CN103570488B - A kind of method of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene - Google Patents
A kind of method of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene Download PDFInfo
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- CN103570488B CN103570488B CN201210255247.9A CN201210255247A CN103570488B CN 103570488 B CN103570488 B CN 103570488B CN 201210255247 A CN201210255247 A CN 201210255247A CN 103570488 B CN103570488 B CN 103570488B
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- diisopropylbenzene
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Abstract
The invention provides a kind of method of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene, the method with the mixing diisopropylbenzene(DIPB) in biphenol device for raw material, to prepare for the purpose of m-Diisopropylbenzene.Adopt the good H beta-molecular sieve of isomerization performance, and adopt modified with organic acids, significantly reduced the content (being less than 1.0%) of adjacent diisopropylbenzene(DIPB) in mixing diisopropylbenzene(DIPB) by isomerization reaction, and directly carry out rectifying to product, in the finished product, m-Diisopropylbenzene purity reaches more than 98.0%; Also improve the stability of catalyzer, for suitability for industrialized production provides the foundation simultaneously.The method can improve the utility value mixing diisopropylbenzene(DIPB) in biphenol device on the one hand, obtain market being worth the higher and ever-increasing m-Diisopropylbenzene of demand, reduce mixing diisopropylbenzene(DIPB) (particularly m-Diisopropylbenzene and adjacent diisopropylbenzene(DIPB)) separating difficulty on the other hand, reduce material consumption and energy consumption.
Description
Technical field
The invention belongs to the molecular sieve acid catalyzed reaction in Industrial Catalysis field, be specifically related to a kind of method of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene.
Background technology
US Patent No. 4822943 proposes with isopropyl benzene and/or benzene-propylene for raw material, and on ZSM-12 molecular sieve, p-Diisopropylbenzene is produced in reaction.
European patent WO03000629 proposes one with adjacent diisopropylbenzene(DIPB), m-Diisopropylbenzene and benzene for raw material, with β zeolite, mordenite and MCM-22 for catalyzer, the method of m-Diisopropylbenzene is produced by alkylation, disproportionation, transalkylation and isomerization reaction selectivity, effectively adjacent diisopropylbenzene(DIPB) can be converted into m-Diisopropylbenzene, but the active ingredient of catalyzer is MCM-22, and in product, m-Diisopropylbenzene content is lower.
US Patent No. 6753453 proposes on MCM-22 molecular sieve, prepare m-Diisopropylbenzene, but in product, p-Diisopropylbenzene is also more, and m-Diisopropylbenzene is containing quantity not sufficient 20% by benzene and cumene disproportionation reaction.
The production method of Chinese patent 200410052719.X paper examines p-Diisopropylbenzene and used catalyst, but adjacent diisopropylbenzene(DIPB) and m-Diisopropylbenzene are not studied.
Master's thesis " modified beta zeolite catalysis diisopropylbenzene(DIPB) isomerization reaction research ", Zhao Peixia, Dalian University of Technology, 2005, paper examines is at H beta-molecular sieve, and on the H beta-molecular sieve of mineral acid and ammonium salt modification thereof and the H beta-molecular sieve of hydroxyl organic acid and ammonium salt modification thereof, p-Diisopropylbenzene isomery turns to the ability of m-Diisopropylbenzene, contraposition transformation efficiency is up to 52.92%, the isomerization ability of adjacent diisopropylbenzene(DIPB) is not related in literary composition, but for the mixing diisopropylbenzene(DIPB) that ortho position content is higher, due to ortho position and a position boiling point closely, existing technology separation cannot be utilized to go out high purity m-Diisopropylbenzene, the waste of the mixing diisopropylbenzene(DIPB) causing ortho position content higher.
Document " temperature, air speed are on impact beta-zeolite catalyst mixing diisopropylbenzene(DIPB) isomerization reaction ", Zhang Chunyong etc., petrochemical complex, the 33rd volume the 6th phase, 2004, author is on beta-zeolite catalyst, under having investigated differing temps and mass space velocity, p-Diisopropylbenzene isomery turns to the ability of m-Diisopropylbenzene, but catalyst stability is poor, along with the carrying out of reaction, p-Diisopropylbenzene transformation efficiency significantly declines.Also do not relate to the isomerization ability of adjacent diisopropylbenzene(DIPB) in literary composition, due in three kinds of isomer of diisopropylbenzene(DIPB), the diffusion energy barrier at ortho position is the highest, at identical conditions, more difficultly to penetrate in the twelve-ring duct of beta-zeolite catalyst, is unfavorable for the carrying out reacted.
Document " on molecular sieve catalyst diisopropylbenzene(DIPB) isomerization reaction ", Zhao Peixia etc., Industrial Catalysis, the 13rd volume the 1st phase, 2005, describe with beta-molecular sieve be catalyzer for p-Diisopropylbenzene isomerization reaction, p-Diisopropylbenzene isomery is turned to m-Diisopropylbenzene, reduce mixing diisopropylbenzene(DIPB) in contraposition content, thus isolate the higher m-Diisopropylbenzene of purity, do not relate to the reaction at ortho position, but compare with p-Diisopropylbenzene, adjacent diisopropylbenzene(DIPB) is separated with m-Diisopropylbenzene is more difficult.
Document " ammonium salt modification is on the impact of the acidity of beta-molecular sieve and catalysis diisopropylbenzene(DIPB) isomerization reaction performance thereof ", Zhao Peixia etc., petrochemical complex, 34th volume the 6th phase, 2005, investigated tribasic organic acid ammonium salt and traditional ammonium nitrate to the impact of beta-molecular sieve modification p-Diisopropylbenzene isomerization reaction, p-Diisopropylbenzene transformation efficiency is higher, but does not relate to the reactivity worth of citric acid-modified beta catalyst and the isomerization performance of ortho position diisopropylbenzene(DIPB).
US Patent No. 7102043 provides a kind of method that selectivity produces p-Diisopropylbenzene, it with isopropyl benzene and propylene for raw material, on ZSM-12 molecular sieve, mixing diisopropylbenzene(DIPB) is produced in alkylation, rectifying separation goes out m-Diisopropylbenzene, and on ZSM-12 molecular sieve, making its isomery turn to p-Diisopropylbenzene, rectifying separation goes out p-Diisopropylbenzene.
US Patent No. 7432405 proposes to produce m-Diisopropylbenzene and adjacent diisopropylbenzene(DIPB) by cumene disproportionation selective action on TEA-mordenite, in product, adjacent diisopropylbenzene(DIPB) content is less than 1%, and n-proplbenzene and tri-isopropyl benzene content also very low, but total diisopropylbenzene(DIPB) content is no more than 30%.
Chinese patent 200810011124.4 provides a kind of method of shape selective catalysis cracking m-Diisopropylbenzene, mainly the shape selective catalysis cracking of p-Diisopropylbenzene, but and the conversion of not mentioned adjacent diisopropylbenzene(DIPB).
In a word, have the following disadvantages in prior art:
1, the utility value mixing diisopropylbenzene(DIPB) in biphenol device is not high, and the m-Diisopropylbenzene purity obtained is not high;
2, the stability of catalyzer is not high, is difficult to suitability for industrialized production;
3, the separating difficulty mixing diisopropylbenzene(DIPB) (particularly m-Diisopropylbenzene and adjacent diisopropylbenzene(DIPB)) is comparatively large, and material consumption and energy consumption higher.
Summary of the invention
The object of this invention is to provide a kind of method of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene, described high ortho position mixing diisopropylbenzene(DIPB) refers to the mixing diisopropylbenzene(DIPB) that ortho position content is higher, is from the mixing diisopropylbenzene(DIPB) in biphenol device.
The present invention for raw material, take zeolite molecular sieve as catalyzer with the mixing diisopropylbenzene(DIPB) in biphenol device, carries out isomerization reaction to mixing diisopropylbenzene(DIPB), and optionally the adjacent diisopropylbenzene(DIPB) of isomerization, retains m-Diisopropylbenzene, simultaneously by-product isopropyl benzene; Carry out rectifying to product again, in the finished product, m-Diisopropylbenzene purity reaches 98%(m/m, mass percent) more than, adjacent diisopropylbenzene(DIPB) content is no more than 2%(m/m).
The present invention is with the mixing diisopropylbenzene(DIPB) in biphenol device for raw material, to prepare for the purpose of m-Diisopropylbenzene.Adopt the good H beta-molecular sieve (catalyzer is from Dalian University of Technology) of isomerization performance, and adopt citric acid-modified, method of modifying: carry out ion-exchange by beta-zeolite molecular sieve powder and 0.1 mol/L citric acid water-bath, treatment temp is 80 DEG C, liquid-solid ratio is 10(weight ratio), time is 4h, afterwards suction filtration, washing, dry, then extruded moulding, roasting 4h at 540 DEG C, obtains the H zeolite beta molecular sieve of citric acid-modified; Significantly reduced the content (being less than 1.0%, m/m) of adjacent diisopropylbenzene(DIPB) in mixing diisopropylbenzene(DIPB) by isomerization reaction, and carry out rectifying to product, in the finished product, m-Diisopropylbenzene purity reaches 98.0%(m/m) more than, adjacent diisopropylbenzene(DIPB) content is no more than 2%.Also improve the stability of catalyzer, for suitability for industrialized production provides the foundation simultaneously.
The method of isomerization m-Diisopropylbenzene of the present invention, with the mixing diisopropylbenzene(DIPB) in biphenol device for raw material, the key step of its reaction is: take zeolite molecular sieve as catalyzer, is preferably H beta-molecular sieve, react in fixed-bed reactor, its reaction conditions is:
(1) pressure is 3.2MPa, and temperature is 195 DEG C, and mass space velocity is 2.58 ~ 3.01h
-1; Or
(2) pressure is 1.0 ~ 3.0MPa, and temperature is 180 ~ 200 DEG C, and mass space velocity is 1.72h
-1.
Raw material enters reaction system through double plunger Micro-metering Pumps, entered by reactor lower part, product flows out continuously from reactor top, accumulates in knockout drum, intermittent type takes out the liquid product in knockout drum, and adjacent diisopropylbenzene(DIPB) content in liquid product is less than 1.0%(m/m)
.use rectifying tower to be separated to described liquid product, rectifying tower Optimization Theory stage number is about 85, obtains the m-Diisopropylbenzene that isopropyl benzene and purity are more than 98.0% (m/m).
The beneficial effect of the method for the invention comprises:
1, the utility value mixing diisopropylbenzene(DIPB) in biphenol device can be improved, therefrom obtain the m-Diisopropylbenzene that purity is higher, that is, obtain market being worth the higher and ever-increasing m-Diisopropylbenzene of demand, for the oxidation of next step m-Diisopropylbenzene provides acceptable material;
2, also improve the stability of catalyzer, for suitability for industrialized production provides the foundation simultaneously;
3, mixing diisopropylbenzene(DIPB) (particularly m-Diisopropylbenzene and adjacent diisopropylbenzene(DIPB)) separating difficulty can also be reduced, reduce material consumption and energy consumption.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
Wherein, Reference numeral implication is: 1---biphenol device; 2---double plunger Micro-metering Pumps; 3---fixed-bed reactor; 4---knockout drum; 5---rectifying tower; 6---mix diisopropylbenzene(DIPB) raw material in biphenol device; 7---take zeolite molecular sieve as catalyzer; 8---liquid product; 9---isopropyl benzene and purity are the m-Diisopropylbenzene of more than 98%.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment 1
With H beta-molecular sieve for catalyzer, loading catalyst in fixed-bed reactor; Be raw material (6) with mixing diisopropylbenzene(DIPB) in biphenol device (1); Raw material, through double plunger Micro-metering Pumps (2), enters reaction in fixed-bed reactor (3) by reactor lower part; Its reaction conditions is: pressure is 3.2MPa, and temperature is 195 DEG C, and mass space velocity is 3.01h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulates in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, and adjacent diisopropylbenzene(DIPB) in the product content is less than 1.0%(m/m)
.
The rectifying tower (5) that described liquid product uses theoretical plate number to be about 85 is separated, obtains isopropyl benzene and purity is 98.0%(m/m) more than m-Diisopropylbenzene (9).
Embodiment 2
With H beta-molecular sieve for catalyzer, loading catalyst in fixed-bed reactor; Be raw material (6) with mixing diisopropylbenzene(DIPB) in biphenol device (1); Raw material, through double plunger Micro-metering Pumps (2), enters reaction in fixed-bed reactor (3) by reactor lower part; Its reaction conditions is: pressure is 3.2MPa, and temperature is 195 DEG C, and inlet amount is mass space velocity is 2.58h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulates in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, and adjacent diisopropylbenzene(DIPB) in the product content is less than 1.0%(m/m).
The rectifying tower (5) that described liquid product uses theoretical plate number to be about 85 is separated, obtains the m-Diisopropylbenzene (9) that isopropyl benzene and purity are more than 98.0% (m/m).
Embodiment 3
With H beta-molecular sieve for catalyzer, loading catalyst in fixed-bed reactor; Be raw material (6) with mixing diisopropylbenzene(DIPB) in biphenol device (1); Raw material, through double plunger Micro-metering Pumps (2), enters reaction in fixed-bed reactor (3) by reactor lower part; Its reaction conditions is: pressure is 1.0MPa, and temperature is 200 DEG C, and mass space velocity is 1.72h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulates in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, and adjacent diisopropylbenzene(DIPB) in the product content is less than 1.0%(m/m).
The rectifying tower (5) that described liquid product uses theoretical plate number to be about 85 is separated, obtains the m-Diisopropylbenzene (9) that isopropyl benzene and purity are more than 98.0% (m/m).
Embodiment 4
With H beta-molecular sieve for catalyzer, loading catalyst in fixed-bed reactor; Be raw material (6) with mixing diisopropylbenzene(DIPB) in biphenol device (1); Raw material, through double plunger Micro-metering Pumps (2), enters reaction in fixed-bed reactor (3) by reactor lower part; Its reaction conditions is: pressure is 3.0MPa, and temperature is 180 DEG C, and mass space velocity is 1.72h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulates in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, and adjacent diisopropylbenzene(DIPB) in the product content is less than 1.0%(m/m).
The rectifying tower (5) that described liquid product uses theoretical plate number to be about 85 is separated, obtains the m-Diisopropylbenzene (9) that isopropyl benzene and purity are more than 98.0% (m/m).
Claims (4)
1. a method for high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene, it is characterized in that, the method comprises the following steps:
Step one, be raw material (6) with mixing diisopropylbenzene(DIPB) in biphenol device (1), raw material is passed into reaction in fixed-bed reactor (3), fixed-bed reactor are filled with zeolite [molecular sieve in (3), and this zeolite [molecular sieve is the H zeolite beta molecular sieve adopting citric acid-modified;
Wherein, fixed-bed reactor reaction conditions is:
Pressure is 3.2MPa, and temperature is 195 DEG C, and mass space velocity is 2.58 ~ 3.01h
-1;
Step 2, reacted product flows out continuously from fixed-bed reactor top, accumulates in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, and adjacent diisopropylbenzene(DIPB) content in liquid product is less than 1.0%(m/m);
Step 3, uses rectifying tower (5) to be separated to described liquid product, obtains isopropyl benzene and m-Diisopropylbenzene (9).
2. the method for claim 1, it is characterized in that wherein said method of modifying: carry out ion-exchange by beta-zeolite molecular sieve powder and 0.1 mol/L citric acid water-bath, treatment temp is 80 DEG C, and liquid-solid ratio is 10(weight ratio), the time is 4h, suction filtration afterwards, washing, dries, then extruded moulding, roasting 4h at 540 DEG C, obtains the H zeolite beta molecular sieve of citric acid-modified.
3. method as claimed in claim 2, is characterized in that, raw material, through double plunger Micro-metering Pumps (2), enters reaction in fixed-bed reactor (3) by reactor lower part.
4. method as claimed in claim 3, is characterized in that, to described liquid product use theoretical plate number be 85 rectifying tower (5) be separated, obtain the m-Diisopropylbenzene (9) that isopropyl benzene and purity are more than 98.0% (m/m).
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| CN201210255247.9A CN103570488B (en) | 2012-07-23 | 2012-07-23 | A kind of method of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene |
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| CN201210255247.9A CN103570488B (en) | 2012-07-23 | 2012-07-23 | A kind of method of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB763182A (en) * | 1953-06-29 | 1956-12-12 | Distillers Co Yeast Ltd | Improvements in or relating to preparation of m- and p-diisopropylbenzene |
| GB809908A (en) * | 1954-07-30 | 1959-03-04 | Bataafsche Petroleum | A continuous process for preparing meta di-isopropylbenzene |
| US4547604A (en) * | 1980-03-14 | 1985-10-15 | Pcuk Produits Chimiques Ugine Kuhlmann | Selective isopropylation of cumene to meta-diisopropylbenzene |
| WO2002026671A1 (en) * | 2000-09-25 | 2002-04-04 | Exxonmobil Chemical Patents Inc. | Maximizing meta-isomers in the production of dialkylbenzene compounds |
| CN1345708A (en) * | 2000-09-28 | 2002-04-24 | 中国石油化工股份有限公司 | Method for preparing alkylbenzene by position rearrangement reaction of substituted alkyl on benzene ring |
-
2012
- 2012-07-23 CN CN201210255247.9A patent/CN103570488B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB763182A (en) * | 1953-06-29 | 1956-12-12 | Distillers Co Yeast Ltd | Improvements in or relating to preparation of m- and p-diisopropylbenzene |
| GB809908A (en) * | 1954-07-30 | 1959-03-04 | Bataafsche Petroleum | A continuous process for preparing meta di-isopropylbenzene |
| US4547604A (en) * | 1980-03-14 | 1985-10-15 | Pcuk Produits Chimiques Ugine Kuhlmann | Selective isopropylation of cumene to meta-diisopropylbenzene |
| WO2002026671A1 (en) * | 2000-09-25 | 2002-04-04 | Exxonmobil Chemical Patents Inc. | Maximizing meta-isomers in the production of dialkylbenzene compounds |
| CN1345708A (en) * | 2000-09-28 | 2002-04-24 | 中国石油化工股份有限公司 | Method for preparing alkylbenzene by position rearrangement reaction of substituted alkyl on benzene ring |
Non-Patent Citations (1)
| Title |
|---|
| 择形催化裂化制备间二异丙苯的研究;赵其献;《中国优秀硕士学位论文全文数据库工程科技I辑》;20120715(第7期);第39页第1段,表6.1，40页最后1段，42页倒数第4段和倒数第1段，表6.3，第41页倒数第2段 * |
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