US20080139383A1 - Hydrogenation of aromatic compounds - Google Patents
Hydrogenation of aromatic compounds Download PDFInfo
- Publication number
- US20080139383A1 US20080139383A1 US12/021,809 US2180908A US2008139383A1 US 20080139383 A1 US20080139383 A1 US 20080139383A1 US 2180908 A US2180908 A US 2180908A US 2008139383 A1 US2008139383 A1 US 2008139383A1
- Authority
- US
- United States
- Prior art keywords
- catalyst
- benzene
- hydrogenation
- cyclohexane
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 50
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 230000007704 transition Effects 0.000 claims abstract description 13
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 210
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 239000010949 copper Substances 0.000 claims description 21
- -1 copper modified nickel catalyst Chemical class 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052702 rhenium Inorganic materials 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000047 product Substances 0.000 description 27
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 239000012535 impurity Substances 0.000 description 19
- 239000002904 solvent Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- 238000009835 boiling Methods 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 15
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 14
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 14
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 7
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004454 trace mineral analysis Methods 0.000 description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- VYWLNKBAMVZVAJ-UHFFFAOYSA-N cyclohexane cyclohexene Chemical compound C1=CCCCC1.C1CCCCC1 VYWLNKBAMVZVAJ-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FGNLEIGUMSBZQP-UHFFFAOYSA-N cadaverine dihydrochloride Chemical compound Cl.Cl.NCCCCCN FGNLEIGUMSBZQP-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- B01J35/613—
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- B01J35/615—
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- B01J35/633—
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- B01J35/635—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/75—Cobalt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a process for hydrogenation of aromatic compounds such as the hydrogenation of benzene to cyclohexane and the supported nickel catalyst modified with up to 0.9 wt. % Cu therefore.
- Cyclohexane is the main precursor for the production of nylon products and as such, the demand remains strong. Cyclohexane was first obtained by the direct fractional distillation of suitable crude petroleum refinery streams. Now the major portion of cyclohexane is obtained from the direct hydrogenation of benzene. Conventionally the reaction is carried out in vapor or mixed phase using a fixed bed reaction. The reactor temperature is controlled to be between 350 to 500° F. Higher temperatures can lead to thermodynamic limitations on benzene conversion, thermal cracking and increased byproduct. In general, the amount of byproducts in the effluent stream from a hydrogenation reactor increases with hydrogenation temperature or conversion of benzene or both.
- Peterson in U.S. Pat. No. 2,373,501, discloses a liquid phase process for the hydrogenation of benzene to cyclohexane wherein a temperature differential is maintained between the top of the catalyst bed where benzene is fed and the outlet where substantially pure cyclohexane is withdrawn.
- the temperature differential is due to the change in the exothermic heat of reaction released as less and less benzene is converted as the concentration of benzene decreases.
- the top of the catalyst bed is at a higher temperature than the lower catalyst bed. Hydrogen is supplied countercurrent to the benzene/cyclohexane flow.
- Temperature control coils are disposed within the reactor to maintain the temperature differential if the exothermic heat of reaction is not sufficient or to cool the bed if too much heat is released.
- Peterson recognizes that although the bulk of his reaction takes place in the liquid phase a portion of the benzene and cyclohexane will be vaporized, especially near the top of the reactor where the benzene concentration is highest and conversion is highest.
- a reflux condenser is provided to condense the condensable material and return it to the reactor. Thus, a substantial portion of the heat of reaction is removed by condensation of the reactants vaporized throughout the reaction.
- Peterson maintains a liquid level above the topmost catalyst bed but allows room for vapors to escape to the condenser where the heat of reaction is removed.
- Larkin et al. in U.S. Pat. No. 5,189,233, disclose another liquid phase process for the hydrogenation of benzene to cyclohexane.
- Larkin et al. utilize high pressure (2500 psig) to maintain the reactants in the liquid state.
- Larkin, et al disclose the use of progressively more active catalyst as the concentration of benzene decreases to control the temperature and unwanted side reactions.
- Hui et al in U.S. Pat. No. 4,731,496, disclose a gas phase process for the hydrogenation of benzene to cyclohexane over a specific catalyst.
- the catalyst reported therein is nickel supported on a mixture of titanium dioxide and zirconium dioxide.
- U.S. Pat. No. 6,750,374 discloses a process for the hydrogenation of benzene using hydrogen containing up to about 15 mole % impurities, such as carbon monoxide and light hydrocarbons with an alumina supported catalyst containing from about 15 to 35 wt. % Ni and from about 1 to 15 wt. % Cu.
- the catalyst may contain additional elements such as Mo, Zn, Co, Fe.
- the present invention is a process and a catalyst used in the process for hydrogenation of aromatic compounds, such as benzene, aniline, naphthalene, phenol and benzene polycarboxylates, by hydrogenating the aromatic compound in the presence of a catalyst comprising from 4 to 14 wt. % Ni, preferably 9 to 10 wt. % Ni and up to about 0.9 wt. % Cu, preferably about 0.2 to 0.4 wt. % Cu deposited on a transition alumina support having a BET surface area from about 40 to 180 m 2 /g, and a pore volume from about 0.3 to about 0.8 cc/g.
- the hydrogenation of aromatic compounds is advantageously carried out in the presence of a high boiling solvent.
- the preferred solvent will have at least 10° F. higher boiling point than the aromatic compound to be hydrogenated and hydrogenated cyclic compound.
- the advantages of using a high boiling solvent are higher productivity of cyclohexane and keeping the temperature of catalytic reaction zone in a desired range.
- the high boiling solvent provides improvement in productivity of the reaction system whether or not the nickel catalyst is modified with copper.
- benzene is present in the reaction stream in an amount of 1 to 60 wt. %, preferentially of 3 to 40 wt. %.
- the hydrogen stream may be pure hydrogen or may contain up to 5 mole % impurities including carbon monoxide.
- the remaining components in the reaction stream can be cyclohexane, a high boiling solvent or a mixture of cyclohexane and a high boiling solvent. If a high boiling solvent is used, the solvent may comprise 10 to 90 wt. %, preferably 20 to 80 wt % of the reaction stream.
- the high boiling solvent may be recovered from the effluent recycle stream and recycled to hydrogenation reactor.
- the content of cyclohexane in the recycle solvent stream can be 0.0 to 80 wt. %, preferably from 0.5 to 30 wt %.
- the present invention also includes a copper modified nickel catalyst used in the hydrogenation of aromatic compound to produce a hydrogenated cyclic compound comprising 4 to 14 wt. % Ni and about 0.2 to 0.4 wt. % Cu deposited on a transition alumina support having a BET surface area from about 40 to 180 m 2 /g and a pore volume from about 0.3 to about 0.8 cc/g.
- This invention pertains to a catalytic hydrogenation process of aromatic compounds such as benzene, aniline, naphthalene and phenol in the presence of improved copper modified nickel-based catalyst supported on a porous support. Hydrogenation of benzene yields cyclohexane. But the hydrogenation product stream from the catalytic reactor contains other undesired by-products such as pentane, cyclopentane, methyl cyclopentane, n-hexane and methyl cyclohexane. The product stream usually contains a trace amount of benzene, up to about 200 ppm by weight. Less than 10 ppm benzene is highly desirable for the production of high purity cyclohexane.
- the amount of by-products in the effluent stream from a hydrogenation reactor increases with hydrogenation temperature or conversion of benzene or both. Especially the amount of the by-products rapidly increases with hydrogenation temperature higher than about 340° F.
- the hydrogenation of aniline yields cyclohexylamine. But the undesired side reactions are deamination, formation of di and triphenylamine and various heavier products.
- An advantage of the present invention is reduced by-products so that simple distillation of hydrogenation product stream produces high purity cyclohexane product.
- the cyclohexane product contains no more than about 50 ppm, preferably no more 30 ppm by weight impurities including unconverted benzene excluding impurities came in with the feed benzene.
- the hydrogenation reactor effluent contains small amounts of cyclohexene. Since cyclohexene can easily be hydrogenated to cyclohexane by recycling the reactor effluent or using a small separate reactor without producing significant amounts of by-product, it is not considered as an undesired by-product.
- the present invention provides a significant improvement of the productivity of cyclohexane as well as reducing total impurities in the product cyclohexane stream from the catalytic reaction zone to less than 10 ppm, if the benzene hydrogenation is carried out in the presence of a heavy solvent such as decalin and decane.
- a heavy solvent such as decalin and decane.
- the hydrogenation reaction can be carried out in any physical device such as catalytic distillation column, fixed bed reactor, boiling point reactor, stirred tank reactor, trickle bed reactors or any combination of these. Since the benzene hydrogenation reaction is exothermic reaction, the hydrogenation reaction for the traditional fixed bed operation is preferably carried out by recycling the reactor effluent stream to dilute the fresh benzene feed, which dilutes the heat of reaction. Although recycling the reactor effluent is not necessary for the catalytic distillation reactor, one may choose to do so.
- the present catalysts preferably comprise Ni and Cu and optionally one or more elements selected from the group consisting of Ag, Ru, Re, Zn, Mo and Pd which are deposited on a support comprising transitional aluminas such as crystalline alumina of gamma, kappa, delta, theta and alpha or a mixture comprised of two or three selected therefrom.
- a preferred nickel content of the catalyst is from about 9 to 10 wt. % and a preferred copper contents is from about 0.2 to 0.4 wt. %.
- the catalyst used in this invention is prepared by depositing nickel and copper on a porous support. Copper serves to improve the catalyst activity and selectivity.
- the catalyst may contain one or more elements as the second optional modifiers from Ag, Ru, Re, Zn, Mo, and Pd.
- the deposition of active metal components can be carried out by any technique such as incipient impregnation, spray coating impregnation.
- the preferred support will have average of size from about 0.5 mm to about 3 mm, preferably from about 1 mm to about 2.5 mm.
- the transition alumina is obtained by calcining at about 850 to about 1200° C., and preferably having the following physical properties after calcining at from 850 to 1200° C.: BET surface from about 40 to about 180 m 2 /g, preferably from 50 to 120 m 2 /g and pore volume from about 0.3 to about 0.8 cc/g.
- the transition alumina is the crystalline alumina of delta, theta, kappa or a mixture composed of two or three from gamma, kappa, delta, theta and alpha.
- the physical shapes of the preferred aluminas in this invention can be any shape such as spheres, extrudates, pellets and granules which preferably have diameters of less than about 1 ⁇ 4 inch, preferably 1 ⁇ 8 inch and less than about 1 ⁇ 2 inch length, and preferably less than 1 ⁇ 4 inch length for extrudates or pellets.
- Deposition of the nickel on a support can be carried out by single or multiple impregnations.
- a solution of the nickel compound is prepared by dissolving a nickel compound or an organo nickel compound in organic solvent or water.
- the examples of the nickel compounds are nickel salts such as nickel nitrate or organo metallic nickel compounds such as nickel acetate, nickel formate, nickel acetylacetonate and nickel alkoxides.
- the impregnation product is dried and calcined at temperature in a range from 200° to 600° C., preferably from 250° to 500° C.
- a commercial 28 wt. % Ni catalyst (1.2 mm diameter trilobe extrudates) was tested to hydrogenate of benzene.
- the crystal form of alumina support of this catalyst is gamma-alumina.
- the physical properties of this catalyst were 113 m 2 /g BET, 0.43 cc/g total nitrogen pore volume and an average pore diameter of 15 nm.
- 50 grams of the catalyst was loaded in a vertically mounted up-flow stainless steel fixed bed reactor (1 inch diameter by 20 inches long). Two thermocouples at each end of catalyst zone were installed to control the reactor temperature.
- the catalyst was supplied by the manufacturer as activated and passivated form, and recommended reactivation at 482° F. in hydrogen gas flow. The catalyst was reactivated at 250° F.
- a spherical gamma-alumina (1.68 mm diameter) support was calcined at 1100° C. for 3 hours.
- the alumina spheres prior to the calcination had 145 m 2 /g BET surface area, a total nitrogen volume of 0.925 cc/g and an average pore diameter of 21.6 nm.
- the diameter of alumina spheres was changed to 1.45 mm, which had 56 m 2 /g BET, a total nitrogen pore volume of 0.701 cc/g and an average pore diameter of 36.2 nm. Its x-ray diffraction indicated mostly theta-alumina with minor amount of delta.
- a mixed solution of nickel nitrate and copper nitrate was prepared by dissolving 86.5 grams of Ni(NO 3 ) 2 ⁇ 2.5H 2 O in 25.95 grams of water. 300 grams of the calcined alumina was placed in a rotary impregnator. The mixed solution was sprayed on rolling alumina spheres inside the rotary impregnator by using a liquid sprayer over a period of about 15 minutes. The content in the rotary impregnator was dried by blowing hot air in at about 200° C. The dried product was calcined at 350° C. for 2 hours.
- the second mixed solution was prepared by dissolving 65 grams of Ni(NO 3 ) 2 ⁇ 6H 2 O and 1.8 grams of Cu(NO 3 ) 2 ⁇ 2.5H 2 O in 19.5 grams of water.
- the second impregnation was performed on the first impregnation product in similar manner to the first impregnation.
- the dried impregnation product was calcined at 380° C. for 2 hours.
- the finished catalyst would contain 9.22 wt % Ni and 0.35 wt. % Cu.
- the physical properties of this catalyst were 60 m 2 /g, 0.56 cc/g total nitrogen pore volume and an average pore diameter of 39 nm. 50 grams of this catalyst was loaded in the same reactor used in the Control Example 1. The catalyst was activated at 250° F. in 300 cc/min gas flow of 33 volume % hydrogen gas in nitrogen for 1.5 hours and then for 3 hours at each 670 and 770° F. by passing 350 cc/min of pure hydrogen gas. The hydrogenation of benzene was carried out under various conditions. The results are listed in Table 2. As shown in Table 2, the hydrogenation reaction product streams from the reactor do not contain any detectable amounts of by-products. The performance of this catalyst is superior to the conventional nickel catalysts.
- a nickel catalyst was prepared according to US Publication No. 2005-0033099-A1.
- Gamma-Alumina (1.3 mm diameter trilobe extrudates) was calcined at about 1000° C. for 3 hours in air.
- the gamma-alumina had 252 m 2 /g BET, a total nitrogen pore volume of 0.571 cc/g and an average pore diameter of 8.85 nm.
- a solution of nickel nitrate was prepared by dissolving 183.6 g Ni(NO 3 ) 2 ⁇ 6H 2 O in 295 grams water.
- This example demonstrates the hydrogenation of benzene with recycle of reactor effluent in the absence of a heavy solvent.
- the feed to the reactor comprises fresh benzene feed and reactor effluent stream, which is cyclohexane.
- This experiment demonstrates hydrogenation of mixed feed stream to hydrogenation, where the mixed feed represents a stream obtained by mixing 1 weight portion of fresh benzene with 3 weight portion of the reactor effluent recycle steam.
- the same catalyst (50 grams) in the Example 2 was in the same reactor used in the Control Example 1.
- the catalyst was activated in same manner to the Example 2.
- a feed mixture of benzene and cyclohexane was prepared.
- the composition of the feed was 0.11 wt % lights, 25.41 wt % benzene and 74.48 wt % cyclohexane.
- the hydrogenation of benzene was carried out under various conditions.
- the impurities in the feed and product streams were analyzed with a trace go analysis method. The result is listed in Table 4.
- the impurities in product streams mostly originated from impurities in the feed.
- the total amount of various impurities (listed in Table 4) produced during the hydrogenation of benzene according to this invention is less than 10 ppm.
- the conversion of benzene could be forced so high that the benzene contents in the reactor effluent streams could be reduced to less than 35 ppm by weight.
- This example demonstrates that it is possible to obtain extremely high conversion (>99.99%) of benzene with a cyclohexane selectivity equivalent to about 99.999 mole %.
- the productivity of cyclohexane at two conditions of the two right columns in Table 4 was 29.2 and 31.8 m/fur per kg catalyst. This is a demonstration of superior catalyst performance compared to the prior art represented by Example 1.
- This example demonstrates the hydrogenation of benzene in the presence of decalin as high boiling solvent, where the conversions of benzene to cyclohexane are close to 100%.
- Example 2 50 grams of the catalyst prepared in the Example 2 was loaded in the same reactor used in the Control Example 1. The catalyst was activated in same manner to the Example 2.
- the feed was a mixture of 0.44 wt % lights, 25.26 wt % benzene and 74.30 wt % decalin.
- the hydrogenation of benzene was carried out under various conditions.
- the impurities in the feeds and product streams were analyzed with a regular GC analysis method and a trace GC analysis method. The results are listed in Table 5.
- the impurities in products under various conditions were mostly originated from impurities in feed.
- the total amount of various impurities produced during the hydrogenation of benzene according to this invention is less than 4 ppm by weight based on 100% cyclohexane.
- the trace amount of benzene in product stream can be reduced to less than 2 ppm in the product cyclohexane by adjusting the flow rate of hydrogen to the hydrogenation reactor at a given feed rate of benzene.
- This example demonstrates the hydrogenation of benzene in the presence of decane as high boiling solvent.
- the conversions of benzene were so high that the benzene contents in the product steams were close to undetectable.
- Example 2 50 grams of the catalyst prepared in the Example 2 was loaded in the same reactor used in the Control Example 1. The catalyst was activated in same manner to the Example 2.
- the feed was a mixture of 0.10 wt % lights, 30.26 wt % benzene and 69.64 wt % decane.
- the hydrogenation of benzene was carried out under various conditions.
- the impurities in the feeds and product streams were analyzed with a regular GC analysis method and a trace GC analysis method. The result is listed in Table 6.
- the impurities in products under various conditions mostly originated from impurities in the feed.
- the total amount of various impurities produced during the hydrogenation of benzene according to this invention is about 11 ppm based on 100% cyclohexane.
- the productivity of cyclohexane was equivalent or better than the case of performing the hydrogenation in the absence of a high boiling solvent in Example 4.
Abstract
A catalyst useful for hydrogenation of aromatic compounds to produce hydrogenated cyclic compound, the catalyst comprising from 4 to 10 wt. % Ni and 0.2 up to about 0.9 wt. % Cu deposited on a transition alumina support having a BET surface area from about 40 to 180 m2/g and pore volume from about 0.3 to about 0.8 cc/g.
Description
- This application, pursuant to 35 U.S.C. § 120, claims benefit to U.S. patent application Ser. No. 11/389,955, filed Mar. 27, 2006. That application is incorporated by reference in its entirety.
- 1. Field of the Invention
- The present invention relates to a process for hydrogenation of aromatic compounds such as the hydrogenation of benzene to cyclohexane and the supported nickel catalyst modified with up to 0.9 wt. % Cu therefore.
- 2. Background
- Cyclohexane is the main precursor for the production of nylon products and as such, the demand remains strong. Cyclohexane was first obtained by the direct fractional distillation of suitable crude petroleum refinery streams. Now the major portion of cyclohexane is obtained from the direct hydrogenation of benzene. Conventionally the reaction is carried out in vapor or mixed phase using a fixed bed reaction. The reactor temperature is controlled to be between 350 to 500° F. Higher temperatures can lead to thermodynamic limitations on benzene conversion, thermal cracking and increased byproduct. In general, the amount of byproducts in the effluent stream from a hydrogenation reactor increases with hydrogenation temperature or conversion of benzene or both.
- Peterson, in U.S. Pat. No. 2,373,501, discloses a liquid phase process for the hydrogenation of benzene to cyclohexane wherein a temperature differential is maintained between the top of the catalyst bed where benzene is fed and the outlet where substantially pure cyclohexane is withdrawn. The temperature differential is due to the change in the exothermic heat of reaction released as less and less benzene is converted as the concentration of benzene decreases. Specifically the top of the catalyst bed is at a higher temperature than the lower catalyst bed. Hydrogen is supplied countercurrent to the benzene/cyclohexane flow. Temperature control coils are disposed within the reactor to maintain the temperature differential if the exothermic heat of reaction is not sufficient or to cool the bed if too much heat is released. Peterson recognizes that although the bulk of his reaction takes place in the liquid phase a portion of the benzene and cyclohexane will be vaporized, especially near the top of the reactor where the benzene concentration is highest and conversion is highest. A reflux condenser is provided to condense the condensable material and return it to the reactor. Thus, a substantial portion of the heat of reaction is removed by condensation of the reactants vaporized throughout the reaction. Peterson maintains a liquid level above the topmost catalyst bed but allows room for vapors to escape to the condenser where the heat of reaction is removed.
- Larkin et al., in U.S. Pat. No. 5,189,233, disclose another liquid phase process for the hydrogenation of benzene to cyclohexane. However, Larkin et al. utilize high pressure (2500 psig) to maintain the reactants in the liquid state. In addition Larkin, et al disclose the use of progressively more active catalyst as the concentration of benzene decreases to control the temperature and unwanted side reactions.
- Hui et al, in U.S. Pat. No. 4,731,496, disclose a gas phase process for the hydrogenation of benzene to cyclohexane over a specific catalyst. The catalyst reported therein is nickel supported on a mixture of titanium dioxide and zirconium dioxide.
- U.S. Pat. No. 6,750,374 discloses a process for the hydrogenation of benzene using hydrogen containing up to about 15 mole % impurities, such as carbon monoxide and light hydrocarbons with an alumina supported catalyst containing from about 15 to 35 wt. % Ni and from about 1 to 15 wt. % Cu. The catalyst may contain additional elements such as Mo, Zn, Co, Fe.
- The present invention is a process and a catalyst used in the process for hydrogenation of aromatic compounds, such as benzene, aniline, naphthalene, phenol and benzene polycarboxylates, by hydrogenating the aromatic compound in the presence of a catalyst comprising from 4 to 14 wt. % Ni, preferably 9 to 10 wt. % Ni and up to about 0.9 wt. % Cu, preferably about 0.2 to 0.4 wt. % Cu deposited on a transition alumina support having a BET surface area from about 40 to 180 m2/g, and a pore volume from about 0.3 to about 0.8 cc/g. The hydrogenation of aromatic compounds is advantageously carried out in the presence of a high boiling solvent. The preferred solvent will have at least 10° F. higher boiling point than the aromatic compound to be hydrogenated and hydrogenated cyclic compound. The advantages of using a high boiling solvent are higher productivity of cyclohexane and keeping the temperature of catalytic reaction zone in a desired range. The high boiling solvent provides improvement in productivity of the reaction system whether or not the nickel catalyst is modified with copper.
- In the production cyclohexane, benzene is present in the reaction stream in an amount of 1 to 60 wt. %, preferentially of 3 to 40 wt. %. The hydrogen stream may be pure hydrogen or may contain up to 5 mole % impurities including carbon monoxide. The remaining components in the reaction stream can be cyclohexane, a high boiling solvent or a mixture of cyclohexane and a high boiling solvent. If a high boiling solvent is used, the solvent may comprise 10 to 90 wt. %, preferably 20 to 80 wt % of the reaction stream. The high boiling solvent may be recovered from the effluent recycle stream and recycled to hydrogenation reactor. The content of cyclohexane in the recycle solvent stream can be 0.0 to 80 wt. %, preferably from 0.5 to 30 wt %.
- The present invention also includes a copper modified nickel catalyst used in the hydrogenation of aromatic compound to produce a hydrogenated cyclic compound comprising 4 to 14 wt. % Ni and about 0.2 to 0.4 wt. % Cu deposited on a transition alumina support having a BET surface area from about 40 to 180 m2/g and a pore volume from about 0.3 to about 0.8 cc/g.
- Other aspects and advantages will be apparent from the following description and the appended claims.
- This invention pertains to a catalytic hydrogenation process of aromatic compounds such as benzene, aniline, naphthalene and phenol in the presence of improved copper modified nickel-based catalyst supported on a porous support. Hydrogenation of benzene yields cyclohexane. But the hydrogenation product stream from the catalytic reactor contains other undesired by-products such as pentane, cyclopentane, methyl cyclopentane, n-hexane and methyl cyclohexane. The product stream usually contains a trace amount of benzene, up to about 200 ppm by weight. Less than 10 ppm benzene is highly desirable for the production of high purity cyclohexane. In general, the amount of by-products in the effluent stream from a hydrogenation reactor increases with hydrogenation temperature or conversion of benzene or both. Especially the amount of the by-products rapidly increases with hydrogenation temperature higher than about 340° F. The hydrogenation of aniline yields cyclohexylamine. But the undesired side reactions are deamination, formation of di and triphenylamine and various heavier products. An advantage of the present invention is reduced by-products so that simple distillation of hydrogenation product stream produces high purity cyclohexane product. Preferably the cyclohexane product contains no more than about 50 ppm, preferably no more 30 ppm by weight impurities including unconverted benzene excluding impurities came in with the feed benzene. The hydrogenation reactor effluent contains small amounts of cyclohexene. Since cyclohexene can easily be hydrogenated to cyclohexane by recycling the reactor effluent or using a small separate reactor without producing significant amounts of by-product, it is not considered as an undesired by-product. The present invention provides a significant improvement of the productivity of cyclohexane as well as reducing total impurities in the product cyclohexane stream from the catalytic reaction zone to less than 10 ppm, if the benzene hydrogenation is carried out in the presence of a heavy solvent such as decalin and decane. An additional advantage of using heavy solvent is substantially less recycle of hydrogen.
- The hydrogenation reaction can be carried out in any physical device such as catalytic distillation column, fixed bed reactor, boiling point reactor, stirred tank reactor, trickle bed reactors or any combination of these. Since the benzene hydrogenation reaction is exothermic reaction, the hydrogenation reaction for the traditional fixed bed operation is preferably carried out by recycling the reactor effluent stream to dilute the fresh benzene feed, which dilutes the heat of reaction. Although recycling the reactor effluent is not necessary for the catalytic distillation reactor, one may choose to do so.
- The present catalysts preferably comprise Ni and Cu and optionally one or more elements selected from the group consisting of Ag, Ru, Re, Zn, Mo and Pd which are deposited on a support comprising transitional aluminas such as crystalline alumina of gamma, kappa, delta, theta and alpha or a mixture comprised of two or three selected therefrom. A preferred nickel content of the catalyst is from about 9 to 10 wt. % and a preferred copper contents is from about 0.2 to 0.4 wt. %. The catalyst used in this invention is prepared by depositing nickel and copper on a porous support. Copper serves to improve the catalyst activity and selectivity. The catalyst may contain one or more elements as the second optional modifiers from Ag, Ru, Re, Zn, Mo, and Pd. The deposition of active metal components can be carried out by any technique such as incipient impregnation, spray coating impregnation. The preferred support will have average of size from about 0.5 mm to about 3 mm, preferably from about 1 mm to about 2.5 mm.
- The transition alumina is obtained by calcining at about 850 to about 1200° C., and preferably having the following physical properties after calcining at from 850 to 1200° C.: BET surface from about 40 to about 180 m2/g, preferably from 50 to 120 m2/g and pore volume from about 0.3 to about 0.8 cc/g. The transition alumina is the crystalline alumina of delta, theta, kappa or a mixture composed of two or three from gamma, kappa, delta, theta and alpha.
- The physical shapes of the preferred aluminas in this invention can be any shape such as spheres, extrudates, pellets and granules which preferably have diameters of less than about ¼ inch, preferably ⅛ inch and less than about ½ inch length, and preferably less than ¼ inch length for extrudates or pellets.
- Deposition of the nickel on a support can be carried out by single or multiple impregnations. A solution of the nickel compound is prepared by dissolving a nickel compound or an organo nickel compound in organic solvent or water. The examples of the nickel compounds are nickel salts such as nickel nitrate or organo metallic nickel compounds such as nickel acetate, nickel formate, nickel acetylacetonate and nickel alkoxides. The impregnation product is dried and calcined at temperature in a range from 200° to 600° C., preferably from 250° to 500° C.
- When the hydrogenation of benzene is carried out in a fixed bed reactor, which is operated in boiling point mode, or in a catalytic distillation reactor, the heat of hydrogenation reaction is utilized to vaporize the product cyclohexane. The result of the vaporization is the internal cooling of the hydrogenation reaction zone. The overhead vapor stream from a catalytic distillation reactor, which is operated in the presence or absence of a high boiling solvent, comprises cyclohexane and hydrogen.
- A commercial 28 wt. % Ni catalyst (1.2 mm diameter trilobe extrudates) was tested to hydrogenate of benzene. The crystal form of alumina support of this catalyst is gamma-alumina. The physical properties of this catalyst were 113 m2/g BET, 0.43 cc/g total nitrogen pore volume and an average pore diameter of 15 nm. 50 grams of the catalyst was loaded in a vertically mounted up-flow stainless steel fixed bed reactor (1 inch diameter by 20 inches long). Two thermocouples at each end of catalyst zone were installed to control the reactor temperature. The catalyst was supplied by the manufacturer as activated and passivated form, and recommended reactivation at 482° F. in hydrogen gas flow. The catalyst was reactivated at 250° F. in 300 cc/min gas flow of 33 volume % hydrogen gas in nitrogen for 1.5 hours and then 575° F. for 5 hours in 350 cc/min flow of pure hydrogen gas. The hydrogenation of benzene was carried out under various conditions. The results are listed in Table 1.
-
TABLE 1 Temperature, ° F. 300 320 340 340 350 360 Pressure, psig 250 250 250 250 250 250 Benzene Rate, ml/min 6 6 11.2 6 6 6 Benzene Conversion, % 18.21 20.21 21.59 17.71 18.41 17.86 Selectivity of cyclohexane and cyclohexene 99.95 99.87 99.91 99.84 99.84 99.82 (mole %) By-products in product stream based on 10)% cyclohexane and cyclohexene combined (wt. ppm) Cyclopentane 439 1114 644 1296 1359 1520 Methylcyclohexane 0 0 7 0 0 0 Hexane 0 0 7 0 0 0 Methyl Cyclopentane 692 1306 472 1546 1669 1881 Sum of by-products 1131 2420 1130 2842 3028 3401 Cyclohexene 854 165 1661 1201 1309 2056 - A spherical gamma-alumina (1.68 mm diameter) support was calcined at 1100° C. for 3 hours. The alumina spheres prior to the calcination had 145 m2/g BET surface area, a total nitrogen volume of 0.925 cc/g and an average pore diameter of 21.6 nm. After calcination, the diameter of alumina spheres was changed to 1.45 mm, which had 56 m2/g BET, a total nitrogen pore volume of 0.701 cc/g and an average pore diameter of 36.2 nm. Its x-ray diffraction indicated mostly theta-alumina with minor amount of delta.
- A mixed solution of nickel nitrate and copper nitrate was prepared by dissolving 86.5 grams of Ni(NO3)2·2.5H2O in 25.95 grams of water. 300 grams of the calcined alumina was placed in a rotary impregnator. The mixed solution was sprayed on rolling alumina spheres inside the rotary impregnator by using a liquid sprayer over a period of about 15 minutes. The content in the rotary impregnator was dried by blowing hot air in at about 200° C. The dried product was calcined at 350° C. for 2 hours.
- The second mixed solution was prepared by dissolving 65 grams of Ni(NO3)2·6H2O and 1.8 grams of Cu(NO3)2·2.5H2O in 19.5 grams of water. The second impregnation was performed on the first impregnation product in similar manner to the first impregnation. The dried impregnation product was calcined at 380° C. for 2 hours.
- Based on the amount of materials used, the finished catalyst would contain 9.22 wt % Ni and 0.35 wt. % Cu. The examination of the catalyst spheres under microscope indicated that the active metal components were deposited in an outer layer of spheres. The average layer thickness was about 0.33 mm. The physical properties of this catalyst were 60 m2/g, 0.56 cc/g total nitrogen pore volume and an average pore diameter of 39 nm. 50 grams of this catalyst was loaded in the same reactor used in the Control Example 1. The catalyst was activated at 250° F. in 300 cc/min gas flow of 33 volume % hydrogen gas in nitrogen for 1.5 hours and then for 3 hours at each 670 and 770° F. by passing 350 cc/min of pure hydrogen gas. The hydrogenation of benzene was carried out under various conditions. The results are listed in Table 2. As shown in Table 2, the hydrogenation reaction product streams from the reactor do not contain any detectable amounts of by-products. The performance of this catalyst is superior to the conventional nickel catalysts.
-
TABLE 2 Temperature, ° F. 300 320 320 340 340 350 360 Pressure, psig 250 250 250 250 250 250 250 Benzene Rate, ml/min 6 6 11.2 11.2 6 6 6 Benzene Conversion, % 24.45 18.69 28.28 21.48 25.59 14.34 19.44 Selectivity of cyclohexane and 100 100 100 100 100 100 100 cyclohexene (mole %) By-products in product stream based on 10)% cyclohexane and cyclohexene combined (wt. ppm) Cyclopentane 0 0 0 0 0 0 0 Methylcyclohexane 0 0 0 0 0 0 0 Hexane 0 0 0 0 0 0 0 Methyl Cyclopentane 0 0 0 0 0 0 0 Sum of by-products 0 0 0 0 0 0 0 Cyclohexene 1613 4734 1285 12088 1549 3115 2235 - A nickel catalyst was prepared according to US Publication No. 2005-0033099-A1. Gamma-Alumina (1.3 mm diameter trilobe extrudates) was calcined at about 1000° C. for 3 hours in air. The gamma-alumina had 252 m2/g BET, a total nitrogen pore volume of 0.571 cc/g and an average pore diameter of 8.85 nm. A solution of nickel nitrate was prepared by dissolving 183.6 g Ni(NO3)2·6H2O in 295 grams water. 300 g of the calcined alumina support was placed in a rotary impregnator and then the nickel nitrate solution was poured on tumbling alumina extrudates in the rotary impregnator. After 15 minutes cold roll, the content in the rotary impregnator was dried at about 200° C. by blowing hot air into the rotary drier. The dried product was calcined at 380° C. for 2 hours. Based on the amount of nickel nitrate used to prepare this catalyst, the finished catalyst would have 11 wt % Ni on alumina support. Measurement of the physical properties of the finished catalyst indicated 133 m2/g BET surface area, a total nitrogen pore volume of 0.622 cc/g and an average pore diameter of 18.6 nm.
- 50 grams of this catalyst was loaded in the same reactor used in the Control Example 1. The catalyst was activated in identical manner to the Example 2. The hydrogenation of benzene was carried out under various conditions. The results are listed in Table 3. Comparing the performance data of this catalyst in Table 3 with those in the Table 1 of the Control Example 1 indicates a superior performance of this catalyst to conventional nickel catalysts, although it was not as good as the catalyst in the Example 2.
-
TABLE 3 Temperature, ° F. 300 320 340 340 350 360 Pressure, psig 250 250 250 250 250 250 Benzene Rate, ml/min 6 6 11.2 6 6 6 Benzene Conversion, % 18.92 28.28 21.48 25.59 14.34 19.44 Selectivity of cyclohexane and cyclohexene 100.00 100.00 99.97 99.94 99.95 99.97 (mole %) By-products in product stream based on 10)% cyclohexane and cyclohexene combined (wt. ppm) Cyclopentane 0 0 225 493 386 273 Methylcyclohexane 0 0 0 0 0 0 Hexane 0 0 0 0 0 0 Methyl Cyclopentane 0 0 0 0 0 0 Sum of by-products 0 0 225 493 386 273 Cyclohexene 555 846 890 565 765 1846 - This example demonstrates the hydrogenation of benzene with recycle of reactor effluent in the absence of a heavy solvent. But the feed to the reactor comprises fresh benzene feed and reactor effluent stream, which is cyclohexane. This experiment demonstrates hydrogenation of mixed feed stream to hydrogenation, where the mixed feed represents a stream obtained by mixing 1 weight portion of fresh benzene with 3 weight portion of the reactor effluent recycle steam.
- The same catalyst (50 grams) in the Example 2 was in the same reactor used in the Control Example 1. The catalyst was activated in same manner to the Example 2. A feed mixture of benzene and cyclohexane was prepared. The composition of the feed was 0.11 wt % lights, 25.41 wt % benzene and 74.48 wt % cyclohexane. The hydrogenation of benzene was carried out under various conditions. The impurities in the feed and product streams were analyzed with a trace go analysis method. The result is listed in Table 4. The impurities in product streams mostly originated from impurities in the feed. All combined, the total amount of various impurities (listed in Table 4) produced during the hydrogenation of benzene according to this invention is less than 10 ppm. The conversion of benzene could be forced so high that the benzene contents in the reactor effluent streams could be reduced to less than 35 ppm by weight. This example demonstrates that it is possible to obtain extremely high conversion (>99.99%) of benzene with a cyclohexane selectivity equivalent to about 99.999 mole %. The productivity of cyclohexane at two conditions of the two right columns in Table 4 was 29.2 and 31.8 m/fur per kg catalyst. This is a demonstration of superior catalyst performance compared to the prior art represented by Example 1.
-
TABLE 4 Temperature - in, ° F. 144 158 145 160 159 160 Temperature - out, ° F. 299 329 310 300 322 322 Pressure, psig 230 230 230 230 230 230 Hydrogen Rate, cc/min 155 185 287.5 340 500 500 Flow rate of feed sole, ml/min 6 6 11.2 11 29.6 10.5 WHSV, h−1 5.8 5.8 10.8 10.8 9.2 10.1 Benzene Conversion, % 77.26 99.81 74.21 83.26 100 99.99 Productivity of cyclohexane 29.2 31.8 (m/hr/kg) Trace Analysis (wt. ppm) Feed Isopentane 1.7 1.2 1.9 0.9 1.0 1.8 1.9 Methylpentane 12.5 12.0 14.3 12.7 13.1 10.9 10.9 Pentane 1.3 1.9 1.6 1.6 1.8 1.7 1.8 Cyclopentane 5.9 8.1 6.4 7.2 7.4 5.8 5.9 Hexane 13.5 13.3 15.3 13.9 14.0 12.4 12.5 Methyl Cyclopentane 11.1 12.4 13.1 12.1 12.2 10.8 10.9 Benzene — 5.78* 0.05* 6.59* 4.27* 9.9 34.2 Cyclohexane — — — — — — — Cyclohexene 4.7 14.8 5.5 24.9 4.8 4.5 0 Methyl cyclohexane 7.2 8.9 7.6 8.7 9.4 9.3 9.4 Toluene 3.1 3.2 3.2 2.3 1.7 0 0 *Weight % - This example demonstrates the hydrogenation of benzene in the presence of decalin as high boiling solvent, where the conversions of benzene to cyclohexane are close to 100%.
- 50 grams of the catalyst prepared in the Example 2 was loaded in the same reactor used in the Control Example 1. The catalyst was activated in same manner to the Example 2. The feed was a mixture of 0.44 wt % lights, 25.26 wt % benzene and 74.30 wt % decalin. The average total combined impurities in the feed, which boil at temperatures near to cyclohexane, were about 14.8 ppm. The hydrogenation of benzene was carried out under various conditions. The impurities in the feeds and product streams were analyzed with a regular GC analysis method and a trace GC analysis method. The results are listed in Table 5. The impurities in products under various conditions were mostly originated from impurities in feed. All combined, the total amount of various impurities produced during the hydrogenation of benzene according to this invention is less than 4 ppm by weight based on 100% cyclohexane. The trace amount of benzene in product stream can be reduced to less than 2 ppm in the product cyclohexane by adjusting the flow rate of hydrogen to the hydrogenation reactor at a given feed rate of benzene.
- Surprisingly no trace amount of cyclohexene in any product stream was found. The productivity of cyclohexane was at least 40% higher than carrying out hydrogenation in the absence of a high boiling solvent in Example 4.
-
TABLE 5 Temperature - in, ° F. 218 220 219 220 Temperature - out, ° F. 322 330 328 333 Pressure, psig 230 230 230 230 Hydrogen Rate, cc/min 400 430 385 405 Flow rate of feed sole, ml/min 15 15 13 13 WHSV, h−1 16 16 13.9 13.9 Benzene Conversion, % 100 100 100 100 Productivity of cyclohexane 50.9 50.9 44.2 44.3 (m/hr/kg) Trace Analysis (wt. ppm) Feed Isopentane 1.0 1.4 1.2 1.6 0.3 Pentane 1 0.3 0.3 0.3 0.3 Cyclopentane 0 0.6 0.4 0.3 0.3 Hexane 5.0 0.4 0.3 1.3 1.3 Methyl Cyclopentane 1.1 0.6 0.4 0.4 0.4 Benzene — 14.9 5.1 0.3 0.3 Cyclohexane — — — — — Cyclohexene 0.2 0 0 0 0 Methyl cyclohexane 4.7 7.0 6.7 6.7 6.5 Toluene 2.1 0 0 0 0 - This example demonstrates the hydrogenation of benzene in the presence of decane as high boiling solvent. The conversions of benzene were so high that the benzene contents in the product steams were close to undetectable.
- 50 grams of the catalyst prepared in the Example 2 was loaded in the same reactor used in the Control Example 1. The catalyst was activated in same manner to the Example 2. The feed was a mixture of 0.10 wt % lights, 30.26 wt % benzene and 69.64 wt % decane. The average total combined impurities (excluding benzene) in the feed, which boil at temperatures near to cyclohexane, was about 5.77 ppm. The hydrogenation of benzene was carried out under various conditions. The impurities in the feeds and product streams were analyzed with a regular GC analysis method and a trace GC analysis method. The result is listed in Table 6. The impurities in products under various conditions mostly originated from impurities in the feed. All combined, the total amount of various impurities produced during the hydrogenation of benzene according to this invention is about 11 ppm based on 100% cyclohexane. The productivity of cyclohexane was equivalent or better than the case of performing the hydrogenation in the absence of a high boiling solvent in Example 4.
-
TABLE 6 Temperature - in, ° F. 165 165 164 Temperature - out, ° F. 335 327 334 Pressure, psig 230 230 230 Hydrogen Rate, cc/min 400 400 450 Flow rate of feed sole, ml/min 9 8.5 10 WHSV, h−1 9.6 8 11 Benzene Conversion, % 100 100 100 Productivity of cyclohexane 36.4 32.6 40.5 (m/hr/kg) Trace Analysis (wt. ppm) Feed Isopentane 0.2 0.2 0.3 0.2 Cyclopentane 0.1 0.9 1.0 0.9 Methyl Pentane <0.1 0.1 0.2 <0.1 Hexane 0.2 0.9 1.0 0.5 Methyl Cyclopentane 1.7 2.4 2.4 2.0 Benzene — 0.02 <0.01 0.02 Cyclohexane 2.5 — — — Cyclohexene <0.1 1.4 1.3 0 Methyl cyclohexane 2.3 4.6 4.4 4.5 Toluene 1.7 0 0 0 - While the disclosure includes a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments may be devised which do not depart from the scope of the present disclosure. Accordingly, the scope should be limited only by the attached claims.
Claims (16)
1. A copper modified nickel catalyst useful for the hydrogenation of aromatic compound to produce a hydrogenated cyclic compound, the catalyst comprising
4 to 10 wt. % Ni and about 0.2 to 0.9 wt. % Cu deposited on a transition alumina support having a BET surface area from about 40 to 180 m2/g and a pore volume from about 0.3 to about 0.8 cc/g.
2. The catalyst according to claim 1 wherein the catalyst contains one or more modifiers selected from the group consisting of Ag, Ru, Re, Zn, Mo and Pd.
3. The catalyst according to claim 1 wherein the Cu content is about 0.2 to 0.4 wt. %.
4. The catalyst according to claim 1 wherein the Ni content of the catalyst is about 9 to 10 wt %.
5. The catalyst according to claim 1 :
wherein the Ni content of the catalyst is about 9 to 10 wt %;
wherein the Cu content is about 0.2 to 0.4 wt. %; and
wherein the catalyst contains one or more modifiers selected from the group consisting of Ag, Ru, Re, Zn, Mo and Pd.
6. The catalyst according to claim 1 , wherein the transition alumina support is obtained by calcining at a temperature in the range from about 850 to about 1200° C.
7. The catalyst according to claim 1 , wherein the transition alumina support has a BET surface area from about 50 to about 120 m2/g.
8. The catalyst according to claim 1 , wherein the transition alumina comprises one or more of delta alumina, theta alumina, and kappa alumina.
9. A copper modified nickel catalyst useful for the hydrogenation of benzene to produce cyclohexane, the catalyst comprising
4 to 10 wt. % Ni and about 0.2 to 0.9 wt. % Cu deposited on a transition alumina support having a BET surface area from about 40 to 180 m2/g and a pore volume from about 0.3 to about 0.8 cc/g.
10. The catalyst according to claim 9 wherein the catalyst contains one or more modifiers selected from the group consisting of Ag, Ru, Re, Zn, Mo and Pd.
11. The catalyst according to claim 9 wherein the Cu content is about 0.2 to 0.4 wt. %.
12. The catalyst according to claim 9 wherein the Ni content of the catalyst is about 9 to 10 wt %.
13. The catalyst according to claim 9 :
wherein the Ni content of the catalyst is about 9 to 10 wt %;
wherein the Cu content is about 0.2 to 0.4 wt. %; and
wherein the catalyst contains one or more modifiers selected from the group consisting of Ag, Ru, Re, Zn, Mo and Pd.
14. The catalyst according to claim 9 , wherein the transition alumina support is obtained by calcining at a temperature in the range from about 850 to about 1200° C.
15. The catalyst according to claim 9 , wherein the transition alumina support has a BET surface area from about 50 to about 120 m2/g.
16. The catalyst according to claim 9 , wherein the transition alumina comprises one or more of delta alumina, theta alumina, and kappa alumina.
Priority Applications (1)
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US11/389,955 US7348463B2 (en) | 2006-03-27 | 2006-03-27 | Hydrogenation of aromatic compounds |
US12/021,809 US20080139383A1 (en) | 2006-03-27 | 2008-01-29 | Hydrogenation of aromatic compounds |
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US (2) | US7348463B2 (en) |
EP (1) | EP1999101A4 (en) |
JP (1) | JP2009531426A (en) |
KR (1) | KR20080108140A (en) |
CN (2) | CN102172531A (en) |
RU (1) | RU2391326C1 (en) |
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US20100280294A1 (en) * | 2007-10-19 | 2010-11-04 | Peter Birke | Catalyst for the hydrogenation of unsaturated hydrocarbons and process for its preparation |
US8518851B2 (en) * | 2007-10-19 | 2013-08-27 | Shell Oil Company | Catalyst for the hydrogenation of unsaturated hydrocarbons and process for its preparation |
US8841498B2 (en) * | 2007-10-19 | 2014-09-23 | Shell Oil Company | Catalyst for the hydrogenation of unsaturated hydrocarbons and process for its preparation |
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US20110201847A1 (en) * | 2008-05-30 | 2011-08-18 | Woelk Hans-Joerg | Method for the production of nanocrystalline nickel oxides |
US8759249B2 (en) * | 2008-05-30 | 2014-06-24 | Sued-Chemie Ip Gmbh & Co. Kg | Method for the production of nanocrystalline nickel oxides |
CN102925935A (en) * | 2012-11-13 | 2013-02-13 | 上海应用技术学院 | Preparation method and application of nickel-copper-aluminum oxide catalysis separation composite membrane |
US11673125B2 (en) | 2016-08-18 | 2023-06-13 | The University Of Chicago | Metal oxide-supported earth-abundant metal catalysts for highly efficient organic transformations |
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Also Published As
Publication number | Publication date |
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RU2008142366A (en) | 2010-05-10 |
KR20080108140A (en) | 2008-12-11 |
JP2009531426A (en) | 2009-09-03 |
TW200736209A (en) | 2007-10-01 |
EP1999101A4 (en) | 2009-08-19 |
CN102172531A (en) | 2011-09-07 |
CN101045669A (en) | 2007-10-03 |
US20070225531A1 (en) | 2007-09-27 |
RU2391326C1 (en) | 2010-06-10 |
EP1999101A1 (en) | 2008-12-10 |
US7348463B2 (en) | 2008-03-25 |
CN101045669B (en) | 2011-07-13 |
WO2007126421A1 (en) | 2007-11-08 |
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