CN103102240B - Synthesis method of sec-butylbenzene - Google Patents
Synthesis method of sec-butylbenzene Download PDFInfo
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- CN103102240B CN103102240B CN201110359431.3A CN201110359431A CN103102240B CN 103102240 B CN103102240 B CN 103102240B CN 201110359431 A CN201110359431 A CN 201110359431A CN 103102240 B CN103102240 B CN 103102240B
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Abstract
The invention relates to a synthesis method of sec-butylbenzene. The synthesis method mainly solves the problems that a synthetic catalyst containing molecular sieve sec-butylbenzene in the prior art is instable in activity and low in sec-butylbenzene selectivity. According to the synthesis method, the sec-butylbenzene which do not contain tert-butyl benzene basically can be stably synthesized by optimizing a novel molecular sieve alkylated catalyst under the conditions that the reaction temperature is 100-280 DEG C, the reaction pressure is 1.0-6.0MPa, the space velocity is 0.1-20h<-1> and the molar ratio of benzene to olefin is about 2-20, wherein the novel molecular sieve alkylated catalyst has the capabilities of keeping high conversion rate of hybrid linear butylene and high selectivity of sec-butylbenzene for a long peroid. The sec-butylbenzene with high purity can be obtained by rectification and the like in a high-yield manner, and the synthesis method can be used for industrial production of sec-butylbenzene synthesis.
Description
Technical field
The present invention relates to petrochemical industry, be specifically related to a kind of synthetic method of sec-butylbenzene.
Background technology
Sec-butylbenzene, as a kind of solvent and a kind of organic raw material or important chemical intermediate (producing phenol and methylethylketone), progressively obtains people's extensive concern in recent years.
At present, the method one of synthesizing sec-butyl benzene is with AlCl
3be catalyzer with solid phosphoric acid, with butylene and benzene alkylation synthesizing sec-butyl benzene, the method not only produces sec-butylbenzene, and produce the by product of different amount, mainly isobutyl-benzene, tert.-butylbenzene, dibutyl benzene and tributyl benzene, in these compounds, dibutyl benzene and tributyl benzene are easily separated from reaction mixture and it then can produce extra sec-butylbenzene by transalkylation.But the boiling point of isobutyl-benzene, sec-butylbenzene and tert.-butylbenzene is 172.8 DEG C, 173.5 DEG C and 169 DEG C respectively, be therefore difficult to by rectifying, these compounds are separated from each other.
U.S. Patent No. 5,059,736 describe the method preparing sec-butylbenzene from benzene and n-butene.It is included under uniform liquid aluminum chloride complex catalyst exists and makes benzene and n-butene reaction, used catalyst comprises aluminum chloride, hydrogenchloride and aromatic hydrocarbons, the amount being wherein used as the aluminum chloride of complex catalyst component is the 0.5-5.0% of benzene used, temperature of reaction is 20-70 DEG C, and as by product formed the amount of isobutyl-benzene and the weight ratio of sec-butylbenzene be not more than 0.01: 1.
Nineteen ninety, U.S. Patent No. 4,891,458 methods disclosing alkylation for aromatic hydrocarbons (as benzene) or transalkylation, it comprises under at least partial liquid phase conditions and under the catalyzer existed containing β zeolite exists, makes aromatic hydrocarbons and C
2-C
4olefin alkylation or the contact of many alkylaromatic hydrocarbons transalkylation contact substance.Although preferred alkene is ethene and propylene, it is said that suitable olefin alkylating agents comprises ethene, propylene, 1-butylene, trans-2-butene and cis-2-butene or its mixture.When benzene and n-butene or many butylbenzenes react, it is said that reaction product comprises sec-butylbenzene, but this patent is the relevant discovery based on laboratory substantially, therefore from industrialization, still there is a big difference.
A kind of method preparing phenol and methylethylketone disclosed in Chinese patent CN 101006033A contains benzene and carbon four and is included in comprising β zeolite or have under alkylating agent condition
with
the molecular sieve catalyst contact of the x-ray diffraction pattern of the d-spacer maximum value at place, specifically comprises the molecular sieve being selected from zeolite beta, mordenite, USY, MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2, MCM-36, MCM-49, MCM-56, UZM-8 and composition thereof in alkylation catalyst.The method finds make in benzene alkylation with linear butene, and zeolite beta zeolite is used as the sec-butylbenzene that catalyzer can produce lower concentration isobutyl-benzene and tert.-butylbenzene.But the catalyst life showing this invention use in this patent Example is partially short, preferred MCM-22 and containing the catalyzer of zeolite beta when the cycle of the longest 13 days, 2-butylene transformation efficiency undulation is large, particularly when using mixed butene charging, change fluctuation is more obvious, as during containing 65Wt% β/35% alumina binder, the 5th day 48.5% is dropped to very soon from the 2-butylene transformation efficiency 97.5% of first day, the selectivity of sec-butylbenzene drops to 70% from the highest 83%, catalyst catalytic performance can not meet long-term operation, illustrate that this invention is still in laboratory study level thus, larger gap is also had from industrial applications.
A kind of method preparing sec-butylbenzene is described in international monopoly W02006015824A1, with benzene and ethene as raw material, with the MCM-22 of Pd modification as catalyzer, in autoclave, carry out alkylated reaction, temperature 220 DEG C, pressure 3.9MPa, benzene alkene, than 3.25, under the condition of reaction times 4h, it is said that the transformation efficiency of ethene is 100%, in product, the massfraction of sec-butylbenzene can reach 99.5%, and the massfraction of ethylbenzene is 0.5%.
A kind of method preparing phenol and methylethylketone disclosed in Chinese patent CN101384533A makes benzene and C under comprising under alkylating conditions and comprise the alkylation catalyst existence of at least one MCM-22 family molecular sieves
4alkylating agent comprises the alkylate stream effluent of sec-butylbenzene with preparation, wherein implements contact in multiple reaction zone and provides C to each reaction zone
4alkylating agent, sec-butylbenzene fraction reclaims from this alkylate stream effluent and comprises the sec-butylbenzene of at least 95%, is less than the C8+ alkene of 100 weight ppm, is less than isobutyl-benzene and the tert.-butylbenzene of 0.5 % by weight.But the consumption showing the alkylation catalyst catalyzer containing at least one MCM-22 family molecular sieves that this invention uses in this patent Example is generally all less than 1g, sec-butylbenzene synthesising reacting time is general, and very short (1 hour to 188 hours is not etc., no longer than 200 hours), simultaneously butene conversion and sec-butylbenzene selectivity undulation large, also illustrate that this invention is still in laboratory and explores or lab scale research level thus, also have larger gap from industrial applications.
Summary of the invention
Technical problem to be solved by this invention is exist in prior art active unstable containing molecular sieve sec-butylbenzene synthetic catalyst, the problem that sec-butylbenzene selectivity is not high, preferred a kind of energy long period keeps the novel alkylation catalyst at least containing rich aluminium beta-molecular sieve having industrial prospect of various arch types butylene high conversion, sec-butylbenzene highly selective, high stable yield can synthesize the low sec-butylbenzene containing or do not contain tert.-butylbenzene under suitable reaction conditions, highly purified sec-butylbenzene product can be obtained by high yield by processes such as rectifying.
The present invention solves the problems of the technologies described above adopted technical scheme:
A kind of synthetic method of sec-butylbenzene, using silica alumina ratio be less than 20 allitic beta-zeolite or allitic beta-zeolite mix as molecular sieve allcylation catalyst with one or more in MCM race zeolite, with the mixture of one or more in carbon four-wire type organic compound for raw material, and add benzene, at temperature of reaction 100-280 DEG C, reaction pressure 1.0-6.0MPa, feedstock weight hourly space velocity 0.1-20h
-1condition under, synthesizing tertiary butyl benzene mass content is not higher than 1% or not containing the sec-butylbenzene of tert.-butylbenzene; The mixture of one or more in described carbon four-wire type organic compound is: the mixture of the iso-butylene containing 0-0.5wt% and the n-butene of 99.5-100wt%; Or containing one or more in the butane of 0.5-90wt%, with the iso-butylene of 0-0.5wt%, the mixture of 10-99wt% n-butene; The mol ratio 2-20 of benzene and alkene.
One or more in described butane choose the mixture of normal butane and Trimethylmethane.
Described temperature of reaction is 120-270 DEG C, and reaction pressure is 1.5-4.5MPa, and feedstock weight hourly space velocity is 0.2-10h
-1.
Described temperature of reaction is preferably 140-250 DEG C; Reaction pressure is preferably 1.8-3.5MPa; Feedstock weight hourly space velocity is preferably 0.4-5h
-1.
Described MCM race zeolite comprises MCM-22, MCM-36, MCM-49 or MCM-56.
React last synthetic product by rectifying, obtain tert.-butylbenzene mass content not higher than 1% or not containing the sec-butylbenzene of tert.-butylbenzene.
The present invention is by preferably long period keeping, the novel molecular sieve alkylation catalyst at least containing rich aluminium beta-molecular sieve of various arch types butylene high conversion, sec-butylbenzene highly selective, under the above-described reaction conditions, with not containing or the low mixed c 4 linear butene containing iso-butylene and benzene direct alkylation stablize the sec-butylbenzene that synthesis do not contain tert.-butylbenzene substantially, synthetic effluent can obtain highly purified sec-butylbenzene product by process height yields such as rectifying, can be used in the industrial production of sec-butylbenzene synthesis.
In order to illustrate that object of the present invention gives following examples, they do not limit the scope of the invention.
Embodiment
Embodiment 1: use butene-1 for sec-butylbenzene synthesis during carbon four raw material
20g is shaped at least loading in the tubular reactor of isothermal, upwards flowing, the fixed bed that internal diameter is 20mm containing rich aluminium beta-molecular sieve catalyzer (60% (massfraction) molecular sieve/40% (massfraction) binding agent etc.) of cylindric (diameter 1mm), gap, catalyst in reactor two ends quartz sand is filled.Benzene to be full of after reactor assembly progressively increasing temperature and pressure, to reach 145 DEG C in temperature of reaction, by butene-1 (iso-butylene content is less than 0.5%) incision reactor when reaction pressure reaches 2.0MPa, control weight hourly space velocity 3h
-1and benzene alkene mol ratio is carry out sec-butylbenzene building-up reactions under the condition of 3, along with the change appropriate change reaction conditions of butene-1 transformation efficiency such as can improve temperature of reaction etc. when C 4 olefin transformation efficiency obviously declines, such as when transformation efficiency often decline 0.5-1 percentage point time can on put forward temperature of reaction 1 DEG C.Analyze synthetic product composition by on-line chromatograph, the transformation efficiency of butene-1, sec-butylbenzene selectivity and production time are in table 1.Can obtain through rectifying the sec-butylbenzene that purity is more than 99.5% by cooling the synthetic product obtained.
Table 1
Embodiment 2: use the positive and negative butene-2 of mixing for sec-butylbenzene synthesis during carbon four raw material
20g is shaped at least loading in the tubular reactor of isothermal, upwards flowing, the fixed bed that internal diameter is 20mm containing rich aluminium beta-molecular sieve catalyzer (60% (massfraction) molecular sieve/40% (massfraction) binding agent etc.) of cylindric (diameter 1mm), gap, catalyst in reactor two ends quartz sand is filled.Benzene to be full of after reactor assembly progressively increasing temperature and pressure, reach 148 DEG C in temperature of reaction, when reaction pressure reaches 2.0MPa, by butene-2, (iso-butylene content is less than 0.5%, maleic-255.2%, anti-butene-2 44.6%) incision reactor, control weight hourly space velocity 8h
-1and benzene alkene mol ratio is 15, along with the change appropriate change reaction conditions of mixed butene-2 transformation efficiency such as can improve temperature of reaction etc. when C 4 olefin transformation efficiency obviously declines, such as when transformation efficiency often decline 0.5-1 percentage point time can on put forward temperature of reaction 1 DEG C.Analyze synthetic product composition by on-line chromatograph, the transformation efficiency of butene-2, sec-butylbenzene selectivity and production time are in table 2.Can obtain through rectifying the sec-butylbenzene that purity is more than 99.5% by cooling the synthetic product obtained.
Table 2
Embodiment 3: use mixed butene-1 and positive and negative butene-2 to be sec-butylbenzene synthesis during carbon four raw material
50g is shaped at least loading in the tubular reactor of isothermal, upwards flowing, the fixed bed that internal diameter is 20mm containing rich aluminium beta-molecular sieve catalyzer (60% (massfraction) molecular sieve/40% (massfraction) binding agent etc.) of cylindric (diameter 1mm), gap, catalyst in reactor two ends quartz sand is filled.Benzene to be full of after reactor assembly progressively increasing temperature and pressure, 147 DEG C are reached in temperature of reaction, when reaction pressure reaches 2.0MPa, by mixed butene, (iso-butylene content is less than 0.5%, butene-1 50.2%, maleic-2 25.2%, anti-butene-2 24.2%) incision reactor, control weight hourly space velocity 5h
-1and benzene alkene mol ratio is 8, along with the change appropriate change reaction conditions of mixed butene-1 and butene-2 total conversion rate such as can improve temperature of reaction etc. when C 4 olefin transformation efficiency obviously declines, such as when transformation efficiency often decline 0.5-1 percentage point time can on put forward temperature of reaction 1 DEG C.Analyze synthetic product composition by on-line chromatograph, the transformation efficiency of total butylene, sec-butylbenzene selectivity and production time are in table 3.Can obtain through rectifying the sec-butylbenzene that purity is more than 99.5% by cooling the synthetic product obtained.
Table 3
Embodiment 4: sec-butylbenzene when carbon four is carbon four raw material after using industrial mixed ether synthesizes
100g is shaped at least loading in the tubular reactor of isothermal, upwards flowing, the fixed bed that internal diameter is 30mm containing rich aluminium beta-molecular sieve catalyzer (66% (massfraction) molecular sieve/34% (massfraction) binding agent etc.) of cylindric (diameter 1mm), gap, catalyst in reactor two ends quartz sand is filled.Benzene to be full of after reactor assembly progressively increasing temperature and pressure, 146 DEG C are reached in temperature of reaction, when reaction pressure reaches 2.0MPa, by carbon after industrial mixed ether four, (iso-butylene content is less than 0.5%, butene-1 17.8%, maleic-2 12.9%, anti-butene-2 19.7%, normal butane 8.7%, Trimethylmethane 40.5%) incision reactor, control weight hourly space velocity 5h
-1and benzene alkene mol ratio is 15 carry out sec-butylbenzene building-up reactions, along with the change appropriate change reaction conditions of butene conversion total in carbon after ether four such as can improve temperature of reaction etc. when C 4 olefin transformation efficiency obviously declines, such as when transformation efficiency often decline 0.5-1 percentage point time can on put forward temperature of reaction 1 DEG C.Analyze synthetic product composition by on-line chromatograph, total butene conversion, sec-butylbenzene selectivity and production time are in table 4.Can obtain through rectifying the sec-butylbenzene that purity is more than 99.4% by cooling the synthetic product obtained.
Table 4
Embodiment 5: the mixed butene after using industrial ether after carbon four concentrate is sec-butylbenzene synthesis during raw material
100g is shaped at least loading in the tubular reactor of isothermal, upwards flowing, the fixed bed that internal diameter is 30mm containing rich aluminium beta-molecular sieve catalyzer (66% (massfraction) molecular sieve/34% (massfraction) binding agent etc.) of cylindric (diameter 1mm), gap, catalyst in reactor two ends quartz sand is filled.Benzene to be full of after reactor assembly progressively increasing temperature and pressure, 150 DEG C are reached in temperature of reaction, when reaction pressure reaches 2.0MPa, by the mixed butene after carbon four concentrate after industrial ether, (iso-butylene content is less than 0.5%, butene-1 35.3%, maleic-2 25.0%, anti-butene-2 39.5%) incision reactor, control weight hourly space velocity 3h
-1and benzene alkene mol ratio is 10 carry out sec-butylbenzene building-up reactions, along with the change appropriate change reaction conditions of total butene conversion such as can improve temperature of reaction etc. when C 4 olefin transformation efficiency obviously declines, such as when transformation efficiency often decline 0.5-1 percentage point time can on put forward temperature of reaction 1 DEG C.Analyze synthetic product composition by on-line chromatograph, total butene conversion, sec-butylbenzene selectivity and production time are in table 5.Can obtain through rectifying the sec-butylbenzene that purity is more than 99.4% by cooling the synthetic product obtained.
Table 5
Embodiment 6: the mixed butene after using industrial ether after carbon four concentrate is sec-butylbenzene synthesis during raw material
100g is shaped at least loading in the tubular reactor of isothermal, upwards flowing, the fixed bed that internal diameter is 30mm containing rich aluminium beta-molecular sieve catalyzer (40% (massfraction) rich aluminium beta-molecular sieve/26% (massfraction) MCM-22 molecular sieve/34% (massfraction) binding agent etc.) of cylindric (diameter 1mm), gap, catalyst in reactor two ends quartz sand is filled.Benzene to be full of after reactor assembly progressively increasing temperature and pressure, 150 DEG C are reached in temperature of reaction, when reaction pressure reaches 2.0MPa, by the mixed butene after carbon four concentrate after industrial ether, (iso-butylene content is less than 0.5%, butene-1 35.3%, maleic-2 25.0%, anti-butene-2 39.5%) incision reactor, control weight hourly space velocity 3h
-1and benzene alkene mol ratio is 10 carry out sec-butylbenzene building-up reactions, along with the change appropriate change reaction conditions of total butene conversion such as can improve temperature of reaction etc. when C 4 olefin transformation efficiency obviously declines, such as when transformation efficiency often decline 0.5-1 percentage point time can on put forward temperature of reaction 1 DEG C.Analyze synthetic product composition by on-line chromatograph, total butene conversion, sec-butylbenzene selectivity and production time are in table 6.Can obtain through rectifying the sec-butylbenzene that purity is more than 99.4% by cooling the synthetic product obtained.
Table 6
Claims (5)
1. the synthetic method of a sec-butylbenzene, it is characterized in that, using silica alumina ratio be less than 20 allitic beta-zeolite or allitic beta-zeolite mix as molecular sieve allcylation catalyst with one or more in MCM race zeolite, with the mixture of one or more in carbon four-wire type organic compound for raw material, and add benzene, at temperature of reaction 100-280 DEG C, reaction pressure 1.0-6.0MPa, feedstock weight hourly space velocity 0.1-20h
-1condition under react, react last synthetic product and obtain tert.-butylbenzene mass content not higher than 1% or not containing the sec-butylbenzene of tert.-butylbenzene by rectifying; The mixture of one or more in described carbon four-wire type organic compound is: the mixture of the iso-butylene containing 0-0.5wt% and the n-butene of 99.5-100wt%; Or containing one or more in the butane of 0.5-90wt%, with the iso-butylene of 0-0.5wt%, the mixture of 10-99wt% n-butene; The mol ratio 2-20 of benzene and alkene.
2. the method for claim 1, is characterized in that, one or more in described butane choose the mixture of normal butane and Trimethylmethane.
3. the method for claim 1, is characterized in that, described temperature of reaction is 120-270 DEG C, and reaction pressure is 1.5-4.5MPa, and feedstock weight hourly space velocity is 0.2-10h
-1.
4. the method as described in claim 1 or 3, is characterized in that, described temperature of reaction is 140-250 DEG C; Reaction pressure 1.8-3.5MPa; Feedstock weight hourly space velocity is 0.4-5h
-1.
5. the method for claim 1, is characterized in that, described MCM race zeolite comprises MCM-22, MCM-36, MCM-49 or MCM-56.
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|---|---|---|---|---|
| CN101006033A (en) * | 2004-08-13 | 2007-07-25 | 埃克森美孚化学专利公司 | Process for producing phenol and methyl ethyl ketone |
| CN101274764A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Preparation for nanometer allitic beta-zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101006033A (en) * | 2004-08-13 | 2007-07-25 | 埃克森美孚化学专利公司 | Process for producing phenol and methyl ethyl ketone |
| CN101274764A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Preparation for nanometer allitic beta-zeolite |
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