CN103570488A - Method for preparing m-diisopropylbenzene by isomerising high-ortho-position mixed diisopropylbenzene - Google Patents
Method for preparing m-diisopropylbenzene by isomerising high-ortho-position mixed diisopropylbenzene Download PDFInfo
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- CN103570488A CN103570488A CN201210255247.9A CN201210255247A CN103570488A CN 103570488 A CN103570488 A CN 103570488A CN 201210255247 A CN201210255247 A CN 201210255247A CN 103570488 A CN103570488 A CN 103570488A
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- diisopropylbenzene
- dipb
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Abstract
The invention provides a method for preparing m-diisopropylbenzene by isomerising high-ortho-position mixed diisopropylbenzene. The purpose of the invention is to prepare m-diisopropylbenzene by taking mixed diisopropylbenzene in a diphenol device as the raw material. An H beta molecular sieve having better isomerisation performance is adopted; modification is carried out by adopting organic acid; the content of ortho-diisopropylbenzene in mixed diisopropylbenzene is obviously reduced through isomerisation reaction (less than 1.0%); the product is directly rectified; the purity of the final product, namely m-diisopropylbenzene, is above 98.0%; simultaneously, the stability of a catalyst is also increased; and basis is provided for industrial production. Due to the method disclosed by the invention, on the one hand, the utilization value for mixing diisopropylbenzene in the diphenol device can be increased; m-diisopropylbenzene having higher market value and increasing quantity demand is obtained; on the other hand, the separation difficulty of mixed diisopropylbenzene (especially m-diisopropylbenzene and ortho-diisopropylbenzene) is reduced; and the material consumption and the energy consumption are reduced.
Description
Technical field
The invention belongs to the molecular sieve acid catalyzed reaction in Industrial Catalysis field, be specifically related to the method for a kind of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene processed.
Background technology
US Patent No. 4822943 proposes take isopropyl benzene and/or benzene-propylene is raw material, and on ZSM-12 molecular sieve, p-Diisopropylbenzene is produced in reaction.
European patent WO03000629 proposition is a kind of take adjacent diisopropylbenzene(DIPB), m-Diisopropylbenzene and benzene as raw material, take β zeolite, mordenite and MCM-22 as catalyzer, by alkylation, disproportionation, transalkylation and isomerization reaction selectivity, produce the method for m-Diisopropylbenzene, can effectively adjacent diisopropylbenzene(DIPB) 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.
Chinese patent 200410052719.X mainly investigates production method and the used catalyst of p-Diisopropylbenzene, but adjacent diisopropylbenzene(DIPB) and m-Diisopropylbenzene is not studied.
Master's thesis < < modified beta zeolite catalysis diisopropylbenzene(DIPB) isomerization reaction research > >, Zhao Peixia, Dalian University of Technology, 2005, mainly investigated the beta-molecular sieve at H, and on the H beta-molecular sieve of the H beta-molecular sieve of mineral acid and ammonium salt modification thereof and 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 that does not relate to adjacent diisopropylbenzene(DIPB) in literary composition, but for the higher mixing diisopropylbenzene(DIPB) of ortho position content, due to ortho position and a position boiling point very approaching, cannot utilize existing technology to isolate high purity m-Diisopropylbenzene, cause the waste of the mixing diisopropylbenzene(DIPB) that ortho position content is higher.
Document < < temperature, air speed affect > > to what mix diisopropylbenzene(DIPB) isomerization reaction on beta-zeolite catalyst, Zhang Chunyong etc., petrochemical complex, the 33rd the 6th phase of volume, 2004, author is on beta-zeolite catalyst, investigated under 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.In literary composition, also do not relate to the isomerization ability of adjacent diisopropylbenzene(DIPB), in three kinds of isomer due to diisopropylbenzene(DIPB), the diffusion energy barrier at ortho position is the highest, under identical condition, in the more difficult twelve-ring duct that is penetrated into beta-zeolite catalyst, is unfavorable for the carrying out of reaction.
Diisopropylbenzene(DIPB) isomerization reaction > > on document < < molecular sieve catalyst, Zhao Peixia etc., Industrial Catalysis, the 13rd the 1st phase of volume, 2005, recorded and take beta-molecular sieve as catalyzer is for p-Diisopropylbenzene isomerization reaction, p-Diisopropylbenzene isomery is turned to m-Diisopropylbenzene, reduce and mix contraposition content in diisopropylbenzene(DIPB), thereby isolate the m-Diisopropylbenzene that purity is higher, do not relate to the reaction at ortho position, but compare with p-Diisopropylbenzene, adjacent diisopropylbenzene(DIPB) is more difficult separated with m-Diisopropylbenzene.
The modification of document < < ammonium salt affects > > to the acidity of beta-molecular sieve and catalysis diisopropylbenzene(DIPB) isomerization reaction performance thereof, Zhao Peixia etc., petrochemical complex, the 34th the 6th phase of volume, 2005, investigated the impact on the isomerization reaction of beta-molecular sieve modification p-Diisopropylbenzene of ternary organic acid ammonium salt and traditional ammonium nitrate, 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 selectivity to produce the method for p-Diisopropylbenzene, it take isopropyl benzene and propylene is raw material, on ZSM-12 molecular sieve, alkylation is produced and is mixed diisopropylbenzene(DIPB), 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 by cumene disproportionation effect selectivity, to produce m-Diisopropylbenzene and adjacent diisopropylbenzene(DIPB) 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 the method for a kind of shape selective catalysis cracking m-Diisopropylbenzene processed, is mainly the shape selective catalysis cracking of p-Diisopropylbenzene, but and the conversion of not mentioned adjacent diisopropylbenzene(DIPB).
In a word, in prior art, have the following disadvantages:
1, in biphenol device, mix the utility value of diisopropylbenzene(DIPB) not high, the m-Diisopropylbenzene purity obtaining is not high;
2, the stability of catalyzer is not high, is difficult to suitability for industrialized production;
3, mix the separating difficulty of diisopropylbenzene(DIPB) (particularly m-Diisopropylbenzene and adjacent diisopropylbenzene(DIPB)) larger, and material consumption and energy consumption higher.
Summary of the invention
The method that the object of this invention is to provide a kind of high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene processed, 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 mixing diisopropylbenzene(DIPB) that the present invention be take in biphenol device is raw material, take zeolite molecular sieve as catalyzer, to mixing diisopropylbenzene(DIPB), carries out isomerization reaction, and optionally the adjacent diisopropylbenzene(DIPB) of isomerization, retains m-Diisopropylbenzene, simultaneously by-product isopropyl benzene; Again product is carried out to rectifying, 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 that the mixing diisopropylbenzene(DIPB) of take in biphenol device is raw material, take and prepares m-Diisopropylbenzene as object.Adopt the good H beta-molecular sieve of isomerization performance (catalyzer is from Dalian University of Technology), and adopt citric acid-modified, method of modifying: will in beta-zeolite molecular sieve powder and 0.1 mol/L citric acid water-bath, carry out ion-exchange, treatment temp is 80 ℃, liquid-solid ratio is 10(weight ratio), time is 4h, and suction filtration, washs afterwards, dry, then extruded moulding, roasting 4h at 540 ℃, obtains the H zeolite beta molecular sieve of citric acid-modified; Obviously reduced the content (be less than 1.0%, m/m), and product carried out to rectifying, in the finished product, m-Diisopropylbenzene purity reaches 98.0%(m/m) of adjacent diisopropylbenzene(DIPB) in mixing diisopropylbenzene(DIPB) by isomerization reaction more than, adjacent diisopropylbenzene(DIPB) content is no more than 2%.Also improved the stability of catalyzer, for suitability for industrialized production provides the foundation simultaneously.
The method of isomerization of the present invention m-Diisopropylbenzene processed, the mixing diisopropylbenzene(DIPB) of take in biphenol device is raw material, and the key step of its reaction is: take zeolite molecular sieve as catalyzer, be preferably H beta-molecular sieve, in fixed-bed reactor, react, its reaction conditions is:
(1) pressure is 3.2MPa, and temperature is 195 ℃, and mass space velocity is 2.58～3.01h
-1; Or
(2) pressure is 1.0～3.0MPa, and temperature is 180～200 ℃, and mass space velocity is 1.72h
-1.
Raw material enters reaction system through double plunger Micro-metering Pumps, by reactor lower part, entered, product flows out continuously from reactor top, in knockout drum, accumulates, 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)
.to described liquid product, use rectifying tower separated, rectifying tower Optimization Theory stage number is about 85, and obtaining isopropyl benzene and purity is the above m-Diisopropylbenzene of 98.0% (m/m).
The beneficial effect of the method for the invention comprises:
1, can improve the utility value of mixing diisopropylbenzene(DIPB) in biphenol device, therefrom obtain the m-Diisopropylbenzene that purity is higher, that is to say, obtain being worth the higher and ever-increasing m-Diisopropylbenzene of demand on market, for next step m-Diisopropylbenzene oxidation provides acceptable material;
2, also improved the stability of catalyzer simultaneously, for suitability for industrialized production provides the foundation;
3, can also reduce and mix diisopropylbenzene(DIPB) (particularly m-Diisopropylbenzene and adjacent diisopropylbenzene(DIPB)) separating difficulty, 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---in biphenol device, mix diisopropylbenzene(DIPB) raw material; 7---take zeolite molecular sieve as catalyzer; 8---liquid product; 9---isopropyl benzene and purity are more than 98% m-Diisopropylbenzene.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Take H beta-molecular sieve as catalyzer, loading catalyst in fixed-bed reactor; The middle mixing of biphenol device (1) diisopropylbenzene(DIPB) of take is raw material (6); 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 ℃, and mass space velocity is 3.01h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulation in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, adjacent diisopropylbenzene(DIPB) content in product is less than 1.0%(m/m)
.
To described liquid product, use theoretical plate number to be about 85 rectifying tower (5) separation, obtaining isopropyl benzene and purity is 98.0%(m/m) above m-Diisopropylbenzene (9).
Take H beta-molecular sieve as catalyzer, loading catalyst in fixed-bed reactor; The middle mixing of biphenol device (1) diisopropylbenzene(DIPB) of take is raw material (6); 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 ℃, and inlet amount is that mass space velocity is 2.58h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulation in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, adjacent diisopropylbenzene(DIPB) content in product is less than 1.0%(m/m).
To described liquid product, use theoretical plate number to be about 85 rectifying tower (5) separation, obtaining isopropyl benzene and purity is the above m-Diisopropylbenzene (9) of 98.0% (m/m).
Take H beta-molecular sieve as catalyzer, loading catalyst in fixed-bed reactor; The middle mixing of biphenol device (1) diisopropylbenzene(DIPB) of take is raw material (6); 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 ℃, and mass space velocity is 1.72h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulation in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, adjacent diisopropylbenzene(DIPB) content in product is less than 1.0%(m/m).
To described liquid product, use theoretical plate number to be about 85 rectifying tower (5) separation, obtaining isopropyl benzene and purity is the above m-Diisopropylbenzene (9) of 98.0% (m/m).
Take H beta-molecular sieve as catalyzer, loading catalyst in fixed-bed reactor; The middle mixing of biphenol device (1) diisopropylbenzene(DIPB) of take is raw material (6); 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 ℃, and mass space velocity is 1.72h
-1.In fixed-bed reactor, reacted product flows out continuously from reactor top, accumulation in knockout drum (4), and intermittent type takes out the liquid product (8) in knockout drum, adjacent diisopropylbenzene(DIPB) content in product is less than 1.0%(m/m).
To described liquid product, use theoretical plate number to be about 85 rectifying tower (5) separation, obtaining isopropyl benzene and purity is the above m-Diisopropylbenzene (9) of 98.0% (m/m).
Claims (6)
1. a method for high ortho position mixing diisopropylbenzene(DIPB) isomerization m-Diisopropylbenzene processed, is characterized in that, the method comprises the following steps:
Step 1, the middle mixing of biphenol device (1) diisopropylbenzene(DIPB) of take is raw material (6), and raw material is passed into reaction in fixed-bed reactor (3), fixed-bed reactor are filled with zeolite [molecular sieve in (3);
Wherein fixed-bed reactor reaction conditions is:
Pressure is 3.2MPa, and temperature is 195 ℃, and mass space velocity is 2.58～3.01h
-1; Or
Pressure is 1.0～3.0MPa, and temperature is 180～200 ℃, and mass space velocity is 1.72h
-1;
Step 2, reacted product flows out continuously from fixed-bed reactor top, accumulation in knockout drum (4), intermittent type takes out the liquid product (8) in knockout drum, adjacent diisopropylbenzene(DIPB) content in liquid product is less than 1.0%(m/m);
Step 3, is used rectifying tower (5) separation to described liquid product, obtains isopropyl benzene and m-Diisopropylbenzene (9).
2. the method for claim 1, is characterized in that, zeolite [molecular sieve is H zeolite beta molecular sieve.
3. method as claimed in claim 2, is characterized in that, described H zeolite beta molecular sieve adopts citric acid-modified.
4. method as claimed in claim 3, it is characterized in that wherein said method of modifying: will in beta-zeolite molecular sieve powder and 0.1 mol/L citric acid water-bath, carry out ion-exchange, treatment temp is 80 ℃, and liquid-solid ratio is 10(weight ratio), the time is 4h, suction filtration afterwards, washing, dries, then extruded moulding, roasting 4h at 540 ℃, obtains the H zeolite beta molecular sieve of citric acid-modified.
5. the method as described in claim 1-4, is characterized in that, raw material, through double plunger Micro-metering Pumps (2), enters reaction in fixed-bed reactor (3) by reactor lower part.
6. the method as described in claim 1-5, is characterized in that, to described liquid product, uses theoretical plate number to be about 85 rectifying tower (5) separation, and obtaining isopropyl benzene and purity is 98.0%(m/m) above m-Diisopropylbenzene (9).
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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 |
-
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- 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 (2)
| Title |
|---|
| 牛瑾: "多异丙苯在改性β沸石上的反应研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 赵其献: "择形催化裂化制备间二异丙苯的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
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