CN111675594A - Method for producing cyclohexylbenzene by benzene hydroalkylation - Google Patents
Method for producing cyclohexylbenzene by benzene hydroalkylation Download PDFInfo
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- CN111675594A CN111675594A CN202010665066.8A CN202010665066A CN111675594A CN 111675594 A CN111675594 A CN 111675594A CN 202010665066 A CN202010665066 A CN 202010665066A CN 111675594 A CN111675594 A CN 111675594A
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- Prior art keywords
- benzene
- material flow
- hydroalkylation
- cyclohexylbenzene
- catalyst
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 191
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- OQXMLPWEDVZNPA-UHFFFAOYSA-N 1,2-dicyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1C1CCCCC1 OQXMLPWEDVZNPA-UHFFFAOYSA-N 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 34
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 34
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 238000010555 transalkylation reaction Methods 0.000 claims description 13
- 238000010544 hydroalkylation process reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000005804 alkylation reaction Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 6
- 208000012839 conversion disease Diseases 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006004 Quartz sand Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C07C2/74—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition with simultaneous hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C07C2523/72—Copper
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- C07C2529/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
The invention discloses a method for producing cyclohexylbenzene by benzene hydroalkylation. It is characterized in that benzene and hydrogen generate a first material flow under the action of a hydroalkylation catalyst, and the first material flow is rectified and separated to obtain C-rich material flow6And a third stream rich in cyclohexylbenzene. When the benzene content in the second material flow is more than 60 wt%, the second material flow is completely circulated back to the hydroalkylation reactor, when the benzene content is less than 60 wt%, the second material flow reacts under the action of the dehydrogenation catalyst, and the material flow rich in benzene is recycled to the hydroalkylation reactor after separation. The third stream is separated to produce cyclohexylbenzene and a fourth stream rich in dicyclohexylbenzene which is transalkylated to produce cyclohexylbenzene. The method improves the product yield, and greatly reduces the cost and energy consumption of the dehydrogenation process because the second material flow is subjected to the concentrated dehydrogenation reaction.
Description
Technical Field
The invention relates to a method for producing cyclohexylbenzene by benzene hydroalkylation, belonging to the technical field of chemical industry.
Background
The production of phenol from cyclohexylbenzene is an emerging technology, which is advantageous in that it coproduces cyclohexanone, rather than acetone. In this process, cyclohexylbenzene is first oxidized to form its hydroperoxide, which is then cleaved in the presence of an acid catalyst to yield phenol and cyclohexanone.
The process for synthesizing the cyclohexylbenzene by the direct benzene hydroalkylation method comprises the following steps: under the action of a multifunctional catalyst, benzene is firstly subjected to metal-catalyzed selective hydrogenation to generate cyclohexene, and the generated cyclohexene and unconverted benzene are subjected to acid-catalyzed alkylation reaction to generate cyclohexylbenzene. The process has the advantages of rich benzene source, simple process, low cost and the like, and is suitable for large-scale industrial production.
At present, the process for producing cyclohexylbenzene by a benzene hydroalkylation method inevitably produces cyclohexane, methylcyclopentane and dicyclohexylbenzene, wherein the cyclohexane, methylcyclopentane and benzene are difficult to separate due to similar boiling points, so that the separation and conversion of byproducts must be considered in the production process in order to achieve better product yield and lower cost and energy consumption. In order to achieve the purpose, the byproduct cyclohexane needs to be dehydrogenated to form raw material benzene, and the dicyclohexylbenzene is subjected to transalkylation to obtain the product cyclohexylbenzene.
CN 102177109A discloses a method for preparing cyclohexylbenzene, which is rich in C6The stream is continuously subjected to dehydrogenation and returned to the hydroalkylation reaction. In the usual case, C6The ratio of cyclohexane to methylcyclopentane in the material flow is less than 10%, so that most of the material in the dehydrogenation reactor is benzene, the energy consumption is increased, and the reaction efficiency is low. Even if it is combined with C6The stream is divided into a benzene-rich stream and a cyclohexane-rich stream, which is subjected to dehydrogenation, and then a separation step is added before dehydrogenation, which undoubtedly also increases energy consumption and complicates the production process.
For the benzene hydrogenation alkylation to produce the cyclohexylbenzene, the simple process flow and the low cost are the targets of large-scale industrial production.
Disclosure of Invention
It is an object of the present invention to provide a process for the hydroalkylation of benzene to produce cyclohexylbenzene in which process C6The material flow is directly recycled to the alkylation reaction step when the benzene content is more than 60 percent; when the benzene content is less than 60%, the material is subjected to dehydrogenation reaction, so that not only is the energy consumption saved, but also the dehydrogenation reaction is facilitated.
The invention relates to a method for producing cyclohexylbenzene by benzene hydroalkylation. It is characterized in that under the action of a hydroalkylation catalyst, benzene and hydrogen contact and react to generate a first material flow, and the first material flow is rectified and separated to obtain C-rich material6And a third stream rich in cyclohexylbenzene. When the second stream contains more than 60 wt% benzene, the second stream is recycled to the hydroalkylation reactor, and when the second stream contains less than 60 wt% benzene, the second stream is subjected to dehydrogenation catalystDehydrogenation reaction is carried out under the action of the catalyst, and then the material flow rich in benzene is recycled to the hydroalkylation reactor after separation. The third stream is separated to obtain crude cyclohexylbenzene and a fourth stream rich in dicyclohexylbenzene, and the fourth stream is subjected to transalkylation reaction under the action of a transalkylation catalyst to further generate cyclohexylbenzene to obtain a fifth stream, and the fifth stream can be combined with the first stream.
A process for the hydroalkylation of benzene to produce cyclohexylbenzene as described above, characterized by being C-rich6Comprises benzene, cyclohexane and methylcyclopentane. Due to C6The second material flow also contains a small amount of low-boiling linear or branched alkane due to the recycling of the materials after the dehydrogenation separation.
The hydroalkylation catalyst as described above is characterized by being a molecular sieve catalyst supporting metallic ruthenium, wherein the molecular sieve is one or a mixture of any two of beta molecular sieve, MCM-22 molecular sieve and mordenite. The hydroalkylation catalyst is formed during use, and the binder for forming may be SB powder or alumina sol. The loading capacity of the ruthenium oxide is 0.1-1 wt%.
The method for producing the cyclohexylbenzene by benzene hydroalkylation is characterized in that the hydroalkylation reaction temperature is 150-200 ℃, the reaction pressure is 0.5-2.5 MPa, and the mass space velocity of benzene is 1-3 h-1The molar ratio of hydrogen to benzene is 0.5 to 1.5. The hydroalkylation reaction device can adopt a sectional reactor or a sectional feeding or catalytic rectification reactor.
The method for producing cyclohexylbenzene by benzene hydroalkylation is characterized in that the dehydrogenation catalyst contains 10-30% of copper oxide, the dehydrogenation reaction temperature is 150-250 ℃, and the reaction pressure is 0.5-1.5 MPa. The material after dehydrogenation reaction is separated by a rectifying tower to remove methylcyclopentane dehydrogenation products, namely methylcyclopentadiene and most of straight-chain or branched alkane, wherein the straight-chain or branched alkane is distilled from the top of the tower, and the methylcyclopentadiene exists at the bottom of the tower.
A benzene hydroalkylation as described above to produce cyclohexylbenzeneThe method is characterized in that the transalkylation catalyst is β molecular sieve, the silicon-aluminum ratio is 30-100, the transalkylation reaction temperature is 150-200 ℃, the reaction pressure is 0.5-2.0 MPa, and the mass space velocity of dicyclohexylbenzene is 0.5-2 h-1The mass ratio of dicyclohexylbenzene to benzene is 1: 3-6, β molecular sieves are synthesized by a hydrothermal method, and synthesized raw powder is treated by nitric acid.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the illustrated examples.
The feedstock benzene for the hydroalkylation step may be selected from any commercially available commercial product or reagent, requiring a purity of no less than 99%; the hydrogen used as the feedstock for the hydroalkylation step may be selected from conventional hydrogen and is required to have a purity of not less than 99%.
Example 1
Preparation of a hydroalkylation catalyst:
at room temperature, 0.36g of RuCl was weighed3·3H2Dissolving O in 80g of deionized water, adding 30g of molecular sieve, stirring for 10min, heating to 60 ℃, dropwise adding 10% ammonium carbonate solution until the pH value is more than 8, stopping dropwise adding, stirring for 30min, measuring the pH value, if the pH value is less than 8, dropwise adding 10% ammonium carbonate solution again until the pH value is more than 8, stirring for 30min again, measuring the pH value, repeating the steps until the pH value is more than 8, and continuously stirring for 2 h. Filtering, washing, drying, roasting, tabletting, and sieving.
Preparation of dehydrogenation catalyst:
silica sol or white carbon black is used as a silicon source, a copper-silicon catalyst is prepared by an ammonia distillation method, and the dehydrogenation catalyst contains 22.5 percent of copper oxide.
Preparation of transalkylation catalyst:
synthesizing beta molecular sieve raw powder by a hydrothermal method, and performing an acid treatment step to obtain the transalkylation catalyst, wherein the silicon-aluminum ratio is 40.
Example 2
4g of alkylation catalyst is filled in the middle section of a reaction tube, quartz sand is respectively added at two ends of the reaction tube, the hydroalkylation catalyst is reduced at the reduction temperature of 250 DEG C. The hydroalkylation reaction conditions are as follows: the space velocity of benzene is 2.0h-1The reaction temperature is 180 ℃, the reaction pressure is 2.0MPa, and the molar ratio of the hydrogen to the benzene is 0.5. Pure benzene is used for feeding, sampling analysis is carried out after 24 hours of reaction, the reaction conversion rate is 40.4%, and the selectivity of the cyclohexylbenzene is 75.6%.
Rectifying the first material flow obtained after the hydrogenation alkylation reaction by a rectifying column to obtain the material flow rich in C693.31% benzene, 6.58% cyclohexane, 0.08% methylcyclopentane, and 84.96% cyclohexylbenzene and 11.10% dicyclohexylbenzene in the third stream. The second material flow is recycled to the step of the hydrogenation alkylation reaction, the third material flow is separated by negative pressure rectification to obtain crude cyclohexylbenzene with the purity of more than 97.5 percent and a fourth material flow rich in dicyclohexylbenzene, and the benzene content of the fourth material flow is 3.24 percent, and the dicyclohexylbenzene content is 82.75 percent. The fourth material flow and the raw material benzene enter a transalkylation reaction tube, 4g of catalyst is filled in the reaction tube, two ends of the reaction tube are filled with quartz sand, and the transalkylation reaction conditions are as follows: the space velocity of dicyclohexylbenzene is 1.0h-1The reaction temperature is 170 ℃, the reaction pressure is 1.0MPa, and the mass ratio of dicyclohexylbenzene to benzene is 1: 3. After 24h the reaction was sampled for analysis and dicyclohexylbenzene conversion was 50.5% and cyclohexylbenzene selectivity was 95.6%, a fifth stream was obtained after the transalkylation reaction, which could be combined with the first stream.
The second material flow containing 93.31 percent of benzene, 6.58 percent of cyclohexane and 0.08 percent of methyl cyclopentane is subjected to once circulating hydroalkylation reaction, and after 24 hours of reaction, sampling analysis shows that the reaction conversion rate is 41.1 percent and the selectivity of the cyclohexylbenzene is 74.8 percent. The materials after the reaction are separated to obtain the C-rich material6The composition of the material flow is 86.12 percent of benzene, 13.70 percent of cyclohexane and 0.18 percent of methyl cyclopentane.
The second material flow containing 93.31 percent of benzene, 6.58 percent of cyclohexane and 0.08 percent of methyl cyclopentane is subjected to four times of circulating hydrogenation alkylation reactions, and after 24 hours of reaction, sampling analysis shows that the reaction conversion rate is 40.7 percent and the selectivity of the cyclohexylbenzene is 74.7 percent. The materials after the reaction are separated to obtain the C-rich material6The composition of the material flow is 63.94 percent of benzene, 35.50 percent of cyclohexane and methyl cyclopentyl0.53 percent of alkane.
The second material flow containing 93.31 percent of benzene, 6.58 percent of cyclohexane and 0.08 percent of methyl cyclopentane is subjected to five times of circular hydroalkylation reactions, and after 24 hours of reaction, sampling analysis shows that the reaction conversion rate is 38.9 percent and the selectivity of cyclohexylbenzene is 74.7 percent. The materials after the reaction are separated to obtain the C-rich material6The composition of the feed stream of (1) was 56.92% benzene, 42.48% cyclohexane and 0.60% methylcyclopentane.
The second material flow containing 93.31 percent of benzene, 6.58 percent of cyclohexane and 0.08 percent of methyl cyclopentane is subjected to six times of circular hydrogenation alkylation reaction, and after 24 hours of reaction, sampling analysis shows that the reaction conversion rate is 34.8 percent and the selectivity of the cyclohexylbenzene is 74.7 percent.
A second material flow with the composition of 56.92 percent of benzene, 42.48 percent of cyclohexane and 0.60 percent of methyl cyclopentane is subjected to dehydrogenation reaction, 4g of dehydrogenation catalyst is filled in a reaction tube, quartz sand is filled at two ends of the reaction tube, and the reduction temperature of the dehydrogenation catalyst is 300 ℃. Dehydrogenation reaction conditions: the space velocity of cyclohexane is 2.0h-1The reaction temperature is 220 ℃, and the reaction pressure is 1.0 MPa. After 24 hours of reaction, sampling analysis shows that the conversion rate of cyclohexane is 88.4%, the selectivity is 97.6%, the conversion rate of methyl cyclopentane is 87.1%, and the selectivity is 96.2%. Rectifying and separating the reacted material, wherein the separated cyclohexane, methylcyclopentane and cyclohexane dehydrogenation product benzene can be recycled to the hydrogenation alkylation reaction, and the dehydrogenation product methylcyclopentane is left in the residue of the rectifying still.
Claims (6)
1. The invention relates to a method for producing cyclohexylbenzene by benzene hydroalkylation, which is characterized in that benzene and hydrogen contact and react to generate a first material flow under the action of a hydroalkylation catalyst, and the first material flow is rectified and separated to obtain a C-rich material flow6And a third stream rich in cyclohexylbenzene; when the benzene content in the second material flow is more than 60 wt%, the second material flow is completely circulated back to the hydroalkylation reactor, when the benzene content in the second material flow is less than 60 wt%, the second material flow is subjected to dehydrogenation reaction under the action of a dehydrogenation catalyst, and then the second material flow is separated, and the material flow rich in benzene is recycled to the hydroalkylation reactor; third materialThe streams are separated to provide crude cyclohexylbenzene and a fourth stream rich in dicyclohexylbenzene which is transalkylated with benzene over a transalkylation catalyst to further form cyclohexylbenzene to provide a fifth stream which may be combined with the first stream.
2. The process of claim 1 for the hydroalkylation of benzene to produce cyclohexylbenzene, characterized by being C-rich6Comprises benzene, cyclohexane and methylcyclopentane.
3. The process of claim 1 for the hydroalkylation of benzene to produce cyclohexylbenzene, wherein: the hydroalkylation catalyst is a molecular sieve catalyst loaded with metallic ruthenium, the loading capacity of ruthenium oxide is 0.1-1 wt%, and the molecular sieve is one or a mixture of any two of beta molecular sieve, MCM-22 molecular sieve and mordenite.
4. The method for producing cyclohexylbenzene by benzene hydroalkylation according to claim 1, wherein the hydroalkylation reaction temperature is 150 to 200 ℃, the reaction pressure is 0.5 to 2.5MPa, and the mass space velocity of benzene is 1 to 3 hours-1The molar ratio of hydrogen to benzene is 0.5 to 1.5.
5. The process of claim 1, wherein the dehydrogenation catalyst comprises 10-30% copper oxide, the dehydrogenation temperature is 150-250 ℃, and the reaction pressure is 0.5-1.5 MPa.
6. The method of claim 1, wherein the transalkylation catalyst is β molecular sieve, the silica-alumina ratio is 30-100, the transalkylation reaction temperature is 150-200 ℃, the reaction pressure is 0.5-2.0 MPa, and the mass space velocity of dicyclohexylbenzene is 0.5-2 h-1The mass ratio of dicyclohexylbenzene to benzene is 1: 3-6.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177109A (en) * | 2008-10-10 | 2011-09-07 | 埃克森美孚化学专利公司 | Process for making cyclohexylbenzene |
| CN103261126A (en) * | 2010-12-17 | 2013-08-21 | 埃克森美孚化学专利公司 | Process of producing cyclohexylbenzene |
| CN104066704A (en) * | 2011-10-17 | 2014-09-24 | 埃克森美孚化学专利公司 | Process for producing cyclohexylbenzene |
| CN104105679A (en) * | 2012-02-08 | 2014-10-15 | 埃克森美孚化学专利公司 | Process for producing cyclohexylbenzene |
| CN104136402A (en) * | 2012-02-27 | 2014-11-05 | 埃克森美孚化学专利公司 | Hydroalkylation process |
| CN106311214A (en) * | 2016-07-31 | 2017-01-11 | 湘潭大学 | Dehydrogenation catalyst for non-precious metal and preparation method thereof |
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2020
- 2020-07-10 CN CN202010665066.8A patent/CN111675594A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102177109A (en) * | 2008-10-10 | 2011-09-07 | 埃克森美孚化学专利公司 | Process for making cyclohexylbenzene |
| CN103261126A (en) * | 2010-12-17 | 2013-08-21 | 埃克森美孚化学专利公司 | Process of producing cyclohexylbenzene |
| CN104066704A (en) * | 2011-10-17 | 2014-09-24 | 埃克森美孚化学专利公司 | Process for producing cyclohexylbenzene |
| CN104105679A (en) * | 2012-02-08 | 2014-10-15 | 埃克森美孚化学专利公司 | Process for producing cyclohexylbenzene |
| CN104136402A (en) * | 2012-02-27 | 2014-11-05 | 埃克森美孚化学专利公司 | Hydroalkylation process |
| CN106311214A (en) * | 2016-07-31 | 2017-01-11 | 湘潭大学 | Dehydrogenation catalyst for non-precious metal and preparation method thereof |
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