value.
4. by the described method of claim 1, it is characterized in that the operating pressure 0.4-1.0MPa of product knockout tower, operating temperature 40-100 ℃, reflux ratio 2-60, number of theoretical plate 60-200 piece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110735A CN1050311C (en) | 1994-08-01 | 1994-08-01 | Producing method of high purity butylene-1 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110735A CN1050311C (en) | 1994-08-01 | 1994-08-01 | Producing method of high purity butylene-1 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1116126A true CN1116126A (en) | 1996-02-07 |
| CN1050311C CN1050311C (en) | 2000-03-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110735A Expired - Fee Related CN1050311C (en) | 1994-08-01 | 1994-08-01 | Producing method of high purity butylene-1 |
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| CN (1) | CN1050311C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605873A (en) * | 2006-12-28 | 2009-12-16 | 环球油品有限责任公司 | From mixed C 4The apparatus and method of separating 1-butylene in the charging |
| CN101973835A (en) * | 2010-10-18 | 2011-02-16 | 天津市泰旭物流有限公司 | Technology for purifying butylene by adopting chemical separation method |
| CN101362671B (en) * | 2008-09-12 | 2011-09-07 | 中国石油化工股份有限公司 | Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery |
| CN101519337B (en) * | 2009-03-25 | 2012-12-05 | 中国石油化工股份有限公司 | Method for fine desulfurization of high-sulfur C4 of refineries |
| CN114456029A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method and apparatus for producing 1-butene from tetracarbon |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1747435A1 (en) * | 1990-06-07 | 1992-07-15 | Научно-производственное объединение по разработке и внедрению нефтехимических процессов "Леннефтехим" | Method of 1,4-diacetoxybutane synthesis |
| RU2032649C1 (en) * | 1992-01-16 | 1995-04-10 | Акционерное общество закрытого типа Промышленно-финансовая группа Ассоциации "Внедрение" | Process for preparing both isoprene and 3-methylbutene-1 |
-
1994
- 1994-08-01 CN CN94110735A patent/CN1050311C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101605873A (en) * | 2006-12-28 | 2009-12-16 | 环球油品有限责任公司 | From mixed C 4The apparatus and method of separating 1-butylene in the charging |
| CN101605873B (en) * | 2006-12-28 | 2014-02-26 | 环球油品有限责任公司 | Apparatuses and methods for separating butene-1 from a mixed c4 feed |
| CN101362671B (en) * | 2008-09-12 | 2011-09-07 | 中国石油化工股份有限公司 | Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery |
| CN101519337B (en) * | 2009-03-25 | 2012-12-05 | 中国石油化工股份有限公司 | Method for fine desulfurization of high-sulfur C4 of refineries |
| CN101973835A (en) * | 2010-10-18 | 2011-02-16 | 天津市泰旭物流有限公司 | Technology for purifying butylene by adopting chemical separation method |
| CN114456029A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Method and apparatus for producing 1-butene from tetracarbon |
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| Publication number | Publication date |
|---|---|
| CN1050311C (en) | 2000-03-15 |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER OWNER: SINOPEC QILU PETRO-CHEMICAL CORP. Effective date: 20070727 |
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