CN103664474B - The method of ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene - Google Patents
The method of ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene Download PDFInfo
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- CN103664474B CN103664474B CN201210324484.6A CN201210324484A CN103664474B CN 103664474 B CN103664474 B CN 103664474B CN 201210324484 A CN201210324484 A CN 201210324484A CN 103664474 B CN103664474 B CN 103664474B
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- diethylbenzene
- ethylbenzene
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Abstract
The present invention relates to a kind of method of ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene, mainly solve prior art and there is the lower problem of p-Diethylbenzene selectivity.The present invention by adopting with ethylbenzene and ethanol for reaction raw materials, temperature of reaction 210 ~ 450 DEG C, reaction pressure 0.5 ~ 4.5MPa, weight ethylene air speed 0.2 ~ 1.0 hour
-1, under the condition of ethylbenzene/ethanol mol ratio 2 ~ 8, reaction raw materials and catalyst exposure generate p-Diethylbenzene; Described catalyzer, with weight parts, comprises following component: a) SiO of 40 ~ 80 parts
2/ Al
2o
3mol ratio is the MWW type molecular sieve of 10 ~ 100; B) technical scheme of binding agent of 20 ~ 60 parts solves this problem preferably, can be used in the industrial production of ethylbenzene and alcohol production p-Diethylbenzene.
Description
Technical field
The present invention relates to a kind of method of ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene.
Background technology
P-Diethylbenzene is a kind of important Organic Chemicals, main application is the special strippant of p-Xylene unit adsorption separation process, also can be used to produce Vinylstyrene, be further used for the properties-correcting agent of ion exchange resin, synthetic rubber divinylbenzene and polystyrene and the polymerization single polymerization monomer of unsaturated polyester glass steel etc.
The production of p-Diethylbenzene mainly contains two kinds of techniques, and the first technique adopts the rectificating method of mixing diethylbenzene to purify out p-Diethylbenzene.This technology takes the lead in being developed the seventies in last century by Uop Inc., but there is the shortcomings such as raw material sources are single, separating energy consumption is high, facility investment is large, is not widely used always.The second technique be ethylbenzene and ethene under the effect of catalyzer, utilize the shape selectivity of molecular sieve to produce p-Diethylbenzene.Some companies are constantly devoted to carry out to molecular sieve the research that modification obtains high purity p-Diethylbenzene technology, and such as US Patent No. 4100217 adopts ZSM-23 molecular screen to be active constituent, produce p-Diethylbenzene by ethylbenzene and ethylene reaction.US Patent No. 4094921 carries out steam treatment and pre-carbon deposit to improve the shape selectivity of catalyzer to the ZSM-5 molecular sieve of more than 1 micron.United States Patent (USP) 4128592 pairs of ZSM-5 molecular sieves carry out steam treatment and in conjunction with phosphorus-magnesium-modified, to improve the shape selectivity of p-Diethylbenzene.US Patent No. 4465886, US5406015, US5530170 etc. all adopt siliceous organic compound to carry out modification to improve the shape selectivity of p-Diethylbenzene to ZSM-5, ZSM-11, ZSM-23, ZSM-35, ZSM-38, ZSM-48 equimolecular sieve.In addition, Chinese patent CN200410020397.7, CN90101436.2, CN200310116628.X, CN94110202.5 and open source literature " petrochemical complex " 18 volumes the 2nd phase in 1989 92 pages, " petrochemical complex " 21 volumes the 5th phase in 1992 the 289th page, the 1006th page, " petrochemical complex " 33 volume supplementary issue in 2004, " chemical engineering " the 36th volume the 3rd phase in 2008 the 76th page etc. all relate to and adopt ZSM-5 molecular sieve or adopt various method of modifying to produce p-Diethylbenzene to it.
The ethylbenzene that above-mentioned patent or open source literature relate to and ethanol synthesis generate the process of p-Diethylbenzene, and the catalyzer of employing is generally ZSM-5 or modified ZSM-5, there is the problem that p-Diethylbenzene selectivity is lower.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the lower problem of p-Diethylbenzene selectivity, provides a kind of method of new ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene.The method has the high feature of p-Diethylbenzene selectivity.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene, with ethylbenzene and ethanol for reaction raw materials, temperature of reaction 210 ~ 450 DEG C, reaction pressure 0.5 ~ 4.5MPa, weight ethylene air speed 0.2 ~ 1.0 hour
-1, under the condition of ethylbenzene/ethanol mol ratio 2 ~ 8, reaction raw materials and catalyst exposure generate p-Diethylbenzene; Described catalyzer, with weight parts, comprises following component: a) SiO of 40 ~ 80 parts
2/ Al
2o
3mol ratio is the MWW type molecular sieve of 10 ~ 100; B) binding agent of 20 ~ 60 parts.
In technique scheme, the SiO of MWW type molecular sieve
2/ Al
2o
3mol ratio preferable range is 15 ~ 80, and more preferably scope is 20 ~ 70, and most preferred range is 25 ~ 65.Described MWW type molecular sieve preferred version is at least one be selected from MCM-22, MCM-36, MCM-49, MCM-56, PSH-3, SSZ-25, ITQ-1 or ITQ-2, and more preferably scheme is at least one be selected from MCM-22, MCM-36, MCM-49 or MCM-56.Described binding agent preferred version is for being selected from aluminum oxide or silicon oxide.With weight parts, the consumption preferable range of MWW molecular sieve is 50 ~ 75 parts, and the consumption preferable range of binding agent is 25 ~ 50 parts.
Before MWW type molecular sieve in the inventive method is used for reaction, the exchange of known ammonium, dry and roasting technology process can be adopted.Such as ammonium is handed over as the ammonium salt solution by weight concentration 1 ~ 20%, under 50 ~ 90 DEG C of conditions, process 0.5 ~ 24 hour.Above-mentioned treating processes can carry out 3 ~ 5 times.Described ammonium salt is selected from least one in ammonium nitrate, ammonium chloride, ammonium sulfate, ammoniacal liquor or ammonium acetate.Described exchange generally also comprises filtration, water-washing step.Drying step is process 1 ~ 10 hour at 100 ~ 140 DEG C.Calcination steps is process 1 ~ 10 hour at 500 ~ 550 DEG C.
The preparation method of the catalyzer in the present invention is: by MWW type molecular sieve and binding agent extruded moulding, drying, roasting, both can obtain catalyzer.
The inventive method adopts with SiO
2/ Al
2o
3be 10 ~ 100 MWW type molecular sieve be active constituent, improve the selectivity of p-Diethylbenzene, compared with ZSM-5 molecular sieve, p-Diethylbenzene selectivity improves 3 ~ 9 percentage points, achieves good technique effect.
Further instruction is given to the present invention below by embodiment.
Embodiment
[embodiment 1]
By 70 grams of SiO
2/ Al
2o
3be that the MCM-22 molecular sieve of 25 and the aluminum oxide of 30 grams mediate extruded moulding, oven dry, roasting, then use 10%(wt) ammonium nitrate solution exchange 4 times at 80 DEG C, dry, roasting obtain p-Diethylbenzene catalyst A.
[embodiment 2]
By 74 grams of SiO
2/ Al
2o
3be that the MCM-56 molecular sieve of 20 and the aluminum oxide of 30 grams mediate extruded moulding, oven dry, roasting, then use 10%(wt) ammonium nitrate solution exchange 4 times at 80 DEG C, dry, roasting obtain p-Diethylbenzene catalyst B.
[embodiment 3]
By 52 grams of SiO
2/ Al
2o
3be that the MCM-49 molecular sieve of 50 and the aluminum oxide of 48 grams mediate extruded moulding, oven dry, roasting, then use 10%(wt) ammonium nitrate solution exchange 4 times at 80 DEG C, dry, roasting obtain p-Diethylbenzene catalyzer C.
[embodiment 4]
By 75 grams of SiO
2/ Al
2o
3be that the MCM-36 molecular sieve of 40 and the aluminum oxide of 25 grams mediate extruded moulding, oven dry, roasting, then use 10%(wt) ammonium nitrate solution exchange 4 times at 80 DEG C, dry, roasting obtain p-Diethylbenzene catalyzer D.
[embodiment 5]
By 75 grams of SiO
2/ Al
2o
3be that the ITQ-2 molecular sieve of 60 and the aluminum oxide of 25 grams mediate extruded moulding, oven dry, roasting, then use 10%(wt) ammonium nitrate solution exchange 4 times at 80 DEG C, dry, roasting obtain p-Diethylbenzene catalyzer E.
[embodiment 6]
By 65 grams of SiO
2/ Al
2o
3be that the MCM-22 molecular sieve of 50 and the aluminum oxide of 35 grams mediate extruded moulding, oven dry, roasting, then use 10%(wt) ammonium nitrate solution exchange 4 times at 80 DEG C, dry, roasting obtain p-Diethylbenzene catalyzer F.
[embodiment 7]
Catalyst A ~ F is carried out ethylbenzene and ethanol alkylation reaction, temperature of reaction is 420 DEG C, and reaction pressure is 1.5MPa, and the mol ratio of ethylbenzene/ethanol is 4.5, and ethanol weight space velocity is 0.4 hour
-1, the loadings of catalyzer is 2.0 grams, and adopt gas chromatographic analysis products therefrom, concrete reaction result is in table 1.
[comparative example]
By 75 grams of SiO
2/ Al
2o
3be that the ZSM-5 molecular sieve of 60 and the aluminum oxide of 25 grams mediate extruded moulding, oven dry, roasting, then use 10%(wt) ammonium nitrate solution exchange 4 times at 50 DEG C, dry, roasting obtain p-Diethylbenzene catalyzer W.Ethylbenzene and ethanol alkylation reaction is carried out according to the condition of [embodiment 7].Reaction result is in table 1.
The response data of table 1 ethylbenzene and ethanol p-Diethylbenzene
| P-Diethylbenzene catalyzer | Ethanol conversion | Ethylbenzene selectivity |
| A | 99.1% | 99.2% |
| B | 97.2% | 94.3% |
| C | 95.1% | 98.5% |
| D | 96.9% | 94.2% |
| E | 94.1% | 97.5% |
| F | 98.7% | 97.9% |
| W | 93.7% | 90.1% |
Claims (7)
1. a method for ethylbenzene and ethanol alkylation Reactive Synthesis p-Diethylbenzene, with ethylbenzene and ethanol for reaction raw materials, temperature of reaction 210 ~ 450 DEG C, reaction pressure 0.5 ~ 4.5MPa, ethanol weight space velocity 0.2 ~ 1.0 hour
-1, under the condition of ethylbenzene/ethanol mol ratio 2 ~ 8, reaction raw materials and catalyst exposure generate p-Diethylbenzene; Described catalyzer, with weight parts, comprises following component: a) SiO of 40 ~ 80 parts
2/ Al
2o
3mol ratio is the MWW type molecular sieve of 10 ~ 100; B) binding agent of 20 ~ 60 parts; Described binding agent is selected from aluminum oxide.
2. the method for ethylbenzene according to claim 1 and ethanol alkylation Reactive Synthesis p-Diethylbenzene, is characterized in that the SiO of MWW type molecular sieve
2/ Al
2o
3mol ratio is 15 ~ 80.
3. the method for ethylbenzene according to claim 2 and ethanol alkylation Reactive Synthesis p-Diethylbenzene, is characterized in that the SiO of MWW type molecular sieve
2/ Al
2o
3mol ratio is 20 ~ 70.
4. the method for ethylbenzene according to claim 3 and ethanol alkylation Reactive Synthesis p-Diethylbenzene, is characterized in that the SiO of MWW type molecular sieve
2/ Al
2o
3mol ratio is 25 ~ 65.
5. the method for ethylbenzene according to claim 1 and ethanol alkylation Reactive Synthesis p-Diethylbenzene, is characterized in that at least one of described MWW type molecular screening in MCM-22, MCM-36, MCM-49, MCM-56, PSH-3, SSZ-25, ITQ-1 or ITQ-2.
6. the method for ethylbenzene according to claim 5 and ethanol alkylation Reactive Synthesis p-Diethylbenzene, is characterized in that at least one of described MWW type molecular screening in MCM-22, MCM-36, MCM-49 or MCM-56.
7. the method for ethylbenzene according to claim 1 and ethanol alkylation Reactive Synthesis p-Diethylbenzene, is characterized in that with weight parts, and the consumption of MWW type molecular sieve is 50 ~ 75 parts, and the consumption of binding agent is 25 ~ 50 parts.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756727A (en) * | 2003-02-28 | 2006-04-05 | Abb路慕斯全球股份有限公司 | Process for the production of alkylaromatics |
| CN101054334A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Application of nano molecular sieve catalyst in alkylation reaction of arene |
| CN102500410A (en) * | 2011-11-25 | 2012-06-20 | 同济大学 | Catalyst for ethylbenzene and ethanol synthesis to realize shape-selectivity alkylation for diethylbenzene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1756727A (en) * | 2003-02-28 | 2006-04-05 | Abb路慕斯全球股份有限公司 | Process for the production of alkylaromatics |
| CN101054334A (en) * | 2007-05-31 | 2007-10-17 | 上海华谊丙烯酸有限公司 | Application of nano molecular sieve catalyst in alkylation reaction of arene |
| CN102500410A (en) * | 2011-11-25 | 2012-06-20 | 同济大学 | Catalyst for ethylbenzene and ethanol synthesis to realize shape-selectivity alkylation for diethylbenzene |
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