CN108530247A - The method that cyclohexene and benzene alkylation prepare cyclohexyl benzene - Google Patents
The method that cyclohexene and benzene alkylation prepare cyclohexyl benzene Download PDFInfo
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- CN108530247A CN108530247A CN201710122151.8A CN201710122151A CN108530247A CN 108530247 A CN108530247 A CN 108530247A CN 201710122151 A CN201710122151 A CN 201710122151A CN 108530247 A CN108530247 A CN 108530247A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of methods that cyclohexene and benzene alkylation prepare cyclohexyl benzene, are included under the conditions of effecting reaction, make the step of benzene and cyclohexene are with molecular sieve catalyst contact synthesizing cyclohexyl benzene；It is characterized in that controlling the concentration of oxygenatedchemicals in cyclohexene, the concentration of oxygenatedchemicals in cyclohexene is made to be less than 1 weight %.This method can be used in the industrial production of benzene and cyclohexene production cyclohexyl benzene.
Description
Technical field
The present invention relates to a kind of methods that cyclohexene and benzene alkylation prepare cyclohexyl benzene.
Background technology
Cyclohexyl benzene is a kind of important fine-chemical intermediate, and the condensation point with higher boiling and nearly room temperature, there have to be special
Physical and chemical performance.Cyclohexyl benzene has anti-overcharge performance, can improve electricity as the additive in lithium-ion battery electrolytes
The security performance in pond, therefore be widely applied in battery industry.In addition, cyclohexyl benzene can also be used for synthesis liquid crystal material
Material.
The peroxidization of cyclohexyl benzene can prepare phenol and cyclohexanone.Phenol is as the staple product in chemical industry
There is extensive use.Industrial production mainly prepares phenol using the peroxidating of isopropylbenzene and sour decomposition reaction at present, but
It is a large amount of acetone of by-product in the reaction process.Compared with cyclohexyl benzene oxidizing process prepares the technique of phenol, cyclohexyl benzene
Oxidation product is phenol and cyclohexanone.The latter is to produce the important source material of caprolactam and nylon, therefore there is no pairs for the route
The Utilizing question of product.
Document US5053571 discloses benzene progress hydroalkylation on the Beta molecular sieves of load Ru and Ni and prepares hexamethylene
The technique of base benzene.Document US5146024 discloses the technique that a kind of benzene hydrogenation alkylation prepares cyclohexyl benzene, and used catalyst is
X either on Y molecular sieve the carried metal Pd catalyst with alkali metal or rare-earth metal modified.Exxon Mobil Corporation exists
US6037513、US7579511、US7847128、US7910778、US8084648、US8106243、US8178728、
US8329956, US8519194, US20100191017, US20110015457, US20110288341, US20120178969 and
CN101687728、CN101754940、CN101796000、CN101925561、CN101998942、CN101998942、
MCM-22 family molecular sieves and at least one hydrogenation metal are then used in CN102015589, CN102177109 and CN103261126
The catalyst system and catalyzing of (Ni, Pd, Pt and Ru) carries out hydroalkylation in a hydrogen atmosphere.Reaction condition is：Temperature is about 140
~175 DEG C, pressure is about 931~1207KPa, and hydrogen benzene mole was than about 0.3~0.65 and about 0.26~1.05 hour-1Benzene
Weight (hourly) space velocity (WHSV).The highest yield of cyclohexyl benzene is about 40%.The above patent has used noble metal catalyst, therefore is produced into
This is higher.Alkylation and Y molecular sieve using Y molecular sieve progress benzene and cyclohexene is announced in patent US20120157718 to bear
Carry a kind of method that hydrogenation metal (Ni, Pd, Pt and Ru) progress benzene hydrogenation alkylated reaction prepares cyclohexyl benzene.Wherein, alkyl
It is larger to change reaction benzene alkene ratio (5-30), causes the yield of cyclohexyl benzene relatively low, increases the cost of product separation.
Document CN1982264 and CN198226 prepares ring using benzene and cyclohexane halide or cyclohexanol by alkylated reaction
The method of hexyl benzene.But cyclohexane halide and cyclohexanol is expensive, and used catalyst to reaction unit corrode compared with
Greatly.It is disclosed in patent CN101219922 using glyoxaline ion liquid and metal halide or three second hydrochloric acid salt ions
Liquid and the method that metal halide is catalyst preparation cyclohexyl benzene.CN101811924 then uses toluenesulfonic acid and pyridines
Ionic liquid is alkylation catalyst.However ionic liquid price is relatively high, is unfavorable for commercial Application, while increasing product
The cost of separation.
Invention content
The present invention is intended to provide a kind of method that new cyclohexene and benzene alkylation prepare cyclohexyl benzene.This method, which has, urges
The characteristics of agent long lifespan.
For achieving the above object, the technical solution adopted by the present invention is as follows：It is prepared by a kind of cyclohexene and benzene alkylation
The method of cyclohexyl benzene, is included under the conditions of effecting reaction, and benzene and cyclohexene is made to contact synthesizing cyclohexyl with molecular sieve catalyst
The step of benzene；Wherein, the concentration for controlling oxygenatedchemicals in cyclohexene makes the concentration of oxygenatedchemicals in cyclohexene be less than 1 weight
Measure %.
As an embodiment of the invention, a concentration of 0~1 weight of oxygenatedchemicals in cyclohexene is preferably controlled
Measure %.
As an embodiment of the invention, a concentration of 0~0.75 weight of oxygenatedchemicals in cyclohexene is preferably controlled
Measure %.
As an embodiment of the invention, a concentration of 0~0.5 weight of oxygenatedchemicals in cyclohexene is preferably controlled
Measure %.
As an embodiment of the invention, a concentration of 0.01ppm~1 of oxygenatedchemicals in cyclohexene is preferably controlled
Weight %.
In above-mentioned technical proposal, the oxygenatedchemicals is derived from the product that cyclohexene is reacted with oxygen.
In above-mentioned technical proposal, the oxygenatedchemicals includes 7-oxa-bicyclo[4.1.0, cyclohexanone, cyclohexanol, cyclohexenol, ring
At least one of hexenone and hexamethylene enediol.
In above-mentioned technical proposal, the molecular sieve catalyst by weight percentage, including following component：A) 40~90%
Zeolite molecular sieve；And b) 10~60% binder.
In above-mentioned technical proposal, the molecular sieve in MWW, BEA, MOR and FAU topological structure molecular sieve extremely
Few one kind；It is preferred that at least one of MCM-22, MCM-49, MCM-56, modenite, Beta molecular sieves and Y type molecular sieve.
In above-mentioned technical proposal, the SiO of the molecular sieve2/Al2O3Molar ratio is 5~100, preferably 10~80.
In above-mentioned technical proposal, the effecting reaction condition includes：100~250 DEG C of reaction temperature, preferably 120~220
DEG C, 0.5~4.0MPa of reaction pressure, preferably 1.0~3.0MPa；Benzene/cyclohexene molar ratio 1.0~10.0, preferably 2.0~8.0；
Cyclohexene weight space velocity 0.1~2 hour-1, preferably 0.2~1 hour-1。
In above-mentioned technical proposal, the binder in aluminium oxide, titanium oxide, zinc oxide and zirconium oxide at least one
Kind.
In above-mentioned technical proposal, make include the steps that oxygenatedchemicals cyclohexene carry out rectifying contained with controlling in cyclohexene
The concentration of oxygen compound is less than 1 weight %.
In above-mentioned technical proposal, make to include that the cyclohexene of oxygenatedchemicals is contacted with activated alumina guard bed with control ring
The concentration of oxygenatedchemicals is less than 1 weight % in hexene.
The present inventor is the study found that under the action of molecular sieve solid acid catalyst alkylated reaction occurs for benzene and cyclohexene
When preparing cyclohexyl benzene, since cyclohexene property is active, after contacting with the air easily generate oxygenatedchemicals, as 7-oxa-bicyclo[4.1.0,
Cyclohexanone, cyclohexanol, cyclohexenol, cyclonene, hexamethylene enediol etc..The presence of these oxygenatedchemicals can urge solid acid
Agent is poisoned, and the decline of catalyst stability is caused.The present invention by control control cyclohexene in oxygenatedchemicals it is dense
Degree makes the concentration of oxygenatedchemicals in cyclohexene be less than 1 weight %, and the service life of catalyst can at least improve 200%, achieve
Preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Specific implementation mode
【Embodiment 1】
Synthesis has MWW topological structure MCM-56 molecular sieves.
The Ludox of 600 grams of 40wt% is taken, 700 grams of water, 38.9 grams of sodium metaaluminate (Al are added2O342wt%) and 2 grams of hydrogen
Sodium oxide molybdena after stirring evenly, adds 125 grams of hexamethylene imines (HMI).Said mixture at room temperature, be aged 100h after,
138 DEG C of crystallization are increased the temperature to, after 40 hours, distilled water is cleaned to neutrality, drying crystallization.X-ray powder diffraction shows
(XRD) the result shows that synthesized product is MCM-56.Wherein above-mentioned reaction mixture is with molar ratio computing:SiO2/Al2O3It is 25,
OH-/SiO2It is 0.093, H2O/SiO2It is 14.72, HMI/SiO2It is 0.32.The MCM-56 molecular sieve silica alumina ratios obtained
SiO2/Al2O3Crystallinity for 24.5, MCM-56 molecular sieves is 99.8%.
The powder sample after 50 grams of dryings is taken, is exchanged 4 times with the ammonium nitrate of 1M, filtering, drying.Later with 20 grams of aluminium oxide
It is sufficiently mixed, and the bar that 5wt% nitric acid is mediated, extruded moulding is 1.6 × 2mm of φ is added, 120 DEG C of dryings 12 hours, 520
DEG C roasting 6 hours, be prepared into the catalyst of needs.
【Embodiment 2】
Synthesize the MCM-22 molecular sieves with MWW topological structures.
Aluminic acid is received into (Al2O335.21wt%, Na2O 31.12wt%) 14.5 grams be dissolved in 990 grams of water, hydroxide is added
6.18 grams of sodium is allowed to dissolve, and 49.5 grams of organic amine template hexamethylene imine is then added in the case of stirring, adds
Ludox (SiO240wt%) 150 grams, it is to be mixed uniformly after, the material proportion (molar ratio) of reactant is:SiO2/Al2O3=
20, OH-/SiO2=0.3, R/SiO2=0.5, H2O/SiO2=60.After stirring 30 minutes, it is fitted into stainless steel cauldron, is stirring
In 150 DEG C of crystallization 30 hours in the case of mixing.Then it cools down, the solid product of filtering for crystallizing, and recycles crystalline mother solution.Above-mentioned solid
Crystallized product is using filter, washing, drying.It is MCM-22 that X-ray diffractometer, which measures gained crystal,.SiO is obtained through chemical analysis2/
Al2O3Molar ratio is 18.
The powder sample after 50 grams of dryings is taken, is exchanged 4 times with the ammonium nitrate of 1M, filtering, drying.Later, it is aoxidized with 20 grams
Aluminium is sufficiently mixed, and the bar that 5wt% nitric acid is mediated, extruded moulding is 1.6 × 2mm of φ is added, 120 DEG C of dryings 12 hours,
520 DEG C roast 6 hours, are prepared into the catalyst of needs.
【Embodiment 3】
Synthesize the Beta molecular sieves with BEA topological structures.
By 600g 40wt.% Ludox, 38.9g sodium aluminates (alumina content 42wt.%), 70.6g 25wt.% tetrems
Base ammonium hydroxide (TEAOH), 5.0g diethylamine (DEA), 168.0g tetraethylammonium bromides (TEABr), 16.0g sodium hydroxides,
The ammonium hydroxide of 136.0g 25wt.%, 925.1g water mix, and are stirred evenly under room temperature.Then it is transferred in stainless steel autoclave,
155 DEG C of crystallization temperature reacts 50 hours.After reaction, it is filtered, washed, drying crystalline product.Wherein, in reaction mixture
With molar ratio computing SiO2/A12O3=35, TEAOH/SiO2=0.05, DEA/SiO2=0.01, TEABr/SiO2=0.3, NaOH/
SiO2=0.05, NH4OH/SiO2=0.2, H2O/SiO2=25, R1/R2=0.2.Product is through obtained by XRD powder diffraction analysis
Crystalline product is Beta zeolites, its crystal grain diameter of transmission electron microscope tem analysis is 10~40nm.SiO is obtained through chemical analysis2/Al2O3
Molar ratio is 20.
The powder sample after 50 grams of dryings is taken, is exchanged 4 times with the ammonium nitrate of 1M, filtering, drying.Later, it is aoxidized with 20 grams
Aluminium is sufficiently mixed, and the bar that 5wt% nitric acid is mediated, extruded moulding is 1.6 × 2mm of φ is added, 120 DEG C of dryings 12 hours,
520 DEG C roast 6 hours, are prepared into the catalyst of needs.
【Embodiment 4】
Synthesize the Y type molecular sieve with FAU topological structures.
Colloidal state directed agents are prepared first, by 20.0g H2O, 4.0g NaOH and 2.1g sodium aluminates (20% solution) solution fills
Point dissolving is mixed to uniform, then 22.7g silicic acid is gradually added in above-mentioned solution under stiring, at room temperature fully oscillation 1h
Afterwards, aged overnight at room temperature；By 261.9g H2O, 0.28gNaOH and 20.6g sodium aluminate, which are sufficiently mixed, to mix, by 284.8g
Silicic acid is gradually added portionwise in the case where being sufficiently stirred into above-mentioned mixed solution and fiercely vibrates 1h, and the directed agents 50g of preparation is added
Enter and vibrates 1h into above-mentioned mixed solution.Then it transfers the material into stainless steel cauldron.The mistake after crystallization 10h at 100 DEG C
Filter, washing, drying crystalline product.It is Y type molecular sieve through the crystalline product obtained by XRD powder diffraction analysis.
Powder sample after taking 50g to dry is exchanged 4 times with the ammonium nitrate of 1M, filtering, drying.It is filled later with 20g aluminium oxide
Divide mixing, and the bar that 5wt% nitric acid is mediated, extruded moulding is 1.6 × 2mm of φ, 120 DEG C of dryings 12 hours, 500 DEG C are added
Roasting 6 hours, is prepared into the catalyst of needs.
【Embodiment 5】
Synthesize the mordenite molecular sieve with MOR topological structures.
19gNaOH is dissolved in 40g H under stiring2In O, 14.3 sodium aluminates are mixed with above-mentioned NaOH solution, stirring is extremely
Quan Rong.497gH is being added in above-mentioned mixed solution2O dilutes, and 245.5g 40wt.% Ludox is added in above-mentioned solution and is stirred
It will be transferred in stainless steel autoclave, 170 DEG C of crystallization temperature, react 24 hours after solution after 30min.After reaction, it filters, wash
It washs, drying crystalline product.It is modenite through the crystalline product obtained by XRD powder diffraction analysis.
Powder sample after taking 50g to dry is exchanged 4 times with the ammonium nitrate of 1M, filtering, drying.Later, with 20g aluminium oxide
It is sufficiently mixed, and the bar that 5wt% nitric acid is mediated, extruded moulding is 1.6 × 2mm of φ is added, 120 DEG C of dryings 12 hours, 500
DEG C roasting 6 hours, be prepared into the catalyst of needs.
【Embodiment 6】
It will【Embodiment 1-5】4.0 grams of catalyst be seated in fixed bed reactors respectively, then pass to cyclohexene and benzene
Mixed material, the mass fraction of cyclohexene is 19.1% in mixture.The mass fraction of oxygenatedchemicals wherein in cyclohexene
For 0.3wt%.Reaction condition is：Cyclohexene weight space velocity is 0.4h-1, 170 DEG C of reaction temperature, reaction pressure 2.0MPa.Reaction
The results are shown in Table 1.
Table 1
【Embodiment 7】
It will【Embodiment 1-5】4.0 grams of the catalyst of synthesis is seated in fixed bed reactors respectively, then passes to cyclohexene
With the mixed material of benzene, the mass fraction of cyclohexene is 19.1% in mixture, the quality of oxygenatedchemicals wherein in cyclohexene
Score is 0.6wt%.Reaction condition is：Cyclohexene weight space velocity is 0.4h-1, reaction temperature is 170 DEG C, and reaction pressure is
2.0MPa.Reaction result is as shown in table 2.
Table 2
【Comparative example】
It will【Embodiment 1-5】4.0 grams of the catalyst of synthesis is seated in fixed bed reactors respectively, then passes to cyclohexene
With the mixed material of benzene, the mass fraction of cyclohexene is 19.1% in mixture, the quality of oxygenatedchemicals wherein in cyclohexene
Score is 1.5wt%.Reaction condition is：Cyclohexene weight space velocity is 0.4h-1, reaction temperature is 170 DEG C, and reaction pressure is
2.0MPa.Reaction result is as shown in table 3.
Table 3
Claims (17)
1. a kind of method that cyclohexene and benzene alkylation prepare cyclohexyl benzene, is included under the conditions of effecting reaction, make benzene and hexamethylene
The step of alkene is with molecular sieve catalyst contact synthesizing cyclohexyl benzene；It is characterized in that control cyclohexene in oxygenatedchemicals it is dense
Degree makes the concentration of oxygenatedchemicals in cyclohexene be less than 1 weight %.
2. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that make cyclohexene
A concentration of 0~1 weight % of middle oxygenatedchemicals.
3. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that make cyclohexene
A concentration of 0~0.75 weight % of middle oxygenatedchemicals.
4. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that make cyclohexene
A concentration of 0~0.5 weight % of middle oxygenatedchemicals.
5. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that make cyclohexene
The weight of a concentration of 0.01ppm~1 % of middle oxygenatedchemicals.
6. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that described oxygen-containing
Compound is derived from the product that cyclohexene is reacted with oxygen.
7. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that described oxygen-containing
Compound includes at least one of 7-oxa-bicyclo[4.1.0, cyclohexanone, cyclohexanol, cyclohexenol, cyclonene and hexamethylene enediol.
8. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that the molecule
Sieve catalyst by weight percentage, including following component：A) 40~90% zeolite molecular sieve；And b) 10~60% bonding
Agent.
9. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that the molecule
Screened from at least one of MWW, BEA, MOR and FAU topological structure molecular sieve.
10. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 9, which is characterized in that described point
Son is screened from least one of MCM-22, MCM-49, MCM-56, modenite, Beta molecular sieves and Y type molecular sieve.
11. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that described point
The SiO of son sieve2/Al2O3Molar ratio is 5~100.
12. the method for preparing cyclohexyl benzene according to cyclohexene described in claim 11 and benzene alkylation, which is characterized in that described point
The SiO of son sieve2/Al2O3Molar ratio is 10~80.
13. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that described to have
Validity response condition includes：100~250 DEG C, 0.5~4.0MPa of reaction pressure of reaction temperature, benzene/cyclohexene molar ratio 1.0~
10.0, cyclohexene weight space velocity 0.1~2 hour-1。
14. the method for preparing cyclohexyl benzene according to cyclohexene described in claim 13 and benzene alkylation, which is characterized in that described to have
Validity response condition includes：120~220 DEG C of reaction temperature, reaction pressure are 1.0~3.0MPa, and benzene/cyclohexene molar ratio is 2.0
~8.0, cyclohexene weight space velocity is 0.2~1 hour-1。
15. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that described viscous
It ties agent and is selected from least one of aluminium oxide, titanium oxide, zinc oxide and zirconium oxide.
16. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that make include
The cyclohexene of oxygenatedchemicals carries out the step of rectifying and is less than 1 weight % with the concentration for controlling oxygenatedchemicals in cyclohexene.
17. the method that cyclohexene and benzene alkylation prepare cyclohexyl benzene according to claim 1, which is characterized in that make include
The cyclohexene of oxygenatedchemicals is contacted with activated alumina guard bed is less than 1 weight with the concentration for controlling oxygenatedchemicals in cyclohexene
Measure %.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN116265111A (en) * | 2021-12-16 | 2023-06-20 | 中国科学院大连化学物理研究所 | Molecular sieve, preparation method thereof and application thereof in liquid phase alkylation of benzene and cyclohexene |
| CN116459866A (en) * | 2023-04-26 | 2023-07-21 | 广东工业大学 | Beta molecular sieve catalyst, preparation method thereof and application thereof in preparation of cyclohexylbenzene |
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