Background technology
1,2-cyclohexanediol is white crystals, and molecular formula is C
6h
12o
2, molecular weight is 116.16, and it has suitable, anti-two kinds of isomer, is respectively cis-1,2-cyclohexanediol and anti-form-1,2-cyclohexanediol.Cis-1,2-cyclohexanediol fusing point is 97-99 DEG C, anti-form-1, and 2-cyclohexanediol fusing point is 102-104.5 DEG C, and boiling point is 126 DEG C, can be dissolved in methyl alcohol, chloroform, soluble in water.
Anti-form-1,2-cyclohexanediol cis-1,2-cyclohexanediol
1,2-cyclohexanediol, owing to having two hydroxyls and ring texture in molecule, thus has comparatively active chemical property, can carry out the reactions such as addition, replacement, oxidation, dehydrogenation.1,2-cyclohexanediol is a kind of very important Organic Chemicals, mainly for the manufacture of fine chemical products such as polyester, medicine, agricultural chemicals.Along with developing rapidly of petrochemical complex, recent two decades comes, and the exploitation of cyclohexene derivative cause the pay abundant attention of domestic and international chemical worker.Tetrahydrobenzene is adopted to be that the study on the synthesis work that intermediate product 1, the 2-cyclohexanediol of pyrocatechol prepared by raw material gets more and more people's extensive concerning.
At present, with tetrahydrobenzene as Material synthesis 1, the research method of 2-cyclohexanediol has more, general employing cyclohexene oxide legal system is for 1,2-cyclohexanediol is mainly by being first epoxy cyclohexane by cyclohexene oxide, then epoxy cyclohexane is hydrolyzed and obtains 1,2-cyclohexanediol under acidic medium, and concrete reaction process is:
End is got up, cyclohexene oxide legal system is adopted to be mainly chlorohydrination, two chlorohydrination, phase transfer catalysis process for the method for epoxy cyclohexane, wherein, chlorohydrination, two chlorohydrination are not environmentally eliminated gradually, phase transfer catalysis process adopts precious metal to be catalyzer, hydrolysis epoxy cyclohexane used catalyst is mainly mineral acid, organic acid and organic salt substantially, such as: sulfuric acid, hydrochloric acid, formic acid, acetic acid, acidic ion exchange resin etc.
But due to current cyclohexene oxide severe reaction conditions, oxidized byproduct is many, and namely target product selectivity is lower.Have investigator to propose, for improving the selectivity of object product, must filter out the catalyzer that selectivity is stronger, one is guarantee selective epoxidation, and two is to ensure that over oxidation does not generate the classes such as acid.Therefore, the cyclohexene oxide system that development goal selectivity of product is higher will become the emphasis and key point researched and developed in the future.
As everyone knows, TS-1/H
2o
2oxidation system has good oxidation effectiveness to alkene, and the selectivity of target product is higher, but when being applied to cyclohexene oxide, its primary product is epoxy cyclohexane, and in order to prepare 1, during 2-cyclohexanediol, need to continue through hydrolysis epoxy cyclohexane and obtain, this makes whole preparation process comparatively complicated undoubtedly.
Therefore, one can be developed tetrahydrobenzene can be adopted directly to prepare 1,2-cyclohexanediol, and the higher method of target product selectivity will become the emphasis direction in the future studied.
Embodiment
The invention provides a kind of cyclohexene oxide and prepare 1, the method of 2-cyclohexanediol, the method comprises: under oxidation reaction condition, tetrahydrobenzene, aqueous hydrogen peroxide solution is contacted in organic solvent with titanium-silicon molecular sieve catalyst, wherein, described contact is carried out under acidic substance exist.
According to the present invention, all can realize goal of the invention of the present invention according to preceding method, under preferable case, the weight ratio of described acidic substance and aqueous hydrogen peroxide solution is 0.0005-5: 1, is preferably 0.001-3: 1.
According to the present invention, all goal of the invention of the present invention can be realized according to preceding method, the kind range of choices of acidic substance described in the present invention is wider, be generally in organic carboxyl acid, mineral acid, solid acid, acid-salt one or more, wherein, described organic carboxyl acid can for conventional various organic carboxyl acids, be preferably the organic carboxyl acid of C1-C10, one or more more preferably in the unary organic carboxylic acid of C1-C10 and the binary organic carboxyl acid of C-C10, described solid acid can for conventional various solid acids; Further preferred described acidic substance are one or more in sulfuric acid, phosphoric acid, acetic acid, formic acid, succinic acid, fluoroboric acid, sodium pyrosulfate (potassium), SODIUM PHOSPHATE, MONOBASIC (potassium), Whitfield's ointment, oxalic acid, hexanodioic acid, phthalic acid, p-methyl benzenesulfonic acid and strong acidic ion resin, the present invention to the kind of described strong acidic ion resin without particular requirement, the conventional strong acidic ion resin used all can realize object of the present invention, such as, can be 732 resin cation (R.C.)s.
In the present invention, described contact is carried out referring in whole system containing acidic substance under acidic substance exist, and no matter it is originated, such as when containing acidic substance in described organic solvent (or when organic solvent is acid), then without the need to adding separately acidic substance again in system.
According to the present invention, TS-1/H conventional in the present invention
2o
2solvent in the system of catalysis cyclohexene oxide all can be used as organic solvent of the present invention, wherein, be preferably in alcohol, ether, ketone, acid, halohydrocarbon, ester and nitrogenous organic solvent one or more; Preferred described nitrogenous organic solvent is nitrile.As previously mentioned, described acid can be monoprotic acid and/or the diprotic acid of C1-C10, is preferably monoprotic acid and/or the diprotic acid of C1-C6, is more preferably one or more in formic acid, acetic acid, propionic acid, oxalic acid, o-benzoic acid and caproic acid.The solvent of all the other kinds also can select the solvent of this area routine use, describes in detail no longer one by one at this.
The present inventor also finds in research process, when adopting one or more in alcohol, ketone and nitrile as organic solvent of the present invention, can improve the transformation efficiency of tetrahydrobenzene of the present invention and the yield of target product 1,2-cyclohexanediol further.Further, preferred described organic solvent comprises component A and B component, and described component A is ketone and/or nitrile, and described B component is alcohol; More preferably the weight ratio of described component A and B component is 0.1-50: 1, is preferably 1-20: 1, is more preferably 2-15: 1.
The present inventor studies discovery, and described organic solvent is alcohol and ketone, and when the mass ratio of described ketone and alcohol is 4-9: 1, the transformation efficiency of tetrahydrobenzene and the yield of 1,2-cyclohexanediol can improve further; More preferably, when the mass ratio of described ketone and alcohol is 4-9: 1, the temperature of described contact is 40-150 DEG C.
The present inventor finds equally, and described organic solvent is alcohol and nitrile, and when the mass ratio of described nitrile and alcohol is 2-11: 1, the transformation efficiency of tetrahydrobenzene and the yield of 1,2-cyclohexanediol can improve further; More preferably when the mass ratio of described nitrile and alcohol is 2-11: 1, the temperature of described contact is 50-150 DEG C, is preferably 60-130 DEG C.
In the present invention, adopt the mixed solvent of ketone and/or nitrile and alcohol can realize beneficial effect of the present invention fully, the range of choices of the selection of the kind of described ketone, nitrile, alcohol is wider, for the present invention, under preferable case, described nitrile is mononitriles and/or the dinitrile of C2-C10, be more preferably mononitriles and/or the dinitrile of C2-C6, further preferably, described nitrile is one or more in acetonitrile, succinonitrile, propionitrile, valeronitrile and adiponitrile, is particularly preferably one or more in acetonitrile, succinonitrile and adiponitrile.
Equally, under preferable case, described ketone is the ketone of C3-C10, is more preferably the ketone of C3-C6, one or more more preferably in acetone, butanone, pimelinketone, hexanedione and diacetylmethane.
As previously mentioned, equally, under preferable case, described alcohol is the alcohol of C1-C10, be preferably the alcohol of C1-C6, be more preferably in methyl alcohol, ethanol, propylene glycol, butyleneglycol, hexalin, Pentyl alcohol, Virahol, the trimethyl carbinol and isopropylcarbinol one or more, be more preferably in methyl alcohol, ethanol, propylene glycol, Virahol, the trimethyl carbinol, hexalin and isopropylcarbinol one or more.
Titanium-silicon molecular sieve catalyst described in the present invention can provide with HTS, and also can be shaping titanium-silicon molecular sieve catalyst, can select according to concrete reaction formation, this be the known technology of those skilled in the art, does not repeat them here.
The present invention without particular requirement, can be the hydrogen peroxide of 20-80 % by weight for concentration to the concentration of described aqueous hydrogen peroxide solution (also can be described as hydrogen peroxide), such as, can be the hydrogen peroxide of commercially available 30 % by weight, 50 % by weight, 70 % by weight.
The present invention without particular requirement, can be the reaction conditions of the conventional oxidation system using HTS as catalyzer to the condition of described oxidizing reaction.
Under preferable case, when the described catalyzer containing HTS is HTS, the mass ratio that the condition of described oxidizing reaction generally comprises tetrahydrobenzene, aqueous hydrogen peroxide solution, HTS and organic solvent is 1: 0.02-3.6: 0.01-15: 2-30, is preferably 1: 0.2-2.2: 0.5-5: 3-15; The weight ratio of acidic substance and aqueous hydrogen peroxide solution is 0.0005-5: 1, is preferably 0.005-0.5: 1; The temperature of contact is 40-150 DEG C, is preferably 50-120 DEG C; Pressure is 0.01-2MPa, is preferably 0.1-0.5MPa; Time is 0.1-10h, is preferably 1-5h.Previous reaction condition, general applicable rhythmic reaction system, also can be used for successive reaction, as the reaction in slurry bed.
When the described catalyzer containing HTS is the preformed catalyst containing HTS, the mass ratio that the condition of described oxidizing reaction generally comprises tetrahydrobenzene, aqueous hydrogen peroxide solution and organic solvent is 1: 0.02-3.6: 2-30, is preferably 1: 0.2-2.2: 3-15; The weight ratio of acidic substance and aqueous hydrogen peroxide solution is 0.0005-5: 1, is preferably 0.001-0.5: 1; The temperature of contact is 40-150 DEG C, is preferably 50-120 DEG C; Pressure is 0.01-2MPa, is preferably 0.1-0.5MPa; Liquid hourly space velocity is 0.01-10h
-1, be preferably 0.05-2h
-1; Agent oil volume, than being 0.01-10, is preferably 0.05-5.Previous reaction condition, general applicable successive reaction system, as successive reaction systems such as fixed beds.Liquid hourly space velocity described in the present invention is the definition of the liquid hourly space velocity that this area routine uses, it is a kind of representation of air speed, its meaning is the volume of unit reaction volume (for the reaction adopting solid catalyst, being then unit volume of catalyst) treatment solution phase reaction thing per hour.In the present invention, agent oil volume is than the definition of agent oil volume ratio used for this area routine, is the ratio of the cumulative volume of catalyzer and the cumulative volume of all liquid phase materials.
In the present invention, described pressure refers to the gauge pressure in reaction system.
According to the present invention, HTS in described titanium-silicon molecular sieve catalyst can be conventional HTS, also can be able to be non-modified for modification, at least one in the HTS (as Ti-β) of the preferably HTS (as TS-2) of the HTS (as TS-1) of MFI structure, MEL structure, BETA structure; Be more preferably that to have structural formula be xTiO
2siO
2, wherein, x is 0.0001-0.04, is preferably 0.01-0.03, is more preferably the HTS of 0.015-0.025.
In the present invention, described HTS can be commercially available, also can prepare, prepare the method for described HTS for conventionally known to one of skill in the art, such as, can with reference to [Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1) With Hydrogen Peroxide Journal of Natural Gas Chemistry 2001,10 (4): 295-307] the method preparation described in, also can obtain with reference to the method for Kaolinite Preparation of Catalyst disclosed in CN101279959A.
Be more preferably, the HTS in described titanium-silicon molecular sieve catalyst is MFI structure, and HTS crystal grain is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and described HTS is at 25 DEG C, P/P
0=0.10, adsorption time is that the benzene adsorptive capacity that records under the condition of 1 hour is for being no less than 70 milligrams/gram, hysteresis loop is there is between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm, the HTS with said structure and character is commonly referred to as hollow HTS, commercially be called HTS, its correlation parameter and preparation method thereof can see CN1301599A.
In the present invention, cyclohexanediol is the general designation of cis-1,2-cyclohexanediol and anti-form-1,2-cyclohexanediol.
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
Reagent used in comparative example and embodiment is commercially available chemically pure reagent.In embodiment, the concentration of hydrogen peroxide is 27.5 quality %.
(Hunan Jian Chang company manufactures the Industrial products of HTS described in hollow HTS HTS system CN1301599A used in embodiment, be the HTS of MFI structure through X-ray diffraction analysis, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, crystal grain is hollow crystal grain and the radical length of chamber portion is 15-180 nanometer; This sieve sample at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is 78 milligrams/gram), titanium oxide content is 2.5 % by weight.
Traditional HTS (TS-1) used in embodiment is by document [Cyclohexane Oxidation Catalyzed by Titanium Silicalite (TS-1) With Hydrogen Peroxide Journal of Natural Gas Chemistry 2001,10 (4): 295-307] in the 296th page of 9-24 capable described by (TS-1) sieve sample of preparing of method, titanium oxide content is 2.5 % by weight.
The method preparation described in J.Chem.Soc., Chem.Commun.1997,677-678 such as the Ti-β reference literature Takashi Tatsumi used in embodiment, titanium oxide content is 2.6 % by weight.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, being undertaken quantitatively, all can refer to prior art and carrying out by correcting normalization method, calculating the evaluation indexes such as the transformation efficiency of reactant, the yield of product and selectivity on this basis.
In the present invention, the transformation efficiency calculation formula of tetrahydrobenzene is as follows:
The calculation formula of compositional selecting is as follows:
The calculation formula of component yield is as follows:
Y
1,2-cyclohexanediol=S
1,2-cyclohexanediol× X
tetrahydrobenzene
Wherein, X is transformation efficiency; S is selectivity; Y is yield; M is the quality of component; N is the amount of substance of component; Wherein m
0and n
0represent the quality before reaction and molar weight respectively.
Embodiment 1-21
The HTS taking certain mass is loaded in 250ml tri-mouthfuls of vials, then adds tetrahydrobenzene, hydrogen peroxide, organic solvent and acidic substance in container.Be put in constant temperature oil bath by three mouthfuls of vials, oil bath is placed on temperature control magnetic stirring apparatus.Start magnetic agitation, start reaction, the kind of each material and materials, reaction conditions, the transformation efficiency of tetrahydrobenzene, the selectivity of epoxy cyclohexane and yield are in table 1.
Comparative example 1
According to the method for embodiment 1-21, unlike, do not contain acidic substance, reaction conditions in reaction system in table 1.
As can be seen from Table 1, adopt method of the present invention, can directly prepare 1,2-cyclohexanediol, and in oxidising process the transformation efficiency of tetrahydrobenzene and target product selectivity higher, further, in a preferred embodiment of the invention, adopt the mixture of ketone and/or nitrile and alcohol as solvent compared to the reaction adopting separately a kind of solvent, the transformation efficiency of tetrahydrobenzene is higher, selectivity and the yield of target product 1,2-cyclohexanediol are also higher.
Table 1