Summary of the invention
The object of the invention is a kind of method preparing pyrocatechol providing energy consumption low on the basis of existing technology, and the method 1,2-cyclohexanediol transformation efficiency is high, pyrocatechol selectivity is high, and can carry out continuous seepage.
The present inventor finds, the fixed bed that Ni/ diatomite catalyzer is equipped with in employing conventionally passes into vaporization, overheated 1,2 cyclohexanediol aqueous solution steams, carry out catalytic dehydrogenation and obtain pyrocatechol, consume a large amount of energy, catalyst life only 30h simultaneously, catalyst regeneration process component difficulty is larger.
Simultaneously, the method of pyrocatechol is prepared using tetrahydrobenzene as raw material, first 1 is prepared by cyclohexene oxide, 2-cyclohexanediol, then through extraction, the steps such as distillation obtain 1, 2-cyclohexanediol, then by 1, 2-cyclohexanediol carries out dehydrogenation and obtains pyrocatechol, according to the method preparation neck dihydroxy-benzene, because in industrial application process, the consumption such as solvent is all very large, cause the energy consumption of extraction or distillation very high thus, thus greatly reduce its industrial application value, and can not the present inventor attempts imagination be separated, and directly cyclohexene oxide is obtained mainly comprise 1, the liquid product of 2-cyclohexanediol carries out Oxidative Dehydrogenation for pyrocatechol, so greatly can reduce energy consumption, and greatly can save operation sequence, and this imagination is carried out test discovery, owing to have impact on the dehydrogenation activity of follow-up dehydrogenation catalyst in the liquid product that oxydehydrogenation obtains containing a large amount of negatively charged ion brought by oxide catalyst and positively charged ion, cause certain embodiments efficiency very low, make to prepare pyrocatechol efficiently according to the method, on this basis, the present inventor proposes, the negatively charged ion brought by oxide catalyst in removing liquid product and positively charged ion, it so can be avoided to affect the activity of the dehydrogenation catalyst in follow-up certain embodiments, simultaneously follow-up dehydrogenating technology uses dehydrogenation in liquid phase technology, not only do not need a large amount of water of gasification and raw material, reactant not easily coking on a catalyst in liquid phase reaction simultaneously, substantially prolongs the life-span of catalyzer, thus pyrocatechol can be prepared efficiently, and overcome due to pyrocatechol very easily coking cause catalyzer easy in inactivation and can not the defect of batch production of continuous effective.Based on aforementioned invention thinking, complete the present invention.
For realizing aforementioned object, the invention provides a kind of method preparing pyrocatechol, the method comprises:
(1) under the reaction conditions that cyclohexene oxide is 1,2-cyclohexanediol, tetrahydrobenzene, oxygenant and catalyst exposure are obtained the reaction solution containing 1,2-cyclohexanediol, remove the negatively charged ion in described reaction solution and positively charged ion, obtain dehydrogenation stoste;
(2) under liquid-phase catalysis dehydrogenation condition, described dehydrogenation stoste is contacted with dehydrogenation catalyst.
According to method of the present invention without the need to purifying out 1,2-cyclohexanediol carries out Oxidative Dehydrogenation again for pyrocatechol, dehydrogenation in liquid phase technology can be directly adopted to carry out dehydrogenation, make not only not need a large amount of solvent of gasification and raw material, reactant not easily coking on a catalyst in liquid phase reaction simultaneously, substantially prolongs the life-span of catalyzer, thus pyrocatechol can be prepared efficiently.Make the energy consumption preparing pyrocatechol according to method of the present invention greatly reduce thus, and the yield of pyrocatechol is very high.As can be seen here, method of the present invention very has industrial application value.
Embodiment
The invention provides a kind of method preparing pyrocatechol, the method comprises: cyclohexene oxide is being 1 by (1), under the reaction conditions of 2-cyclohexanediol, tetrahydrobenzene, oxygenant and catalyst exposure are obtained containing 1, the reaction solution of 2-cyclohexanediol, remove the negatively charged ion in described reaction solution and positively charged ion, obtain dehydrogenation stoste; (2) under liquid-phase catalysis dehydrogenation condition, described dehydrogenation stoste is contacted with dehydrogenation catalyst.
In the present invention, described negatively charged ion and positively charged ion refer to negatively charged ion and the positively charged ion of the dehydrogenation catalyst activity that can affect step of the present invention (2).
In the present invention, remove described containing 1, negatively charged ion in the reaction solution of 2-cyclohexanediol and cationic method have multiple, for the present invention, in order to cost-saving, preferably remove and described to comprise the steps: the described reaction solution containing 1,2-cyclohexanediol according to positive sequence or inverted sequence through Zeo-karb and anionite-exchange resin containing the negatively charged ion in the reaction solution of 1,2-cyclohexanediol and cationic method.Such as if desired first remove described containing 1, positively charged ion in the reaction solution of 2-cyclohexanediol, then first can contain 1 by described, the reaction solution of 2-cyclohexanediol contacts with Zeo-karb and removes positively charged ion, and if desired first remove described containing 1, negatively charged ion in the reaction solution of 2-cyclohexanediol, then first can contain 1 by described, the reaction solution of 2-cyclohexanediol contacts with anionite-exchange resin and removes negatively charged ion, in fact, what the present invention did not require described positively charged ion and negatively charged ion removes order, as long as after ensureing to eventually pass Zeo-karb and anionite-exchange resin, containing 1, not containing negatively charged ion and positively charged ion in the reaction solution of 2-cyclohexanediol.
In the present invention, the range of choices of the kind of described Zeo-karb is wider, and can be used in of prior art is sloughed cationic Zeo-karb and all be can be used for the present invention, and the present invention, is not described in detail at this without particular requirement this.Specifically can select according to cationic kind.
In the present invention, the range of choices of the kind of described anionite-exchange resin is wider, and the anionite-exchange resin that can be used in sloughing negatively charged ion of prior art all can be used for the present invention, and the present invention, is not described in detail at this without particular requirement this.Specifically can select according to the kind of negatively charged ion.
According to method of the present invention, be 1 by cyclohexene oxide described in step (1), the reaction conditions of 2-cyclohexanediol generally comprises: pH value is below 5, namely contact described in step (1) and carry out in acid condition, particularly, in specific implementation process, if the reaction system containing described oxygenant, catalyzer and tetrahydrobenzene does not possess acidity, now can by additionally adding the pH value regulating reaction system in acidic substance to described reaction system.
More preferably, be that the reaction conditions of 1,2-cyclohexanediol also comprises by cyclohexene oxide described in step (1): temperature is 30-100 DEG C, be preferably 50-80 DEG C, be preferably 60 DEG C.
According to method of the present invention, described in step (1), the range of choices of the kind of oxygenant is wider, prior art conventional for being that the oxygenant of 1,2-cyclohexanediol all can be used for the present invention by cyclohexene oxide, be hydrogen peroxide or aqueous hydrogen peroxide solution for the preferred described oxygenant of the present invention.
According to method of the present invention, the range of choices of the kind of described catalyzer is wider, prior art to can be used in cyclohexene oxide be 1, the catalyzer of 2-cyclohexanediol all can be used for the present invention, for the present invention, preferred catalyst is one or more in HTS, heteropolyacid salt and an acidic catalyst; Wherein, described an acidic catalyst is preferably one or more in sulfuric acid, phosphoric acid, fluoroboric acid and Phenylsulfonic acid.
According to one of the present invention preferred embodiment, described in preferred steps (1), oxygenant is aqueous hydrogen peroxide solution, and described catalyzer is HTS; Described is 1 by cyclohexene oxide, the reaction conditions of 2-cyclohexanediol comprises: the pH value of contact is below 5, and temperature is 30-100 DEG C, and the time is 2-20h, the mol ratio of tetrahydrobenzene and hydrogen peroxide is 1:(0.2-1.2), the mass ratio of HTS and tetrahydrobenzene is 0.001-0.1:1.More preferably described contact is carried out in the presence of solvent, and the range of choices of the kind of described solvent is wider, and the solvent that prior art uses all can be used for the present invention, such as, can be one or more in water, alkane, alcohol, ketone, nitrile, ester and halohydrocarbon.And in order to reduce the impact of solvent on two group reactions (comprising step (1) and step (2)), preferred described solvent is one or more in dimethylbenzene, toluene, ethanol, propyl alcohol, ethylene glycol, propylene glycol, hexalin, butyleneglycol, octanol, ethyl acetate, glycol dicaproate, glycol diacetate, butyleneglycol diacetate esters, diethylene adipate, butyl phthalate, acetonitrile, adiponitrile, pimelinketone, acetone, isophorone and water.More preferably the mass ratio of described organic solvent and tetrahydrobenzene is (1-30): 1.And as previously mentioned, because previous reaction system does not possess required pH value, therefore can be undertaken regulating the pH value needed for contact by adding acidic substance in reaction system.
Dehydrogenation catalyst can be the various dehydrogenation catalysts of prior art, such as, can be one or more in nickel system dehydrogenation catalyst, palladium system dehydrogenation catalyst, platinum group dehydrogenation catalyst, ruthenium system dehydrogenation catalyst and rhodium system dehydrogenation catalyst.
According to method of the present invention, described in step (2), the active ingredient of dehydrogenation catalyst contains group VIII metal element, for the present invention, preferred described group VIII metal element is one or more in nickel element, palladium element, platinum element, ruthenium element and rhodium element, therefore for the present invention, preferably the described dehydrogenation catalyst containing group VIII metal element is one or more in nickel system dehydrogenation catalyst, palladium system dehydrogenation catalyst, platinum group dehydrogenation catalyst, ruthenium system dehydrogenation catalyst and rhodium system dehydrogenation catalyst.
In the present invention, during preferred described nickel system dehydrogenation catalyst is, nickel content is 10-95 % by weight, and the content of dehydrogenation adjuvant component is 1-15 % by weight, and other is carrier.Wherein, described dehydrogenation adjuvant component be preferably in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate one or more, be more preferably in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard one or more; Described carrier be preferably in silicon-dioxide, aluminium sesquioxide and gac one or more.
In the present invention, in preferred described palladium system dehydrogenation catalyst, palladium content is 0.3-6 % by weight, and the content of dehydrogenation adjuvant component is 1-15 % by weight, and other is carrier.Wherein, described dehydrogenation adjuvant component be preferably in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate one or more, be more preferably in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard one or more; Described carrier be preferably in silicon-dioxide, aluminium sesquioxide and gac one or more.Its preparation method can adopt the preparation method of this area routine, and the present invention is not described in detail at this.
In the present invention, in preferred described platinum group dehydrogenation catalyst, platinum content is 0.3-6 % by weight, and the content of dehydrogenation adjuvant component is 1-15 % by weight, and other is carrier.Wherein, described dehydrogenation adjuvant component be preferably in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate one or more, be more preferably in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard one or more; Described carrier be preferably in silicon-dioxide, aluminium sesquioxide and gac one or more.Its preparation method can adopt the preparation method of this area routine, and the present invention is not described in detail at this.
In the present invention, in preferred described ruthenium system dehydrogenation catalyst, ruthenium content is 0.3-10 % by weight, and the content of dehydrogenation adjuvant component is 1-15 % by weight, and other is carrier.Wherein, described auxiliary agent be preferably in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate one or more, be more preferably in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard one or more; Described carrier be preferably in silicon-dioxide, aluminium sesquioxide and gac one or more.Its preparation method can adopt the preparation method of this area routine, and the present invention is not described in detail at this.
In the present invention, in preferred described rhodium system dehydrogenation catalyst, rhodium content is 0.3-10 % by weight, and the content of dehydrogenation adjuvant component is 1-15 % by weight, and other is carrier.Wherein, described dehydrogenation adjuvant component be preferably in alkali metal sulfates, alkaline carbonate, alkaline earth metal sulphate and alkaline earth metal carbonate one or more, be more preferably in sodium sulfate, potassium sulfate, Lithium Sulphate, magnesium sulfate, calcium sulfate, sodium carbonate, barium sulfate, salt of wormwood and Quilonum Retard one or more; Described carrier one or more its preparation methods be preferably in silicon-dioxide, aluminium sesquioxide and gac can adopt the preparation method of this area routine, and the present invention is not described in detail at this.
According to method of the present invention, described in preferred steps (2), liquid-phase catalysis dehydrogenation condition comprises: the dehydrogenation of cyclohexanediol liquid-phase catalysis, and temperature is 170-350 DEG C, and the mass ratio of dehydrogenation catalyst and dehydrogenation stoste is 1:5-200.Under Above-mentioned catalytic dehydrogenation condition, the dehydrogenation efficiency according to method of the present invention can be improved further.
In the present invention, if not otherwise specified, described contact is carried out all under agitation.
Describe the present invention in detail below by embodiment, but the present invention is not limited to this.
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, reaction-ure conversion-age calculation formula is as follows:
The calculation formula of compositional selecting is as follows:
Wherein, X is transformation efficiency; S is selectivity; M is the quality of component; N is the amount of substance of component; Wherein m
0and n
0divide the quality before representing respective reaction and molar weight.
In embodiments of the invention, catalyzer is method synthesis conventionally or is commercially available.
Embodiment 1
(1) using acetone as organic solvent, by tetrahydrobenzene, hydrogen peroxide (30 quality %) contacts with titanium-silicon molecular sieve TS-1, wherein, tetrahydrobenzene with in the mol ratio of the hydrogen peroxide of hydrogen peroxide for 1:1.2, acetone, the mass ratio of HTS and tetrahydrobenzene is 15:0.05:1, and to add salt acid for adjusting pH value be 4, 3h is contacted at 60 DEG C, obtain containing 1, reaction solution (the cyclohexene conversion rate 98.1% of 2-cyclohexanediol, 1, 2-cyclohexanediol selectivity 98.8%), 1 is contained by described, negatively charged ion (such as chlorion etc.) wherein and positively charged ion (such as titanium ion etc.) is removed through Zeo-karb and anionite-exchange resin successively in the reaction solution of 2-cyclohexanediol, obtain dehydrogenation stoste,
(2) load in reactor by dehydrogenation catalyst, then described dehydrogenation stoste be incorporated in reactor and contact with dehydrogenation catalyst, under liquid-phase catalysis dehydrogenation condition, carry out catalytic dehydrogenation, reaction result is in table 1.
Embodiment 2
Pyrocatechol is prepared according to the method for embodiment 1, unlike, the liquid-phase catalysis dehydrogenation condition of step (2) changes, and the results are shown in Table 1.
Table 1
Comparative example 1
Pyrocatechol is prepared according to the method for embodiment 1, unlike, by step (1) gained reaction solution without Zeo-karb and anionite-exchange resin, directly carry out the dehydrogenation of step (2), all the other conditions are all identical, wherein, and 1,2-cyclohexanediol transformation efficiency is 30%, and pyrocatechol selectivity is 63.3%.
From the result of embodiment, adopt method of the present invention to use tetrahydrobenzene to prepare pyrocatechol, pyrocatechol selectivity is high, and without the need to through middle separating step, simplifies operating process and effectively saved energy consumption.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.