CN104418688A - Method for separating and purifying isobutylene from mixed C4 - Google Patents
Method for separating and purifying isobutylene from mixed C4 Download PDFInfo
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- CN104418688A CN104418688A CN201310360793.3A CN201310360793A CN104418688A CN 104418688 A CN104418688 A CN 104418688A CN 201310360793 A CN201310360793 A CN 201310360793A CN 104418688 A CN104418688 A CN 104418688A
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Abstract
The present invention discloses a method for separating and purifying isobutylene from mixed C4. The method is characterized in that an organic acid and an acid ion liquid catalyst are mixed, the obtained mixed material enters a fixed bed reactor and reacts with mixed C4 to produce tert-butyl ester, the tert-butyl ester crude product is degassed, and the obtained product is subjected to catalytic decomposition to produce isobutylene. The method has characteristics of mild reaction, mild decomposition condition, low production cost, less side effect, simple process, low energy consumption, less pollution, and the resulting isobutylene of more than 99.5%.
Description
Technical field
The present invention relates to a kind of method of separating-purifying iso-butylene, particularly relate to a kind of method of separating-purifying iso-butylene from mixed c 4.
Background technology
Iso-butylene is mainly derived from the by-product C-4-fraction of the by-product C-4-fraction of refinery catalytic cracking unit and petroleum naphtha, solar oil catalytic pyrolysis preparing ethylene device.It is mainly used to produce multiple organic chemical industry's product such as polyisobutene, isoprene-isobutylene rubber, polyisoprene rubber and methacrylic ester.In recent years, along with the development of China's petrochemical industry and the exploitation of iso-butylene derived product, the demand of high-purity isobutylene increased year by year.
Ordinary method is difficult to iso-butylene to be separated from mixed c 4, therefore industrially the feature that iso-butylene chemical reactivity is high is usually utilized, be first derivative that is easy and other Component seperation of mixed c 4 by isobutene conversion, adopt selection chemical reaction to carry out separating-purifying iso-butylene.
The industrial process of iso-butylene mainly contains: sulfuric acid extraction process, methyl tertiary butyl ether (MTBE) cracking process and tert-butyl alcohol dehydration method.
Sulfuric acid extraction process refers to that iso-butylene and sulfuric acid (concentration 45% ~ 65%) selective reaction generate the sulfuric acid tert-butyl ester, and the hydrolysis of the sulfuric acid tert-butyl ester generates the trimethyl carbinol, and the trimethyl carbinol dewaters production iso-butylene again.This method exists that equipment corrosion is serious, production cost is high and the problem such as environmental pollution.
MTBE cracking process refers to that iso-butylene and methyl alcohol react and generates MTBE, MTBE and obtain iso-butylene about 200 DEG C cracking.This method side reaction many (comprising the polymerization etc. of dehydration, iso-butylene between methanol molecules), the technological process of production is long, and later separation process for refining is complicated, and energy consumption is higher.
Tert-butyl alcohol dehydration method refers to that iso-butylene and water react and generates the trimethyl carbinol, and the trimethyl carbinol dewaters production iso-butylene again.This method severe reaction conditions, and iso-butylene hydration and tert-butyl alcohol dehydration reaction per pass conversion low.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of and adopt fixed-bed reactor, the method for separating-purifying iso-butylene from mixed c 4.
The invention provides a kind of method of separating-purifying iso-butylene from mixed c 4, it is characterized in that: comprise the steps: that (1) organic acid enters fixed-bed reactor after mixing with acidic ionic liquid catalysts, generate tert-butyl ester crude product with mixed C 4 reaction; (2) gained tert-butyl ester crude product is after degassed, then catalytic decomposition produces iso-butylene.
Reaction conditions in described step (1) is: the mass ratio of organic acid and ionic-liquid catalyst is 1:1 ~ 5:1, temperature of reaction 25 ~ 35 DEG C, and reaction pressure is 0 ~ 1.0MPa, liquid air speed 0.5 ~ 3.0h
-1.
It is degassed that the middle tert-butyl ester crude product of described step (2) carries out low-temperature reduced-pressure under the condition of temperature 0 ~ 10 DEG C, vacuum tightness 0.09MPa.
In described step (2), the decomposition temperature of tert-butyl ester crude product is 40 ~ 80 DEG C, and pressure is normal pressure.
Described organic acid is acetic acid, propionic acid, the one in butyric acid and phenylformic acid.
Described acidic ionic liquid catalysts is sulfuric acid type ionic-liquid catalyst or sulfonic acid type ion liquid catalyst; Wherein sulfuric acid type ionic-liquid catalyst is the one in sulfuric acid pyrrolidone series, pyridine sulfate serial, sulfuric acid imidazoles series, alkyl sodium sulfate quaternary ammonium series, alkyl sodium sulfate season phosphine series plasma liquid; Sulfonic acid type ion liquid catalyst is the one in sulfonic acid pyrrolidone series, sulfonic acid pyridine series, sulfonic acid imidazoles series, sulfonic alkyl quaternary ammonium series, the serial plasma liquid of sulfonic alkyl season phosphine.Under above-mentioned ionic liquid effect, only have iso-butylene and organic acid reaction to generate corresponding ester in mixed c 4, other component does not participate in reaction, therefore only can produce the organic acid tert-butyl ester, favourable to follow-up decomposition reaction.
Described acidic ionic liquid catalysts and organic acid can recycle.
Detailed technology scheme of the present invention is: organic acid and acidic ionic liquid catalysts are made into uniform mixture by the mass ratio of 1:1 ~ 5:1 by (1), load fixed-bed reactor or by pump delivery to filling Packed fixed-bed reactor, react with mixed c 4;
(2) reaction is 0 ~ 1.0MPa, temperature of reaction 25 ~ 35 DEG C, liquid mass air speed 0.5 ~ 3.0h
-1carry out under condition;
(3), after reacting completely, liquid phase tert-butyl ester crude product is through reactor lower part extraction and collect, by pump delivery to catalytic pyrolysis tower;
(4) tert-butyl ester crude product is first in catalytic pyrolysis tower, and under temperature 0 ~ 10 DEG C, vacuum tightness 0.09MPa condition, carry out low-temperature reduced-pressure degassed;
(5) tert-butyl ester crude product is in catalytic pyrolysis tower, and at normal pressure, temperature 40 ~ 80 DEG C, carry out decomposition reaction, tower top obtains iso-butylene, and tower reactor liquid (catalyzer and organic acid) uses as feedstock circulation.
The method of a kind of separating-purifying iso-butylene from mixed c 4 of the present invention, compared with prior art has the following advantages: (1) adopts acidic ionic liquid catalysts, has started its new application; (2) iso-butylene and organic acid reaction generate the organic acid tert-butyl ester, and the organic acid tert-butyl ester again cracking produces iso-butylene, reaction and decomposition condition gentleness, and production cost is low, and greatly reduces the generation of side reaction; (3) this technique is simple, energy consumption is low, pollution is few; (4) tert-butyl ester crude product cleavage rate is high, and the purity of gained iso-butylene reaches more than 99.5%.
Embodiment
Below by specific embodiment, the invention will be further described:
Embodiment 1
By acetic acid, [N-Methyl pyrrolidone] HSO
4ionic-liquid catalyst is made into uniform mixture, enters, mixed C from fixed-bed reactor top
4enter from fixed-bed reactor bottom.Acetic acid/ionic liquid mass ratio 3:1, acid solution Feed space velocities 0.5h
-1, the mol ratio of acetic acid and iso-butylene is 2:1, esterifier bed temperature 30 DEG C, and reaction pressure is 0.5MPa, the content about 48.5% of tert.-butyl acetate in esterification gained liquid phase crude product.
The reacting coarse product that reactor lower part is collected sends into catalytic pyrolysis tower from bottom, first 0 DEG C, carry out under vacuum tightness 0.09MPa condition degassed, again at normal pressure, cartalytic decomposition effect is carried out under 60 DEG C of conditions, result shows, tert.-butyl acetate cleavage rate is 94.23%, and tower top gained iso-butylene purity is 99.94%, and tower reactor liquid (catalyzer and acetic acid) uses as feedstock circulation.
Embodiment 2
Phenylformic acid, sulfonic acid imidazole ion liquid catalyzer are made into uniform mixture, enter from fixed-bed reactor top, mixed C
4enter from fixed-bed reactor bottom.Phenylformic acid/ionic liquid mass ratio 1:1, acid solution Feed space velocities 1.0h
-1, the mol ratio of phenylformic acid and iso-butylene is 2:1, esterifier bed temperature 25 DEG C, and reaction pressure is 1.0MPa, the content about 51.3% of t-butyl perbenzoate in esterification gained liquid phase crude product.
The reacting coarse product that reactor lower part is collected sends into catalytic pyrolysis tower from bottom, first at 10 DEG C, carry out degassed under vacuum tightness 0.09MPa condition, again at normal pressure, carry out the cartalytic decomposition effect of t-butyl perbenzoate under temperature 80 DEG C of conditions, result shows, t-butyl perbenzoate cleavage rate is 93.57%, tower top gained iso-butylene purity is 99.91%, and tower reactor liquid (catalyzer and phenylformic acid) uses as feedstock circulation.
Embodiment 3
Propionic acid, sulfonic acid pyridine ion liquid catalyzer are made into uniform mixture, load in fixed-bed reactor, mixed C
4enter from fixed-bed reactor bottom.Propionic acid/ionic liquid mass ratio 5:1, acid solution Feed space velocities 3.0h
-1, the mol ratio of propionic acid and iso-butylene is 2:1, esterifier bed temperature 35 DEG C, and reaction pressure is normal pressure, the content about 47.8% of propanoic acid tert-butyl ester in esterification gained liquid phase crude product.
The reacting coarse product of reactor upper collection sends into catalytic pyrolysis tower, first at 5 DEG C, carry out degassed under vacuum tightness 0.09MPa condition, again at normal pressure, carry out the cartalytic decomposition effect of propanoic acid tert-butyl ester under temperature 40 DEG C of conditions, result shows, propanoic acid tert-butyl ester cleavage rate is 96.34%, tower top gained iso-butylene purity is 99.95%, and tower reactor liquid (catalyzer and propionic acid) uses as feedstock circulation.
Claims (8)
1. the method for separating-purifying iso-butylene from mixed c 4, is characterized in that: comprise the steps: that (1) organic acid enters fixed-bed reactor after mixing with acidic ionic liquid catalysts, generate tert-butyl ester crude product with mixed C 4 reaction; (2) gained tert-butyl ester crude product is after degassed, then catalytic decomposition produces iso-butylene.
2. method according to claim 1, is characterized in that: described organic acid is acetic acid, propionic acid, the one in butyric acid, phenylformic acid.
3. method according to claim 1, is characterized in that: described acidic ionic liquid catalysts is sulfuric acid type ionic-liquid catalyst or sulfonic acid type ion liquid catalyst.
4. method according to claim 3, is characterized in that: described sulfuric acid type ionic-liquid catalyst is the one in sulfuric acid pyrrolidone series, pyridine sulfate serial, sulfuric acid imidazoles series, alkyl sodium sulfate quaternary ammonium series, alkyl sodium sulfate season phosphine serial ion liquid.
5. method according to claim 3, is characterized in that: described sulfonic acid type ion liquid catalyst is the one in sulfonic acid pyrrolidone series, sulfonic acid pyridine series, sulfonic acid imidazoles series, sulfonic alkyl quaternary ammonium series, sulfonic alkyl season phosphine serial ion liquid.
6. method according to claim 1, it is characterized in that: the reaction conditions in described step (1) is: the mass ratio of organic acid and ionic-liquid catalyst is 1:1 ~ 5:1, temperature of reaction 25 ~ 35 DEG C, reaction pressure is 0 ~ 1.0MPa, liquid air speed 0.5 ~ 3.0h
-1.
7. method according to claim 1, is characterized in that: it is degassed that the middle tert-butyl ester crude product of described step (2) carries out low-temperature reduced-pressure under the condition of temperature 0 ~ 10 DEG C, vacuum tightness 0.09MPa.
8. method according to claim 1, is characterized in that: in described step (2), the decomposition temperature of tert-butyl ester crude product is 40 ~ 80 DEG C, and pressure is normal pressure.
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| CN201310360793.3A CN104418688A (en) | 2013-08-19 | 2013-08-19 | Method for separating and purifying isobutylene from mixed C4 |
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| CN201310360793.3A CN104418688A (en) | 2013-08-19 | 2013-08-19 | Method for separating and purifying isobutylene from mixed C4 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134176A (en) * | 2018-10-24 | 2019-01-04 | 岳阳富和科技有限公司 | A kind of utilization mixes the manufacturing method of the high-purity isobutene of decomposition production after C4 acetic acid esterified |
Citations (4)
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|---|---|---|---|---|
| GB889289A (en) * | 1959-12-19 | 1962-02-14 | Distillers Co Yeast Ltd | Tertiary butyl acetate |
| GB890760A (en) * | 1959-12-19 | 1962-03-07 | Distillers Co Yeast Ltd | Separation of isobutene from other hydrocarbons |
| US5457228A (en) * | 1990-10-31 | 1995-10-10 | Daicel Chemical Industries, Ltd. | Method for producing lower alkyl acetate |
| CN1884248A (en) * | 2006-07-04 | 2006-12-27 | 湖南长岭石化科技开发有限公司 | Process for preparing and extracting tert-butyl acetate |
-
2013
- 2013-08-19 CN CN201310360793.3A patent/CN104418688A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB889289A (en) * | 1959-12-19 | 1962-02-14 | Distillers Co Yeast Ltd | Tertiary butyl acetate |
| GB890760A (en) * | 1959-12-19 | 1962-03-07 | Distillers Co Yeast Ltd | Separation of isobutene from other hydrocarbons |
| US5457228A (en) * | 1990-10-31 | 1995-10-10 | Daicel Chemical Industries, Ltd. | Method for producing lower alkyl acetate |
| CN1884248A (en) * | 2006-07-04 | 2006-12-27 | 湖南长岭石化科技开发有限公司 | Process for preparing and extracting tert-butyl acetate |
Non-Patent Citations (4)
| Title |
|---|
| YANLONG GU等: "Esterification of aliphatic acids with olefin promoted", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 朱继芳等: "乙酸/乙烯酯化合成乙酸乙酯工艺", 《化学反应工程与工艺》 * |
| 陈晓惠: "高纯异丁烯的制备方法", 《会议论文》 * |
| 陶端健等: "离子液体催化酯化反应的研究进展", 《现代化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134176A (en) * | 2018-10-24 | 2019-01-04 | 岳阳富和科技有限公司 | A kind of utilization mixes the manufacturing method of the high-purity isobutene of decomposition production after C4 acetic acid esterified |
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Application publication date: 20150318 |