CN104876802A - Method for synthesizing cyclohexanol directly through aniline hydrogenation - Google Patents
Method for synthesizing cyclohexanol directly through aniline hydrogenation Download PDFInfo
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- CN104876802A CN104876802A CN201510262328.5A CN201510262328A CN104876802A CN 104876802 A CN104876802 A CN 104876802A CN 201510262328 A CN201510262328 A CN 201510262328A CN 104876802 A CN104876802 A CN 104876802A
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- aniline
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- cyclohexanol
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000012074 organic phase Substances 0.000 claims abstract description 29
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 230000003292 diminished effect Effects 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 6
- 239000002134 carbon nanofiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000000605 extraction Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000011085 pressure filtration Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 29
- 238000004587 chromatography analysis Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000004445 quantitative analysis Methods 0.000 description 13
- 229910052707 ruthenium Inorganic materials 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-O [NH3+]c1ccccc1 Chemical compound [NH3+]c1ccccc1 PAYRUJLWNCNPSJ-UHFFFAOYSA-O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxo-reaction combined with reduction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing cyclohexanol directly through aniline hydrogenation, which comprises the following steps: putting aniline, a catalyst, water and tert-butyl alcohol into a high-pressure reaction kettle, feeding N2 for replacement, heating to 140-200 DEG C, feeding hydrogen until the pressure is 4-8 MPa and maintained, reacting for 4-16h, stopping feeding hydrogen, cooling to room temperature, carrying out reduced-pressure filtration on the obtained object so as to separate the catalyst from reaction liquid, and carrying out extraction separation on the reaction liquid, so that a cyclohexanol-containing organic phase is obtained, wherein the mole ratio of the aniline, the catalyst, the water and the tert-butyl alcohol is 1:(0.0005-0.05):(1-10000):(0.01-10); and the catalyst is a supported metal catalyst. The method disclosed by the invention is an efficient and inexpensive new method, and the yield of cyclohexanol is close to 100%.
Description
Technical field
The present invention relates to a kind of novel method by the direct synthesizing cyclohexanol of aniline hydrogenation, being specially a kind of is raw material with aniline, and the technological process of the direct synthesizing cyclohexanol of load type metal catalyst catalysed aniline hydrogenation, belongs to chemical process technology field.
Background technology
Hexalin is important Organic Chemicals, is the important intermediate of the fine chemicals such as synthesis of caprolactam, hexanodioic acid and medicine, coating, dyestuff.
At present, the synthetic method of hexalin has three kinds substantially.(1) take phenol as raw material, a step shortening prepares hexalin, and this method is relatively simple, but is restricted because phenol price is higher.(2) be raw material with benzene, complete hydrogenation obtains hexanaphthene, then obtains hexalin or pimelinketone through oxidation step.This is the topmost production method of current hexalin, but the oxidising process more complicated of hexanaphthene, selectivity is very low, and condition is harsh, easily sets off an explosion.(3) Asahi Chemical Industry's technique (Mitsui O, Fukuoka Y.Cycloalkanols:JP, 83209150.1983-11-09), and realize industrialization.This technique is divided into two steps: (a) take benzene as raw material, 100 ~ 180 DEG C, 3 ~ 10MPa, ruthenium catalyst condition under carry out Partial hydrogenation reaction prepare tetrahydrobenzene, the transformation efficiency 50% ~ 60% of benzene, the selectivity of tetrahydrobenzene be 80%, 20% by product be hexanaphthene; B (), under supersiliceous zeolite ZSM-5 catalyst action, cyclohexene hydration generates hexalin, and the per pass conversion 10% ~ 15% of tetrahydrobenzene, the selectivity of hexalin can reach 99.13%.This operational path is complicated, and especially the efficiency of partial hydrogenation of benzene synthesizing cyclohexene is not high, thus causes production cost higher.
Therefore, in view of the production status of above-mentioned hexalin, the research and development of its new synthetic process, new technology is subject to the attention of academia and enterprise always.Chinese scholars is devoted to attempt adopting diverse ways to improve traditional cyclohexanol production technique or the exploration new catalyzer of exploitation and catalysis technique to replace traditional technology always.
Based on this, the present invention proposes a kind of novel method by the direct synthesizing cyclohexanol of aniline hydrogenation, is namely raw material with aniline, the technological process of the direct synthesizing cyclohexanol of load type metal catalyst catalysed aniline hydrogenation.
Summary of the invention
The present invention is directed to current cyclohexanol production complex process, the present situation that cost is increased, a kind of novel method of efficient, inexpensive synthesizing cyclohexanol is provided.The hexalin synthetic method of the present invention's structure Ru shown in reacted formula (1), novelty take aniline as raw material, by taking load type metal as catalyzer, the technological process of the direct synthesizing cyclohexanol of hydrogenation.Yield of the present invention is close to 100%.
Technical scheme of the present invention is:
By a method for the direct synthesizing cyclohexanol of aniline hydrogenation, comprise the following steps:
Aniline, catalyzer, water and the trimethyl carbinol are placed in autoclave, logical N
2replace, be then warming up to 140 ~ 200 DEG C, pass into hydrogen to 4 ~ 8MPa and keep, after reaction 4 ~ 16h, stop logical hydrogen, be cooled to room temperature, then filtration under diminished pressure separating catalyst and reaction solution, reaction solution obtains the organic phase containing hexalin after extracting and separating;
Wherein, material mol ratio is aniline: catalyzer: water: the trimethyl carbinol=1:0.0005 ~ 0.05:1 ~ 10000:0.01 ~ 10;
Described catalyzer is load type metal catalyst, and the composition of catalyzer comprises active metal and carrier, and active metal charge capacity is mass percent 0.1 ~ 10%; Catalyzer mole number is with the molar amount of active metal;
Described active metal is Ru.
Described support of the catalyst is gac, carbon nano fiber, CNT (carbon nano-tube), Al
2o
3, SiO
2, TiO
2or molecular sieve.
Described material proportion is preferably: aniline: catalyzer: water: the trimethyl carbinol=1:0.001 ~ 0.02:400 ~ 1400:0.1 ~ 10.
Described temperature of reaction is preferably 160 ~ 200 DEG C.
The described reaction times is preferably 4 ~ 10h.
The present invention compared with prior art has following beneficial effect:
The novel method of the direct synthesizing cyclohexanol of a kind of aniline hydrogenation provided by the present invention, having not yet to see with aniline is the report that the operational path of Material synthesis hexalin is relevant.And compare traditional cyclohexane liquid-phase oxidation method, phenol hydrogenation method and cyclohexene hydration method synthesizing cyclohexanol, method of the present invention has that raw material aniline is cheaply easy to get, building-up process is more simple and direct, reaction yield high, reaction conditions is fairly simple clean, water both also served as raw material as solvent, the trimethyl carbinol, as the second solvent, strengthens the mutual solubility of water and aniline.Experiment proves, method of the present invention prepares hexalin, and the yield of hexalin is close to 100%.And other hexalin synthetic method step is various, efficiency is lower.It is a kind of efficient, inexpensive novel method that aniline of the present invention adds the method that hydroformylation step prepares hexalin, has opened up the technological line of hexalin synthesis.
Embodiment
Substantive features of the present invention and unusual effect can be embodied from following embodiment, but they do not impose any restrictions the present invention, and person skilled in art content according to the present invention can make some nonessential improvement and adjustment.In following embodiment, method therefor is ordinary method if no special instructions, and agents useful for same all can obtain from commercial channels.Below by embodiment, the present invention is further illustrated.
The load type metal catalyst adopted in following embodiment is well known materials, can directly be purchased or adopt to prepare with the following method:
By the RuCl of required charge capacity
3solution is dissolved in the hydrochloric acid soln of 10mol/L or the aqueous solution and is made into steeping fluid, and incipient impregnation is to carrier (gac, carbon nano fiber, CNT (carbon nano-tube), Al
2o
3, SiO
2, TiO
2, molecular sieve) on, after dipping 24h, at 100 DEG C of dry 5h, then at 300 DEG C with H
2reductase 12 h.
Embodiment 1
Aniline 1.5g is added successively, 2% (wt) Ru/MCM-41 (molecular sieve) catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:583:6.5) in autoclave.Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 4.4MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 99.6%.
Embodiment 2
Aniline 1.5g is added successively, 2%Ru/AC catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:583:6.5) in autoclave.Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 4.4MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 99.9%.
Embodiment 3
Aniline 1.5g is added successively, 2%Ru/SiO in autoclave
2catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:583:6.5).Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 4.4MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 99.6%.
Embodiment 4
Aniline 1.5g is added successively, 2%Ru/TiO in autoclave
2catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:583:6.5).Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 4.4MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 97.2%.
Embodiment 5
Aniline 1.5g is added successively, 2%Ru/ γ-Al in autoclave
2o
3catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:583:6.5).Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 4.4MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 76.8%.
Embodiment 6
Aniline 1.5g is added successively, 2%Ru/H β (molecular sieve) catalyzer 0.41g, trimethyl carbinol 10ml and water 170ml (its mol ratio is 1:0.005:583:6.5) in autoclave.Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 4.4MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 99.1%.
Embodiment 7
Aniline 1.5g is added successively, 2%Ru/HZSM-5 (molecular sieve) catalyzer 0.41g, water 10ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:34.3:6.5) in autoclave.Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 7.0MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 47.9%.
Embodiment 8
Aniline 1.5g is added successively, 2%Ru/CNT (CNT (carbon nano-tube)) catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:583:6.5) in autoclave.Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 7.0MPa, after reaction 10h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 96.0%.
Embodiment 9
Aniline 1.5g is added successively, 2%Ru/CNF (carbon nano fiber) catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:583:6.5) in autoclave.Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 8.0MPa, after reaction 5h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 96.7%.
Embodiment 10
Aniline 1.5g is added successively, 2%Ru/MCM-41 (molecular sieve) catalyzer 0.41g, water 200ml and trimethyl carbinol 1ml (its mol ratio is 1:0.005:686:0.65) in autoclave.Logical N
2replace.Then be warming up to 180 DEG C, then pass into hydrogen to reaction pressure 5.0MPa, after reaction 10h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 99.0%.
Embodiment 11
Aniline 1.5g is added successively, 2%Ru/MCM-41 (molecular sieve) catalyzer 0.41g, water 100ml and trimethyl carbinol 10ml (its mol ratio is 1:0.005:343:6.5) in autoclave.Logical N
2replace.Then be warming up to 140 DEG C, then pass into hydrogen to reaction pressure 7.0MPa, after reaction 4h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 80.5%.
Embodiment 12
Aniline 1.5g is added successively, 0.5%Ru/AC catalyzer 0.41g, water 170ml and trimethyl carbinol 10ml (its mol ratio is 1:0.00125:583:6.5) in autoclave.Logical N
2replace.Then be warming up to 160 DEG C, then pass into hydrogen to reaction pressure 8.0MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 92.2%.
Embodiment 13
Aniline 1.5g is added successively, 5%Ru/SiO in autoclave
2catalyzer 0.41g, water 400ml and trimethyl carbinol 10ml (its mol ratio is 1:0.0125:1372:6.5).Logical N
2replace.Then be warming up to 160 DEG C, then pass into hydrogen to reaction pressure 8.0MPa, after reaction 8h, stop logical hydrogen, cooling.Filtration under diminished pressure separating catalyst and reaction solution, reaction solution can obtain organic phase after toluene extracting and separating, and organic phase carries out gas chromatographic analysis.The yield of quantitative Analysis product hexalin is 99.5%.
Unaccomplished matter of the present invention is known technology.
Claims (5)
1., by a method for the direct synthesizing cyclohexanol of aniline hydrogenation, it is characterized by and comprise the following steps:
Aniline, catalyzer, water and the trimethyl carbinol are placed in autoclave, logical N
2replace, be then warming up to 140 ~ 200 DEG C, pass into hydrogen to 4 ~ 8MPa and keep, after reaction 4 ~ 16h, stop logical hydrogen, be cooled to room temperature, then filtration under diminished pressure separating catalyst and reaction solution, reaction solution obtains the organic phase containing hexalin after extracting and separating;
Wherein, material mol ratio is aniline: catalyzer: water: the trimethyl carbinol=1:0.0005 ~ 0.05:1 ~ 10000:0.01 ~ 10;
Described catalyzer is load type metal catalyst, and the composition of catalyzer comprises active metal and carrier, and active metal charge capacity is mass percent 0.1 ~ 10%; Catalyzer mole number is with the molar amount of active metal;
Described active metal is Ru.
2., as claimed in claim 1 by the method for the direct synthesizing cyclohexanol of aniline hydrogenation, it is characterized by described support of the catalyst is gac, carbon nano fiber, CNT (carbon nano-tube), Al
2o
3, SiO
2, TiO
2or molecular sieve.
3., as claimed in claim 1 by the method for the direct synthesizing cyclohexanol of aniline hydrogenation, it is characterized by described material proportion and be preferably: aniline: catalyzer: water: the trimethyl carbinol=1:0.001 ~ 0.02:400 ~ 1400:0.1 ~ 10.
4., as claimed in claim 1 by the method for the direct synthesizing cyclohexanol of aniline hydrogenation, it is characterized by described temperature of reaction and be preferably 160 ~ 200 DEG C.
5., as claimed in claim 1 by the method for the direct synthesizing cyclohexanol of aniline hydrogenation, it is characterized by the described reaction times is preferably 4 ~ 10h.
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| CN201510262328.5A CN104876802B (en) | 2015-05-21 | 2015-05-21 | A kind of method that Hexalin is directly synthesized by aniline hydrogenation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870889A (en) * | 2022-06-07 | 2022-08-09 | 华南农业大学 | Ru-RuO 2 -Nb 2 O 5 Bimetallic catalyst and preparation method and application thereof |
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| US2606925A (en) * | 1949-12-15 | 1952-08-12 | Du Pont | Ruthenium catalyzed hydrogenation process for obtaining aminocyclohexyl compounds |
| CN1634860A (en) * | 2004-11-23 | 2005-07-06 | 中国石化集团南京化学工业有限公司磷肥厂 | Gas distributor in fluidized bed of aniline synthesis and aniline synthesis method |
| USD606925S1 (en) * | 2009-05-19 | 2009-12-29 | The Goodyear Tire & Rubber Company | Tire |
-
2015
- 2015-05-21 CN CN201510262328.5A patent/CN104876802B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2606925A (en) * | 1949-12-15 | 1952-08-12 | Du Pont | Ruthenium catalyzed hydrogenation process for obtaining aminocyclohexyl compounds |
| CN1634860A (en) * | 2004-11-23 | 2005-07-06 | 中国石化集团南京化学工业有限公司磷肥厂 | Gas distributor in fluidized bed of aniline synthesis and aniline synthesis method |
| USD606925S1 (en) * | 2009-05-19 | 2009-12-29 | The Goodyear Tire & Rubber Company | Tire |
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| Title |
|---|
| SHIGEO NISHIMURA ET AL.: "The Hydroxide-Blacks of Ruthenium and Rhodium as Catalysts for the Hydrogenation of Organic Compounds. II.The Effects of Solvents and Added Alkalis in the Hydrogenation of Aniline", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》 * |
| 美国化学会: "Liquid-phase hydrogenation of aniline, along with its conversion products,in the presence of ruthenium on magnesium oxide", 《STN》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114870889A (en) * | 2022-06-07 | 2022-08-09 | 华南农业大学 | Ru-RuO 2 -Nb 2 O 5 Bimetallic catalyst and preparation method and application thereof |
| CN114870889B (en) * | 2022-06-07 | 2023-08-15 | 华南农业大学 | Ru-RuO 2 -Nb 2 O 5 Bimetallic catalyst and preparation method and application thereof |
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