CN103848711A - High-yield production method of phenylcyclohexane - Google Patents
High-yield production method of phenylcyclohexane Download PDFInfo
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- CN103848711A CN103848711A CN201210501059.XA CN201210501059A CN103848711A CN 103848711 A CN103848711 A CN 103848711A CN 201210501059 A CN201210501059 A CN 201210501059A CN 103848711 A CN103848711 A CN 103848711A
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Abstract
The invention discloses a high-yield production method of phenylcyclohexane. The high-yield production method comprises following steps: (1) at the presence of a molecular sieve catalyst with a MWW structure, benzene and cyclohexene are subjected to contact reaction so as to obtain phenylcyclohexane; (2) benzene and poly phenylcyclohexane are subjected to contact reaction so as to obtain more phenylcyclohexane; and (3) obtained products are separated. The product obtained via step (1) and the product obtained via step (2) are separated so as to obtain at least benzene, methyl cyclopentyl benzene, phenylcyclohexane, and poly phenylcyclohexane; benzene obtained via step (3) is recycled to be used in step (1) and/or (2), and poly phenylcyclohexane of the step (2) comes from the step (3). The high-yield production method is high in phenylcyclohexane yield.
Description
Technical field
The invention relates to a kind of method of voluminous phenylcyclohexane, specifically about being reacted the method at interior voluminous phenylcyclohexane with tetrahydrobenzene by benzene a kind of comprising under acid molecular sieve catalyst effect.
Background technology
Phenylcyclohexane is a kind of important chemical intermediate, and it has high boiling point (240 DEG C) and low condensation point (7 DEG C), has special physicochemical property.Phenylcyclohexane can be prepared hydrogen peroxide phenylcyclohexane through peroxidation, and hydrogen peroxide phenylcyclohexane can be prepared phenol and pimelinketone through decomposing.Phenol is a kind of industrial chemicals being in great demand, and pimelinketone is the intermediate of producing hexanolactam and nylon.Phenylcyclohexane also can be used for the additive of electrolyte of lithium-ion secondary battery, can improve the cyclicity of lithium ion battery, has anti-overcharge performance, improves the security (CN 1632983A, CN 1430306, CN 1475038A etc.) of battery.In addition, phenylcyclohexane also can be used for synthetic liquid crystal material, and has the features (CN 1318617A) such as the low and physical properties of high chemical stability, photochemical stability, viscosity is good.
At present, the synthetic process of phenylcyclohexane mainly contain the selective hydrogenation method of hydroalkylation method, biphenyl of benzene and benzene with as reacting of tetrahydrobenzene, hexalin, cyclohexane halide etc. etc.
US Patent No. 3760018 and US 3760019 have reported a kind of employing loaded catalyst (M/SiO
2-Al
2o
3m is rhenium metal, cobalt and nickel etc.) catalytic benzene hydrogenation alkylation prepares the method for phenylcyclohexane, the method is actually the two-step reaction of benzene hydrogenation synthesizing cyclohexene and benzene and tetrahydrobenzene alkylation synthesizing cyclohexyl benzene is united two into one, and the selectivity of phenylcyclohexane is less than 60%; US Patent No. 4268699 provides a kind of and has used improving one's methods of ruthenium and nickel bimetal supported catalyst, though the selectivity of the method phenylcyclohexane be improved, but still undesirable (selectivity of phenylcyclohexane is lower than 80.6%); US Patent No. 20100179351, US 20100197971 and US 7910779 disclose a kind of metal load type catalyst, and (wherein metal is selected from the one in palladium, ruthenium, nickel, zinc, cobalt and tin, carrier is the arbitrary combination of MCM-22 molecular sieve analog), catalytic benzene hydrogenation reaction, the transformation efficiency of benzene increases, but still lower than 60%, the selectivity of phenylcyclohexane is lower than 88%.
Applied Catalysis A:General 143 (1996) 271-281 have reported that benzene and tetrahydrobenzene are at SiO
2scion grafting A1C1
3under catalyst action, carry out liquid reactive method, the transformation efficiency of the method tetrahydrobenzene is 97.9%, and the selectivity of phenylcyclohexane reaches 97%, but the method exists catalyst contamination environment, product to reclaim and purifies problem complicated, that reusing is poor.
CN 1982263A and CN 1982264A have reported that respectively benzene reacts with hexalin or cyclohexane halide the method for preparing phenylcyclohexane, but the common defects of their existence is that hexalin used or cyclohexane halide are expensive and corrodibility used catalyst is larger.
CN 101219922A discloses the method for preparing phenylcyclohexane under the condition that benzene and tetrahydrobenzene are catalyzer at glyoxaline ion liquid and metal halide or triethylamine hydrochloride class ionic liquid and metal halide.CN101811924A has reported that benzene and tetrahydrobenzene are the method that catalyst is prepared phenylcyclohexane at pyridines ionic liquid, but the making processes of ionic liquid is very complicated, cause its price generally more expensive, and ionic liquid is responsive especially to water, meet water rear section and be hydrolyzed easy inactivation, use and repeatedly can lose efficacy afterwards, affected and recycled efficiency, these are all the very large problems that its development of restriction faces, and are unfavorable for industrial application.
WO001244A has reported and has utilized solid acid Y zeolite catalysis benzene to react the method for preparing phenylcyclohexane with tetrahydrobenzene, reacts at 250cm
3berty type reactor in carry out, the transformation efficiency of tetrahydrobenzene is 99.6%, the selectivity of phenylcyclohexane only has 87.7%.
Summary of the invention
The object of this invention is to provide a kind of method of the voluminous phenylcyclohexane that is different from prior art, the method can increase substantially the yield of object product phenylcyclohexane.
A kind of method of voluminous phenylcyclohexane, be included in the process I that the benzene of the catalyzer that contains MWW structure molecular screen under existing and the contact reacts of tetrahydrobenzene obtain phenylcyclohexane, the contact reacts of benzene and many phenylcyclohexanes further obtains the process II of phenylcyclohexane, and sepn process; The product of said process I and said process II at least obtains benzene, methylcyclopentyl benzene, phenylcyclohexane and many phenylcyclohexanes through said sepn process, wherein, the benzene that said sepn process obtains is through cyclically utilizing in process I and/or process II, and in said process II, said many phenylcyclohexanes are from said sepn process.
The present invention also provides the device of the method for implementing above-mentioned voluminous phenylcyclohexane, comprise process I conversion unit, process II conversion unit and for separating of the equipment of process, the conversion unit of said process I comprises benzene opening for feed and tetrahydrobenzene opening for feed, the said equipment for separating of process at least comprises the separable equipment that obtains benzene, the separable equipment that obtains methylcyclopentyl benzene, separable equipment and the separable equipment that obtains many phenylcyclohexanes that obtains phenylcyclohexane, the said separable conversion unit that obtains the equipment of benzene and the conversion unit of said process I and/or said process II is connected and is made benzene cyclically utilizing by pipeline, the conversion unit of said process II comprises many phenylcyclohexanes opening for feed and benzene opening for feed, saidly separablely obtain the equipment of many phenylcyclohexanes and the conversion unit of said process II is connected by pipeline, the conversion unit of said process I and the conversion unit of said process II are connected to separate with the said separable equipment that obtains benzene respectively and obtain benzene.
Method provided by the invention, using MWW molecular sieve as benzene and the active ingredient of the catalyzer of tetrahydrobenzene reaction process I, the selectivity of object product phenylcyclohexane is good, its by product is mainly many phenylcyclohexanes and methylcyclopentyl benzene, in many phenylcyclohexanes wherein, be mainly dicyclohexyl benzene, substantially do not produce thricyclohexyl benzene, and methylcyclopentyl benzene can be used as the high-octane number component of gasoline component; The inventive method also comprises the reaction of sepn process and process II, in process II reaction, many phenylcyclohexanes is further converted to phenylcyclohexane.Method provided by the invention, the yield of phenylcyclohexane is more than 92%.
Brief description of the drawings
The simple process schematic diagram that accompanying drawing 1 is method provided by the invention.
The idiographic flow schematic diagram that accompanying drawing 2 is method provided by the invention, wherein process I carries out in single reactor.
The idiographic flow schematic diagram that accompanying drawing 3 is method provided by the invention, wherein process I carries out in the reactor by multiple series connection.
The concrete block diagram that accompanying drawing 4 is method provided by the invention, wherein process I carries out in the reactor by multiple series connection, and each reactor is made up of two-stage catalytic agent bed.
Embodiment
The method of voluminous phenylcyclohexane provided by the invention, be included in the process I that the benzene of the catalyzer that contains MWW structure molecular screen under existing and the contact reacts of tetrahydrobenzene obtain phenylcyclohexane, the contact reacts of benzene and many phenylcyclohexanes further obtains the process II of phenylcyclohexane, and sepn process; The product of said process I and said process II at least obtains benzene, methylcyclopentyl benzene, phenylcyclohexane and many phenylcyclohexanes through said sepn process, wherein, the benzene cyclically utilizing that said sepn process obtains is in process I and/or process II, and in said process II, said many phenylcyclohexanes are from said sepn process.
In the said process I of method provided by the invention, total mol ratio of benzene and tetrahydrobenzene is preferably (2-15): 1, and more preferably (4-12): 1.Described process I can carry out in single reactor, can be also to carry out in the reactor of two or more series connection.In the time that process I implements in single reactor, benzene feedstock and tetrahydrobenzene enter reactor and carry out contact reacts; In the time that process I implements in multiple tandem reactors, benzene feedstock enters reactor also successively by the each reactor being in series from the entrance of first reactor, tetrahydrobenzene is divided into multiply and enters respectively successively in each reactor, and in the inlet amount of the opening for feed gate ring hexene of each reactor, making the mol ratio of benzene and tetrahydrobenzene in each reactor is (10-25): 1.
In method provided by the invention, in process I, temperature of reaction is preferably 120-280 DEG C, more preferably 150-250 DEG C, 180-220 DEG C most preferably.In process I, reaction pressure is preferably 1.0-5.0MPa, 2.0-4.0MPa more preferably.The liquid hourly space velocity of benzene and tetrahydrobenzene is preferably 0.5-8.0h
-1, more preferably liquid hourly space velocity is 1.0-6.0h
-1.
In method provided by the invention, when process I carries out in multiple reactors in series, because process I reaction is for strong exothermal reaction, between reactor, to there be interchanger or water cooler, so that the temperature of material is adjusted to the temperature that next Reactor inlet needs.
In method provided by the invention, the reaction of described process I, it can be upstriker or downstriker that its reacting fluid flows to, wherein preferred upstriker direction of flow, the reaction mass catalyzer of flowing through from bottom to top reacts.The reaction of process I can select isothermal fixed bed as adopted shell and tube reactor or stirring reactor, also can select insulation fix bed reactor, preferably insulation fix bed reactor.Adopting under the condition of adiabatic reactor, in each reactor, can there is a beds, also can there be two beds.In the time having two beds in a reactor, two beds can be same catalyzer, can be also different catalyzer.
In method provided by the invention, the reaction of said process I is to carry out under the catalyst that contains MWW structure molecular screen.The catalyzer of the said MWW of containing structure molecular screen is that the catalytic active component of catalyzer is the molecular sieve of MWW structure.Said MWW molecular sieve is the molecular sieve described in " ATLAS OF ZEOLITE FRAMEWORKTYPES; Sixth Revised Edition; 2007; P234-235 ", according to the difference of synthetic method, the molecular sieve of this structure has MCM-22, MCM-49, MCM-56 etc. to have the molecular sieve type of different x-ray diffracting spectrum.The present invention preferably adopts MCM-22, the MCM-49 molecular sieve active ingredient as the catalyzer of process I reaction.In Chinese patent CN20041000957.2, a kind of MCM-22 type molecular sieve is disclosed, in document " tri-kinds of Zeolite synthesis of MCM-22, MCM-49 and MCM-56 " (Industrial Catalysis, 2006, the 14th volume, the 54th page) in reported the synthetic method of MCM-22, MCM-49 and tri-kinds of molecular sieves of MCM-56, according to the method in above-mentioned patent and document, the MWW structure molecular screen preparing is the active ingredient of the further preferred catalyzer of process I of the present invention.
In method provided by the invention, in the catalyzer of the said MWW of containing structure molecular screen, can also contain oxide carrier.Said oxide carrier is preferably from Al
2o
3or SiO
2in one or both mixture.In said catalyzer, the content of molecular sieve is 10-95%, and the content of carrier is 5-90%; The content of preferred molecular sieve is 30-80%, and vector contg is 20-70%; More preferably molecular sieve content is 50-70%, and vector contg is 30-50%.
In method provided by the invention, after benzene reacts in the reactor of process I with tetrahydrobenzene, reaction product separates, and obtains benzene, methylcyclopentyl benzene, phenylcyclohexane, many phenylcyclohexanes etc.Benzene wherein recycles after pressurization, and phenylcyclohexane is object product.The reactor that many phenylcyclohexanes enter (comprise dicyclohexyl benzene and thricyclohexyl benzene, be mainly dicyclohexyl benzene) process II after mixing with benzene reacts, and the product of reaction also enters disengaging zone and separates.In method provided by the invention, for the purity of the benzene recycling, be preferably more than 80%, non-aromatics content is below 20%; More preferably more than 90%, non-aromatics content is below 10%; Most preferably more than 95%, non-aromatics content is below 5%.Require as 10-300ppm preferably 20-200ppm, more preferably 30-100ppm for water-content in benzene.
In the reaction conditions of the said process II of method provided by the invention, the temperature of reaction of the transalkylation reaction of benzene and many phenylcyclohexanes is preferably 120-250 DEG C, more preferably 150-240 DEG C; Reaction pressure is preferably 1.0-5.0MPa, more preferably 2.0-3.0MPa; The mol ratio of benzene and many phenylcyclohexanes is preferably 1-20, more preferably 5-15; Liquid hourly space velocity is preferably 0.5-5.0h
-1, 1.0-4.0h more preferably
-1.
In method provided by the invention, the direction of flow of described process II reaction can be upstriker or downstriker, wherein preferred upstriker direction of flow, and the reaction mass catalyzer of flowing through from bottom to top reacts.
In method provided by the invention, the catalyzer of process II reaction used is the catalyzer that contains Y zeolite, molecular sieve is wherein preferably the molecular sieve that Chinese patent CN00107414.8 reports, catalyzer is the described catalyzer of Chinese patent CN00107413.X.The SiO of said Y zeolite in the said process II of the present invention
2/ Al
2o
3for 6-10, preferred 7-9.In method provided by the invention, in the said catalyzer that contains Y zeolite, can also contain oxide carrier.Said oxide carrier is preferably from Al
2o
3or SiO
2in one or both mixture, more preferably aluminum oxide is as the carrier of catalyzer.In said catalyzer, the content of molecular sieve is 10-95%, and the content of carrier is 5-90%; The content of preferred molecular sieve is 30-80%, and vector contg is 20-70%; More preferably molecular sieve content is 50-70%, and vector contg is 30-50%.
The present invention also provides the device of the method for implementing above-mentioned voluminous phenylcyclohexane, comprise process I conversion unit, process II conversion unit and for separating of the equipment of process, the conversion unit of said process I comprises benzene opening for feed and tetrahydrobenzene opening for feed, the said equipment for separating of process at least comprises the separable equipment that obtains benzene, the separable equipment that obtains methylcyclopentyl benzene, separable equipment and the separable equipment that obtains many phenylcyclohexanes that obtains phenylcyclohexane, the said separable conversion unit that obtains the equipment of benzene and the conversion unit of said process I and/or said process II is connected and is made benzene cyclically utilizing by pipeline, the conversion unit of said process II comprises many phenylcyclohexanes opening for feed and benzene opening for feed, saidly separablely obtain the equipment of many phenylcyclohexanes and the conversion unit of said process II is connected by pipeline, the conversion unit of said process I and the conversion unit of said process II are connected to separate with the said separable equipment that obtains benzene respectively and obtain benzene.
Device provided by the invention, wherein, the conversion unit of said process I is made up of multiple independent reactors in series, have benzene opening for feed, and each independent reactor all has tetrahydrobenzene opening for feed at first reactor.
Device provided by the invention, wherein, the said separable equipment that obtains benzene, separablely obtain the equipment of methylcyclopentyl benzene, separable equipment and the separable equipment that obtains many phenylcyclohexanes that obtains phenylcyclohexane also can be expressed as benzene tower, methylcyclopentyl benzene tower, phenylcyclohexane tower and many phenylcyclohexanes tower.In the equipment for separating of process, except above-mentioned said four knockout towers, can also comprise benzene tower benzene treating column afterwards, benzene treating column is in order to remove water and the non-aromatics in benzene, and the conversion unit of benzene treating column and process I and/or process II is connected.In the equipment for separating of process, can also comprise that rectifying tower is to remove the impurity composition of boiling point lower than phenylcyclohexane.
Below by embodiment, method and apparatus of the present invention is further described, illustrate the effect of the reaction process II of reaction process I, benzene and many phenylcyclohexanes of benzene and tetrahydrobenzene in conjunction with schematic flow sheet, but embodiment does not limit the scope of the invention.
The simple process schematic diagram (for graphic simplicity, interchanger, return tank and corresponding pipeline etc. all do not mark in the drawings) of the method that accompanying drawing 1 is voluminous phenylcyclohexane provided by the invention
The simple process schematic diagram of accompanying drawing 1 is described below: the technical process of the method for voluminous phenylcyclohexane comprises reaction zone and disengaging zone two portions, and reaction zone comprises process I reaction zone and process II reaction zone.From after the fresh benzene of pipeline 2 and the mixing of the recovery recycle benzene of pipeline 3, react in process I reaction zone with the tetrahydrobenzene from pipeline 1 respectively, reacted effluent enters disengaging zone through pipeline 4, many phenylcyclohexanes (representing with dicyclohexyl benzene) from pipeline 9 enter reaction zone, reacted effluent enters disengaging zone through pipeline 4, isolate benzene, methylcyclopentyl benzene, phenylcyclohexane, many phenylcyclohexanes, water and non-aromatics impurity, wherein isolated benzene mixes the benzene raw materials as process I and/or process II with fresh benzene through pipeline 3, water and non-aromatics impurity are derived through pipeline 5 and 6 respectively, methylcyclopentyl benzene is derived through pipeline 7, phenylcyclohexane product is derived through pipeline 8, heavies derives through pipeline 9, many phenylcyclohexanes (being mainly dicyclohexyl benzene) are through pipeline 10 and from pipeline 2, after 3 benzene mixes, enter reaction zone and carry out the reaction of process II, reacted effluent enters disengaging zone.
The idiographic flow schematic diagram of a kind of mode of the method that accompanying drawing 2 is voluminous phenylcyclohexane provided by the invention, wherein alkylated reaction is to carry out in single hop reactor.
The idiographic flow schematic diagram of accompanying drawing 2 is described below: respectively from after the fresh benzene of pipeline 8 and the mixing of the recovery benzene of pipeline 21, after pipeline 10 mixes with from the tetrahydrobenzene of pipeline 9, enter in reactor 1 and react, the effluent of reactor 1 enters benzene tower 3 Separation of Benzene through pipeline 11, the isolated part benzene of tower top flows into benzene treating column 4, benzene treating column 4 tower top H through pipeline 13,14
2o and non-aromatics derive through pipeline 17,18 respectively, at the bottom of benzene treating column 4 towers, benzene is divided into two portions through pipeline 20 after pipeline 19 mixes with from the benzene of pipeline 16, a part is through pipeline 21 and the benzene raw materials mixing from the fresh benzene of pipeline 8 as process I reaction, another part enters the reactor 2 of process II through pipeline 22, as the benzene raw materials of process II.The bottom stream of benzene tower 3 flows into methylcyclopentyl benzene tower 5 through pipeline 15, methylcyclopentyl benzene tower 5 tower top effluent methylcyclopentyl benzene are derived through pipeline 23, the bottomsstream flows into phenylcyclohexane tower 6 through pipeline 24, product phenylcyclohexane is derived by tower top through pipeline 25, bottom stream enters many phenylcyclohexanes tower 7 through pipeline 26, the many phenylcyclohexanes of tower top effluent (being mainly dicyclohexyl benzene) through pipeline 27 be mixed into the reactor 2 of process II from the benzene of pipeline 22 in react, at the bottom of tower, heavies derives through pipeline 28.The effluent of process II reactor 2 enters in benzene tower 3 and separates through pipeline 12.
The idiographic flow schematic diagram of a kind of mode of the method that accompanying drawing 3 is voluminous phenylcyclohexane provided by the invention, wherein process I reaction is to carry out in the reactor by multiple series connection.
The idiographic flow schematic diagram of accompanying drawing 3 is described below: reclaim after benzene mixing from fresh benzene and the pipeline 27 of pipeline 10 respectively, through pipeline 13 and from pipeline 11, 12 tetrahydrobenzene is mixed in reactor 1 and reacts, the outlet product of this reactor with from pipeline 14, 15 tetrahydrobenzene is mixed in reactor 2 and reacts, its effluent with from pipeline 14, 16 tetrahydrobenzene is mixed in reactor 3 and proceeds to react, its product enters benzene tower 5 Separation of Benzene through pipeline 17, the benzene that tower top is separated is through pipeline 19, 20 flow into benzene treating column 6, benzene treating column 6 tower top H
2o and non-aromatics derive through pipeline 22,23 respectively, at the bottom of benzene treating column 6 towers, benzene is divided into two portions through pipeline 26 after pipeline 25 mixes with from the benzene of pipeline 24, a part through pipeline 27 with the reactor 1 that is mixed into process I from the fresh benzene of pipeline 10 as benzene raw materials, another part enters in the reactor 4 of process II as benzene raw materials through pipeline 28.The bottom stream of benzene tower 5 flows into methylcyclopentyl benzene tower 7 through pipeline 21, methylcyclopentyl benzene tower 7 tower top effluent methylcyclopentyl benzene are derived through pipeline 29, the bottomsstream flows into phenylcyclohexane tower 8 through pipeline 30, product phenylcyclohexane is derived by tower top through pipeline 31, bottom stream enters many phenylcyclohexanes tower 9 through pipeline 32, the many phenylcyclohexanes of tower top effluent (being mainly dicyclohexyl benzene) through pipeline 33 be mixed into the reactor 4 of process II from the benzene of pipeline 28 in react, at the bottom of tower, heavies derives through pipeline 34.The top effluent of reactor 4 enters in benzene tower 5 and separates through pipeline 18.
The idiographic flow schematic diagram of a kind of mode of the method that accompanying drawing 4 is voluminous phenylcyclohexane provided by the invention, wherein process I carries out in the reactor by multiple series connection, and each reactor is made up of two-stage catalytic agent bed.
The idiographic flow schematic diagram of accompanying drawing 4 is described below: respectively from after the fresh benzene of pipeline 9 and the mixing of the recovery benzene of pipeline 27, with from pipeline 11, after mixing, 12 tetrahydrobenzene reacts on pipeline 10 enters the first paragraph beds of reactor 1, the effluent of first paragraph bed with successively from 13, after 14 tetrahydrobenzene mixes, the second segment bed that enters reactor 1 reacts, the effluent of second segment bed with successively from pipeline 13, after 15 tetrahydrobenzene mixes, enter the first paragraph bed reaction of reactor 2, the first paragraph effluent of reactor 2 with successively from pipeline 13, 16 tetrahydrobenzene enters the second segment bed reaction of reactor 2 after mixing, tower top effluent enters Separation of Benzene in benzene tower 4 through pipeline 17, the benzene that benzene tower 4 tower tops are separated is through pipeline 19, 20 enter benzene treating column 5, benzene treating column 5 tower top effluent H
2o and non-aromatics derive through pipeline 22,23 respectively, the benzene that benzene treating column 5 tower bottom flows go out is divided into two portions through pipeline 26 after pipeline 25 mixes with from the benzene of pipeline 24, a part enters the benzene raw materials as process I in reactor 1 after pipeline 27 mixes with from the fresh benzene of pipeline 9, and another part enters the benzene raw materials as process II in reactor 3 through pipeline 28.The bottomsstream of benzene tower 4 enters methylcyclopentyl benzene tower 6 through pipeline 21, methylcyclopentyl benzene tower 6 tower top effluent methylcyclopentyl benzene are derived through pipeline 29, bottom stream enters in phenylcyclohexane tower 7 through pipeline 30, product phenylcyclohexane is derived from tower top through pipeline 31, bottom stream flows in many phenylcyclohexanes tower 8 through pipeline 32, the many phenylcyclohexanes of tower top effluent (being mainly dicyclohexyl benzene) enter the reaction of carrying out process II in reactor 3 after pipeline 33 mixes with from the benzene of pipeline 28, and at the bottom of tower, heavies derives through pipeline 34.The top effluent of reactor 3 flows into benzene tower 4 through pipeline 18 and separates.
The catalyzer of process I used reaction in embodiment, taking MCM-22 molecular sieve or MCM-49 molecular sieve (Hunan Jian Chang company), as active ingredient, aluminum oxide is binding agent, in catalyzer, the content of contained molecular sieve is 70 % by weight.The catalyzer of process II reaction used in embodiment, molecular sieve is wherein the Y zeolite that Shanghai Xin Nian company produces, SiO
2/ Al
2o
3be 7.5.Molecular sieve is prepared into catalyzer taking aluminum oxide as binding agent, and in catalyzer, the content of molecular sieve is 70 % by weight.
The method of calculation of various data in embodiment:
Reaction process I:
Phenylcyclohexane selectivity=phenylcyclohexane/(methylcyclopentane+hexanaphthene+methylcyclopentyl benzene+cyclopentyl-methyl benzene+phenylcyclohexane+dicyclohexyl benzene+heavies)
Cyclohexyl selectivity=(phenylcyclohexane+dicyclohexyl benzene)/(methylcyclopentane+hexanaphthene+methylcyclopentyl benzene+cyclopentyl-methyl benzene+phenylcyclohexane+dicyclohexyl benzene+heavies)
Reaction process II:
Dicyclohexyl benzene transformation efficiency=(import dicyclohexyl benzene concentration-outlet dicyclohexyl benzene concentration)/import dicyclohexyl benzene concentration
Phenylcyclohexane selectivity=(discharge ring hexyl benzene concentration-import phenylcyclohexane concentration)/[(import dicyclohexyl benzene concentration-outlet dicyclohexyl benzene concentration)+(import benzene concentration-outlet benzene concentration)]
Benzene and tetrahydrobenzene consumption in phenylcyclohexane output/unit time phenylcyclohexane yield=unit time
Embodiment 1
In the fixed-bed reactor of the process I shown in Fig. 2, pack the catalyzer that contains MCM-22 molecular sieve into, reactor is filled with porcelain ball respectively up and down.First in reactor, enter continuously benzene, be warming up to 190 DEG C, pressure-controlling, at 3.0Mpa, after stable, uses ram pump at liquid hourly space velocity 2h
-1under condition, in reactor, add raw material successive reaction by benzene and tetrahydrobenzene mol ratio 12:1.Get the Shimadzu 2010 gas chromatographic analysis product compositions of being furnished with 50m × 0.25mm capillary column and fid detector for sample of reactor top effluent, the transformation efficiency of tetrahydrobenzene reaches 100%, the selectivity of phenylcyclohexane can reach 92.0%, cyclohexyl selectivity is 95.4%, methylcyclopentyl benzene selective 4.3%.The product of reaction enters disengaging zone and isolates successively benzene, methylcyclopentyl benzene, phenylcyclohexane, many phenylcyclohexanes and heavies.
In the fixed-bed reactor of process II, pack the catalyzer that contains Y molecular sieve into, reactor is filled with porcelain ball respectively up and down, benzene is separated with phenylcyclohexane tower many phenylcyclohexanes of obtaining in molar ratio 15:1 after mixing, enter reactor.First in reactor, enter continuously benzene, be warming up to 160 DEG C, pressure-controlling, at 3.0Mpa, after stable, uses ram pump at liquid hourly space velocity 2h
-1under condition, in reactor, add raw material successive reaction.Get the sample of reactor top effluent, with the Shimadzu 2010 gas chromatographic analysis product compositions of being furnished with 50m × 0.25mm capillary column and fid detector, the transformation efficiency of dicyclohexyl benzene reaches 65.8%, and the selectivity of phenylcyclohexane can reach 98.5%.
By the phenylcyclohexane amount of gauge rings hexyl benzene tower, the yield that obtains phenylcyclohexane is 95.2%.
Embodiment 2
In the fixed-bed reactor of three series connection shown in Fig. 3, pack the catalyzer that contains MCM-49 molecular sieve into, reactor is filled with porcelain ball respectively up and down.First in reactor, enter continuously benzene, be warming up to 210 DEG C, pressure-controlling, at 3.0Mpa, after stable, uses ram pump at liquid hourly space velocity 2h
-1under condition, in the first reactor, add raw material successive reaction by benzene/tetrahydrobenzene mol ratio 18:1, the first reactor head effluent enters the second reactor (benzene/tetrahydrobenzene mol ratio is also 18:1) and carries out alkylated reaction after mixing with the second crural ring hexene.The second reactor head effluent enters trialkyl reactor (benzene/tetrahydrobenzene mol ratio is also 18:1) and reacts after mixing with the 3rd crural ring hexene.Take out sample from the 3rd reactor head effluent, with the Shimadzu 2010 gas chromatographic analysis product compositions of being furnished with 50m × 0.25mm capillary column and fid detector, the transformation efficiency of tetrahydrobenzene reaches 100%, the selectivity of phenylcyclohexane can reach 85.0%, cyclohexyl selectivity is 93.0%, methylcyclopentyl benzene selective 6.5%.The product of alkylated reaction enters disengaging zone and isolates successively benzene, methylcyclopentyl benzene, phenylcyclohexane, many phenylcyclohexanes and heavies.
In the fixed-bed reactor of process II, pack the catalyzer that contains Y molecular sieve into, reactor is filled with porcelain ball respectively up and down, benzene is separated with phenylcyclohexane tower many phenylcyclohexanes of obtaining in molar ratio 10:1 after mixing, enter reactor.First in reactor, enter continuously benzene, be warming up to 168 DEG C, pressure-controlling, at 3.0Mpa, after stable, uses ram pump in liquid hourly space velocity 2
h-1under condition, in reactor, add raw material successive reaction.Take out sample from reactor head effluent, with the Shimadzu 2010 gas chromatographic analysis product compositions of being furnished with 50m × 0.25mm capillary column and fid detector, the transformation efficiency of dicyclohexyl benzene reaches 68.0%, and the selectivity of phenylcyclohexane can reach 98.0%.The reaction product of process II reactor enters disengaging zone and separates.
By the phenylcyclohexane amount of gauge rings hexyl benzene tower, the yield that obtains phenylcyclohexane is 92.5%.
Claims (21)
1. the method for a voluminous phenylcyclohexane, be included in the process I that the benzene of the catalyzer that contains MWW structure molecular screen under existing and the contact reacts of tetrahydrobenzene obtain phenylcyclohexane, the contact reacts of benzene and many phenylcyclohexanes further obtains the process II of phenylcyclohexane, and sepn process; The product of said process I and said process II at least obtains benzene, methylcyclopentyl benzene, phenylcyclohexane and many phenylcyclohexanes through said sepn process, wherein, the benzene cyclically utilizing that said sepn process obtains is in process I and/or process II, and in said process II, said many phenylcyclohexanes are from said sepn process.
2. basis the process of claim 1 wherein, one or more in MCM-22, MCM-49 and MCM-56 molecular sieve of the molecular screening of said MWW structure.
3. according to the method for claim 1 or 2, wherein, also contain oxide carrier in said catalyzer, its content is 5-90 % by weight.
4. according to the method for claim 3, wherein, said oxide carrier is selected from Al
2o
3or SiO
2in one or both mixture.
5. according to the process of claim 1 wherein that said process I, the mol ratio of benzene and tetrahydrobenzene are (2-15): 1.
6. according to the method for claim 5, wherein the mol ratio of said benzene and tetrahydrobenzene is (4-12): 1.
7. according to the process of claim 1 wherein, the temperature of reaction of said process I is that 120-280 DEG C, reaction pressure are 1.0-5.0MPa.
8. according to the method for claim 7, wherein, the temperature of reaction of said benzene and tetrahydrobenzene is 150-250 DEG C.
9. method according to Claim 8, wherein, the temperature of reaction of said benzene and tetrahydrobenzene is 180-220 DEG C.
10. according to the method for claim 7, wherein, the reaction pressure of said benzene and tetrahydrobenzene is 2.0-4.0MPa.
11. according to the process of claim 1 wherein that said process I, the liquid hourly space velocity of benzene and tetrahydrobenzene are 0.5-8.0h
-1.
12. according to the method for claim 11, and wherein, said liquid hourly space velocity is 1.0-6.0h
-1.
13. according to the process of claim 1 wherein, the reaction of said process I is carried out in fixed-bed reactor.
14. according to the process of claim 1 wherein, said process I carries out in the fixed-bed reactor of multiple series connection, and said benzene enters from the entrance of first reactor, and said tetrahydrobenzene is divided into multiply and enters respectively successively each reactor.
15. according to the method for claim 14, and the benzene in each reactor and the mol ratio of tetrahydrobenzene are (10-25): 1.
16. according to the process of claim 1 wherein, said process II, and temperature of reaction is that 120-250 DEG C, reaction pressure are 1.0-5.0MPa, and the mol ratio of benzene and many phenylcyclohexanes is 1-20, and liquid hourly space velocity is 0.5-5.0h
-1.
17. according to the method for claim 16, and wherein, said temperature of reaction is that 150-240 DEG C, reaction pressure are 2.0-3.0MPa, and the mol ratio of benzene and many phenylcyclohexanes is 5-15, and liquid hourly space velocity is 1.0-4.0h
-1.
18. for implementing the claims the device of method described in 1-17 any one, comprise process I conversion unit, process II conversion unit and for separating of the equipment of process; The conversion unit of said process I comprises benzene opening for feed and tetrahydrobenzene opening for feed; The said equipment for separating of process at least comprises the separable equipment of benzene, the separable equipment of methylcyclopentyl benzene, separable equipment and the separable equipment that obtains many phenylcyclohexanes that obtains phenylcyclohexane of obtaining of obtaining; The said separable conversion unit that obtains the equipment of benzene and the conversion unit of said process I and/or said process II is connected and is made benzene cyclically utilizing by pipeline; The conversion unit of said process II comprises many phenylcyclohexanes opening for feed and benzene opening for feed, saidly separablely obtain the equipment of many phenylcyclohexanes and the conversion unit of said process II is connected by pipeline, the conversion unit of said process I and the conversion unit of said process II are connected to separate with the said separable equipment that obtains benzene respectively and obtain benzene.
19. according to the device of claim 18, and wherein, the conversion unit of said process I is made up of multiple independent reactors in series, have benzene opening for feed, and each independent reactor all has tetrahydrobenzene opening for feed at first reactor.
20. according to the device of claim 18, wherein, after the said separable equipment that obtains benzene, also have benzene treating column to remove water and the non-aromatics in benzene, and the conversion unit of benzene treating column and process I and/or process II is connected.
21. according to the device of claim 18, wherein, in the said equipment for separating of process, also has rectifying tower to remove the impurity composition of boiling point lower than phenylcyclohexane.
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|---|---|---|---|---|
| CN105233861A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Cyclohexyl benzene catalyst and synthetic method thereof |
| WO2022102600A1 (en) * | 2020-11-13 | 2022-05-19 | Ｅｎｅｏｓ株式会社 | Cyclohexylbenzene production method and cyclohexylbenzene composition using same |
| CN115368935A (en) * | 2022-08-25 | 2022-11-22 | 河南本色化工科技有限责任公司 | Preparation method of polycyclic aromatic hydrocarbon compound |
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| WO2012082232A1 (en) * | 2010-12-17 | 2012-06-21 | Exxonmobil Chemical Patenst Inc. | Process for producing cycloalkylaromatic compounds |
| WO2012087433A1 (en) * | 2010-12-21 | 2012-06-28 | Exxonmobil Chemical Patents Inc. | Process for producing a monocycloalkyl-substituted aromatic compound |
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| WO2012082232A1 (en) * | 2010-12-17 | 2012-06-21 | Exxonmobil Chemical Patenst Inc. | Process for producing cycloalkylaromatic compounds |
| WO2012087433A1 (en) * | 2010-12-21 | 2012-06-28 | Exxonmobil Chemical Patents Inc. | Process for producing a monocycloalkyl-substituted aromatic compound |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233861A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Cyclohexyl benzene catalyst and synthetic method thereof |
| CN105233861B (en) * | 2014-07-11 | 2019-07-09 | 中国石油化工股份有限公司 | The synthetic method of cyclohexyl benzene catalyst and cyclohexyl benzene |
| WO2022102600A1 (en) * | 2020-11-13 | 2022-05-19 | Ｅｎｅｏｓ株式会社 | Cyclohexylbenzene production method and cyclohexylbenzene composition using same |
| CN115368935A (en) * | 2022-08-25 | 2022-11-22 | 河南本色化工科技有限责任公司 | Preparation method of polycyclic aromatic hydrocarbon compound |
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