CN101279892B - Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene - Google Patents
Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene Download PDFInfo
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- CN101279892B CN101279892B CN2007100678062A CN200710067806A CN101279892B CN 101279892 B CN101279892 B CN 101279892B CN 2007100678062 A CN2007100678062 A CN 2007100678062A CN 200710067806 A CN200710067806 A CN 200710067806A CN 101279892 B CN101279892 B CN 101279892B
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- cyclohexanediol
- tetrahydrobenzene
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- catalyzed oxidation
- oxidation preparation
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 20
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 title abstract description 10
- 230000003197 catalytic effect Effects 0.000 title abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 125000003944 tolyl group Chemical group 0.000 claims abstract 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 5
- 235000019253 formic acid Nutrition 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 15
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 12
- ODZTXUXIYGJLMC-UHFFFAOYSA-N 2-hydroxycyclohexan-1-one Chemical compound OC1CCCCC1=O ODZTXUXIYGJLMC-UHFFFAOYSA-N 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AJSHDAOMUKXVDC-UHFFFAOYSA-N butan-1-amine;sulfuric acid Chemical compound CCCC[NH3+].OS([O-])(=O)=O AJSHDAOMUKXVDC-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Abstract
The invention belongs to the glycol preparation technique field through the olefin selective oxidation. The invention aims to provide a method for preparing a 1, 2-cyclohexanediol through the cyclohexene catalytic oxidation. The method for preparing the 1, 2-cyclohexanediol of the invention comprises weighting and putting a given amount of cyclohexene, catalyst, solvent and oxidizing agent in a container for reaction, agitation is needed in the process of reaction, a reaction mixture is obtained after the reaction, and the obtained reaction mixture produces the 1, 2- cyclohexanediol through separation. In the invention, the adopted catalyst is a metal oxide, the solvent is a toluene and the oxidizing agent is a tert-butyl hydroperoxide. The method of preparation has advantages of avoiding the problem of high volume of wastewater in the hydroperoxide process of formic acid, hydrogen peroxide or acetic acid when being used previously, reducing the production cost, further simplified technical process and non harm to the human body of the adopted catalyst, and is an environment-friendly chemical reaction. The method has a simple device and practical and easy process, and is easy for forming the industrial scale.
Description
Technical field
The invention belongs to the alkene selective oxidation and prepare the glycol technical field.
Background technology
1, the 2-cyclohexanediol is a kind of very important organic synthesis raw material, can be used for preparing multiple organic intermediate, be mainly used in industries such as medicine, agricultural chemicals, rubber ingredients, softening agent and liquid crystal material, it also is the raw material of the high-grade thinner of Resins, epoxy, can also be used to dehydrogenation and prepare pyrocatechol, purposes is very extensive.As far back as 1936, people such as Criegee (Ber., 69,2753 (1936)) prepared 1, the 2-cyclohexanediol by the hydrolysis of epoxy cyclohexane.1945, people such as Swern (J.Am.Chem.Soc., 67,1786 (1945)) again with hydrogen peroxide as oxidant, made oxygen carrier with formic acid, tetrahydrobenzene direct oxidation preparation 1, and 2-cyclohexanediol, yield are 65～73%.1949, people such as Mugdan (J.Chem.Soc., 1949,2988) were catalyzer with the tungstic oxide, and Peracetic Acid is oxygenant direct oxidation tetrahydrobenzene preparation 1, and 2-cyclohexanediol, yield are 70%.Most up-to-date techniques are to utilize acetate and diacetyl oxide to replace formic acid to do oxygen carrier, this reaction process complexity, cost height.1981, people such as Gupta (J Chem Soc Perkin, 1,2970 (1981)) as catalyzer, were that feedstock production obtain 1 with epoxy cyclohexane with 4-butyl ammonium hydrogen sulfate or Trichlorobismuthine etc., the 2-cyclohexanediol, and this technological reaction mild condition, yield is higher.Recently, people (U.S.Pat.20040192976) such as Shaorong Cheng are catalyzer with the ion exchange resin of solubility, and the hydrolysis epoxy cyclohexane obtains 1,2-cyclohexanediol in the system of water and hydrogen peroxide, and yield is greater than 95%.People such as Kavtaradze (U.S.Pat.20050038301) use respectively instead-and 2-bromine hexalin and epoxy cyclohexane be at 2-propyl alcohol, prepares cyclohexanediol in phosphoric acid and the saturated sodium bicarbonate system, and yield is respectively 93% and 85%.These two process yields are higher, but initial reactant is 2-bromine ring ethanol or epoxy cyclohexane, but not the direct oxidation tetrahydrobenzene prepares cyclohexanediol, are not the ideal way of preparation cyclohexanediol.People such as Tanaka (U.S.Pat.20050096480) prepare cyclohexanediol with the hydrogen peroxide oxidation tetrahydrobenzene containing under the sulfonic superpolymer existence condition, yield can reach 98%, this method yield is very high, and introduce this superpolymer in the patent and can reclaim, it is the ideal way of synthesizing cyclohexane 1 glycol, but employed superpolymer product in its process, it costs an arm and a leg, the preparation cost height.
Because above-mentioned existing preparation 1, the method of 2-cyclohexanediol adopts formic acid or peracetic acid etc. as oxygen carrier mostly, hydrogen peroxide is as oxygenant, and in preparation process catalyzer such as employed bismuth, tungsten and quaternary ammonium salt and contain sulfonic superpolymer and cost an arm and a leg, so exist a large amount of waste water that in preparation process, can produce, complex steps, complex process, the weak point that cost is high has influenced the suitability for industrialized production of this product.
Summary of the invention
The object of the present invention is to provide a kind of tetrahydrobenzene catalyzed oxidation preparation 1, the method for 2-cyclohexanediol, the present invention prepares 1, and the method for 2-cyclohexanediol is:
A certain amount of tetrahydrobenzene, catalyzer, solvent and oxygenant are put into the container mixing react, the gained reaction mixture obtains product 1 through separation, the 2-cyclohexanediol.
The present invention carries out according to following chemical reaction:
Among the present invention, the catalyzer of employing is a metal oxide, and described metal oxide is Cr
2O
3, MoO
3, WO
3, V
2O
5, Nb
2O
5, TiO
2, SiO
2Perhaps their mixture.
The solvent that adopts is a toluene, and the oxygenant of employing is a tertbutyl peroxide.The weight concentration of tertbutyl peroxide in water is 5%～80%, and more suitable concentration is 20%～70%, and only concentration is 25%～65%.
Temperature of reaction is 20 ℃～200 ℃, is 40～150 ℃ than suitable reaction temperature, and only temperature is at 60～100 ℃.Reaction times is 1～150 hour, and the more suitable reaction times is 6～60 hours.In reaction process, need to stir.
Among the present invention, tetrahydrobenzene is oxidized to target product 1 by tertbutyl peroxide on metal oxide catalyst, and the 2-cyclohexanediol is under temperature of reaction is controlled at 110 ℃ or higher temperature of reaction, as 110 ℃ to 200 ℃, the reaction later stage has a spot of cyclonene and the 2-hydroxy-cyclohexanone generates.
Advantage of the present invention is to have avoided a large amount of wastewater problems in the employed formic acid of forefathers, hydrogen peroxide or the acetate hydroperoxy-process, make production cost reduce, technical process is simpler, and employed catalyzer is harmless, is a kind of environmentally friendly chemical reaction.This square law device is simple, and the practical easily row of technology is easy to form industrially scalable.In addition, for the deep processing of tetrahydrobenzene provides a kind of simple method, has higher industrial application value.The physical environment of both having protected us to depend on for existence has been realized the deep processing and utilization of resource again.
Below by embodiment the present invention is made further and to specify, but the invention is not restricted to these embodiment.
Embodiment 1
In the 50mL round-bottomed flask, add the 0.10g molybdic oxide respectively, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, cool to room temperature, carry out assay products with gas-chromatography, the transformation efficiency of tetrahydrobenzene is 93.0%, 1, the selectivity of 2-cyclohexanediol is 93.5%, and all the other products are cyclonene and 2-hydroxy-cyclohexanone.
Embodiment 2
In the 50mL round-bottomed flask, add the 0.10g Vanadium Pentoxide in FLAKES respectively, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, cool to room temperature, carry out assay products with gas-chromatography, the transformation efficiency of tetrahydrobenzene is 73.7%, 1, the selectivity of 2-cyclohexanediol is 91.2%, and all the other products are epoxy cyclohexane and cyclonene.
Embodiment 3
In the 50mL round-bottomed flask, add the 0.10g Niobium Pentxoxide respectively, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, cool to room temperature, carry out assay products with gas-chromatography, the transformation efficiency of tetrahydrobenzene is 2.7%, 1, the selectivity of 2-cyclohexanediol is 31.3%, and all the other products are epoxy cyclohexane and cyclonene.
Embodiment 4
In the 50mL round-bottomed flask, add the 0.10g chromium sesquioxide respectively, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, cool to room temperature, carry out assay products with gas-chromatography, the transformation efficiency of tetrahydrobenzene is 1.9%, 1, the selectivity of 2-cyclohexanediol is 39.6%, and all the other products are epoxy cyclohexane and cyclonene.
Embodiment 5
In the 50mL round-bottomed flask, add the 0.10g tungstic oxide respectively, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, cool to room temperature, use the gas chromatographic analysis product, the transformation efficiency of tetrahydrobenzene is 2.7%, 1, the selectivity of 2-cyclohexanediol is 21.8%, and all the other products are epoxy cyclohexane and cyclonene.
Embodiment 6
In the 50mL round-bottomed flask, add 10mg, 20mg, 50mg respectively, 100mg, 150mg or 200mg molybdic oxide, and then add 5.0g toluene respectively, 0.063mol (5.166g) tetrahydrobenzene and 0.063mol (65%, 8.74g) tertbutyl peroxide, load onto prolong heated and stirred 6h in 80 ℃ of oil baths, cool to room temperature, use the gas chromatographic analysis product, the transformation efficiency of tetrahydrobenzene and 1, the selectivity of 2-cyclohexanediol is as shown in the table, and all the other products are cyclonene and 2-hydroxy-cyclohexanone.
Embodiment 7
In the 50mL round-bottomed flask, add the 0.10g molybdic oxide respectively, 5.0g toluene, 0.063mol (5.166g) tetrahydrobenzene and 0.063mol (65%, 8.74g) tertbutyl peroxide, load onto prolong respectively at heated and stirred 10h in 60～110 ℃ of oil baths, cool to room temperature, use the gas chromatographic analysis product, the transformation efficiency of tetrahydrobenzene and 1, the selectivity of 2-cyclohexanediol is as shown in the table, and all the other products are cyclonene and 2-hydroxy-cyclohexanone.
Embodiment 8
In the 50mL round-bottomed flask, add the 0.10g molybdic oxide respectively, 5.0g toluene, 0.063mol (5.166g) tetrahydrobenzene and 0.063mol (65%, 8.74g) tertbutyl peroxide, load onto prolong heated and stirred in 60 ℃ of oil baths, carried out assay products every one hour with gas-chromatography in the reaction process, carried out 36 hours up to reaction, the transformation efficiency of tetrahydrobenzene and 1, the selectivity of 2-cyclohexanediol is as shown below:
Embodiment 9
In the 50mL round-bottomed flask, add the 0.10g molybdic oxide earlier, 5.0g toluene, 0.063mol (5.166g) tetrahydrobenzene, add the tertbutyl peroxide (keeping the constant 0.063mol of tertbutyl peroxide total amount) of different concns more respectively, load onto prolong respectively at heated and stirred 10h in 80 ℃ of oil baths, cool to room temperature, use the gas chromatographic analysis product, the transformation efficiency of tetrahydrobenzene and 1, the selectivity of 2-cyclohexanediol is as shown in the table, and all the other products are cyclonene and 2-hydroxy-cyclohexanone.
Embodiment 10
In the 50.0mL round-bottomed flask, add the 0.10g molybdic oxide respectively, 5.0g toluene, 0.063mol (5.166g) tetrahydrobenzene and 0.063mol (65%, 8.74g) tertbutyl peroxide, load onto prolong heated and stirred 12h in 90 ℃ of oil baths, the transformation efficiency of tetrahydrobenzene is 99.0%, 1, the selectivity of 2-cyclohexanediol is 97.5%, and all the other products are cyclonene and 2-hydroxy-cyclohexanone.
Embodiment 11
In the 50.0mL round-bottomed flask, add 0.10g Mo-V (Mo:V=1:1 respectively, mol ratio) catalyzer, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, the transformation efficiency of tetrahydrobenzene is 91.7%, 1, the selectivity of 2-cyclohexanediol is 81.8%, and all the other products are epoxy cyclohexane and cyclonene.
Embodiment 12
In the 50.0mL round-bottomed flask, add 0.10g Mo-Ti (Mo:Ti=1:1 respectively, mol ratio) catalyzer, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, the transformation efficiency of tetrahydrobenzene is 85.2%, 1, the selectivity of 2-cyclohexanediol is 88.5%, and all the other products are epoxy cyclohexane.
Embodiment 13
In the 50.0mL round-bottomed flask, add 0.10g V-Ti (V:Ti=1:1 respectively, mol ratio) catalyzer, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, the transformation efficiency of tetrahydrobenzene is 64.7%, 1, the selectivity of 2-cyclohexanediol is 87.3%, and all the other products are epoxy cyclohexane and cyclonene.
Embodiment 14
In the 50.0mL round-bottomed flask, add 0.10g Mo-V-Ti (Mo:V:Ti=1:1:1 respectively, mol ratio) catalyzer, 5.0g toluene, 0.063mol (5.166g) (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths for tetrahydrobenzene and 0.063mol, the transformation efficiency of tetrahydrobenzene is 85.3%, 1, the selectivity of 2-cyclohexanediol is 98.8%, and all the other products are cyclonene.
Embodiment 15
In the 50.0mL round-bottomed flask, add 0.10g TiO respectively
2, 5.0g toluene, (65%, 8.74g) tertbutyl peroxide is loaded onto prolong heated and stirred 10h in 80 ℃ of oil baths, and the transformation efficiency of tetrahydrobenzene is 0,1, and the selectivity of 2-cyclohexanediol is 0 for 0.063mol (5.166g) tetrahydrobenzene and 0.063mol.
Claims (10)
1. tetrahydrobenzene catalyzed oxidation preparation 1, the method of 2-cyclohexanediol, a certain amount of tetrahydrobenzene, catalyzer, solvent and oxygenant are put into the container mixing to react, need in the reaction process to stir, the gained reaction mixture obtains product 1 through separation, 2-cyclohexanediol, described catalyzer are metal oxide, and described metal oxide is MoO
3, V
2O
5Perhaps they and TiO
2Mixture, described oxygenant is a tertbutyl peroxide.
2. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 1, the method for 2-cyclohexanediol is characterized in that described solvent is a toluene.
3. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 1, the method for 2-cyclohexanediol is characterized in that the weight concentration of oxygenant tertbutyl peroxide in water is 5%～80%.
4. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 3, the method for 2-cyclohexanediol is characterized in that the weight concentration of oxygenant tertbutyl peroxide in water is 20%～70%.
5. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 4, the method for 2-cyclohexanediol is characterized in that the weight concentration of oxygenant tertbutyl peroxide in water is 25%～65%.
6. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 1, the method for 2-cyclohexanediol is characterized in that described temperature of reaction is 20～200 ℃.
7. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 6, the method for 2-cyclohexanediol is characterized in that described temperature of reaction is 40～150 ℃.
8. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 7, the method for 2-cyclohexanediol is characterized in that described temperature of reaction is 60～100 ℃.
9. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 1, the method for 2-cyclohexanediol is characterized in that the reaction times is 1～150 hour.
10. a kind of tetrahydrobenzene catalyzed oxidation preparation 1 according to claim 10, the method for 2-cyclohexanediol is characterized in that the reaction times is 6～60 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100678062A CN101279892B (en) | 2007-04-03 | 2007-04-03 | Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100678062A CN101279892B (en) | 2007-04-03 | 2007-04-03 | Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101279892A CN101279892A (en) | 2008-10-08 |
| CN101279892B true CN101279892B (en) | 2011-04-20 |
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| CN2007100678062A Expired - Fee Related CN101279892B (en) | 2007-04-03 | 2007-04-03 | Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene |
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| EP2797868A4 (en) * | 2011-12-30 | 2015-08-12 | Du Pont | Process for the production of hexanediols |
| US9018423B2 (en) | 2012-04-27 | 2015-04-28 | E I Du Pont De Nemours And Company | Production of alpha, omega-diols |
| CN105646144B (en) * | 2014-12-03 | 2018-04-20 | 苏州亚培克生物科技有限公司 | A kind of preparation method of 1,2 aliphatic glycols |
| CN113952948A (en) * | 2021-11-19 | 2022-01-21 | 常州大学 | Molybdenum oxide catalyst for preparing cyclohexanediol by oxidizing cyclohexene and preparation method and application thereof |
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Non-Patent Citations (2)
| Title |
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| deng jingfa等.a new process for preparing dialdehydes by catalytic oxidation of cyclic olefins with aqueous hydrogen peroxide.《tetrahedron》.1992,第48卷(第17期),3504-3512. * |
| S.A.HOLMES等.Tetraneopentyltitanium Derived Supported Catalysts.《JOURNAL OF CATALYSIS》.1998,(第176期),174-175,表1. * |
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