CN103709010A - Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water - Google Patents

Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water Download PDF

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CN103709010A
CN103709010A CN201410008708.1A CN201410008708A CN103709010A CN 103709010 A CN103709010 A CN 103709010A CN 201410008708 A CN201410008708 A CN 201410008708A CN 103709010 A CN103709010 A CN 103709010A
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arachidis hypogaeae
pericarppium arachidis
water
tetrahydrobenzene
reaction
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CN103709010B (en
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薛伟
姚洁
金长青
李芳�
张东升
王延吉
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Hebei University of Technology
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated

Abstract

The invention discloses a method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water. The method comprises the following steps: adding cyclohexene, tcarboxylic acid and water into a kettle type reactor, wherein the molar ratio of cyclohexene to carboxylic acid to the water is 1:(0.5-6):(5-40); adding a catalyst into a reaction kettle in an amount of 0.01-0.2g based on every millimeter of cyclohexene; charging N2 of which the partial pressure is 0.3-1.5MPa; raising the reaction temperature to 70-150 DEG C, and reacting for 0.5-5 hours to obtain cyclohexanol, wherein the catalyst is a peanut shell carbon-based solid acid catalyst. The cyclohexene conversion rate is 88.0 percent, the cyclohexanol yield is 82.0 percent, the reaction speed is increased, and the reaction time is shortened; moreover, the catalyst used in the method is high in stability, and can be reused easily.

Description

A kind of by tetrahydrobenzene, carboxylic acid and water reaction synthesizing cyclohexanol method
Technical field
The present invention relates to a kind of method by tetrahydrobenzene, carboxylic acid and water reaction synthesizing cyclohexanol, it is characterized in that the method is with tetrahydrobenzene, carboxylic acid and water are raw material, take Pericarppium arachidis hypogaeae carbon-based solid acid as catalyzer, carry out the building-up reactions of hexalin under certain temperature of reaction and reaction times.
Background technology
Hexalin is the intermediate raw material of producing the important Chemicals such as hexanodioic acid, hexanolactam and medicine, coating, dyestuff.Traditional industrial process mainly contains two kinds: phenol hydrogenation method and cyclohexane oxidation process.The raw materials cost of phenol hydrogenation method is higher, and hydrogen gas consumption is large, so the method is eliminated substantially.At present, cyclohexane oxidation process is topmost cyclohexanol production method.The industrial liquid phase oxidation technique that all adopts cobalt salt catalysis, these processing condition are gentle, but on equipment and tube wall, are prone to slagging scorification in reaction process, and impact is produced continuously.Also there is the shortcomings such as poor selectivity (product is hexalin, cyclohexanone mixture, is commonly called as KA oil, selectivity 70%~85%), low conversion rate (7%~12%) and energy consumption height in this process.In addition, owing to can forming explosive mixture after hexanaphthene and air mixed, so cyclohexane oxidation process poor stability.
The eighties in 20th century, Japanese Asahi Kasei Corporation has developed take benzene as raw material, through selecting Hydrogenation for tetrahydrobenzene, then through the technique of preparing cyclohexanol by cyclohexene hydration reaction, and in nineteen ninety by this technique industrialization.The related reaction of this technique all belongs to atomic economy reaction, at aspects such as material consumption, energy consumption and safety, all has obvious advantage.Yet cyclohexene hydration reaction is subject to the restriction of chemical equilibrium, and the ability of the dissolving each other extreme difference of two kinds of reactants (40 ℃ time tetrahydrobenzene the solubleness in water only have 0.05%), this has also limited the carrying out of cyclohexene hydration reaction greatly.
Sundmacher etc. (Ind Eng Chem Res, 2007,46:1099-1104.Org Process Res Dev, 2013,17:343-358) studied the catalytic reaction process by the indirect hydration of tetrahydrobenzene hexalin processed.They utilize tetrahydrobenzene to react with formic acid and generate cyclohexyl formate, and then cyclohexyl formate hydrolysis is obtained to hexalin and formic acid.In theory, formic acid does not consume, and has only played a carrying effect.This technique has overcome the thermodynamical restriction of cyclohexene hydration reaction, and Sundmacher etc. find tetrahydrobenzene to be approached to 100% the hexalin that is converted into by simulation.But this technique has been used two tower reactors, and use ion-exchange resin catalyst, the shortcoming such as have that facility investment is large, complicated operation, catalyst life are short.ZL201010173800.5, in intermittence tank reactor, is used HZSM-5 molecular sieve catalytic through cyclohexyl formate, to prepare hexalin by tetrahydrobenzene and reacts, and hexalin yield is the highest by 65.4%.Yet HZSM-5 molecular sieve catalyst effective acid center density is lower, causes speed of reaction slow, and the reaction times is longer; In addition, because tetrahydrobenzene, under reaction conditions, self-polymeric reaction can occur, and HZSM-5 aperture less (about 0.55nm), the polymkeric substance of generation easily covers surface, active centre, thereby and stops up duct catalyst activity is reduced gradually.If want, make catalyst regeneration, also need through high-temperature roasting, energy consumption is larger.In addition, this patented method is still two step operations, and two-step reaction optimal conditions is separately different, need to be regulated and controled; And adding of raw water need to be by means of high-pressure pump, step is comparatively loaded down with trivial details.(Reactive Polymers, 1992,18 (2): 107-115) studied and by tetrahydrobenzene, through hexalin acetate, prepared hexalin and react such as Chakrabarti.First they utilize tetrahydrobenzene and acetic acidreaction to generate hexalin acetate, thereby then hexalin acetate and butanols are carried out to transesterification reaction obtain hexalin.The catalyzer using in this reaction process is Amberlyst-15 Zeo-karb or Filtrol-24 acid-treated clay, and wherein the performance of Amberlyst-15 is more excellent.Compare with traditional liquid acid catalyst, ion exchange resin has solved catalyst separating, recovery problem, but its price is conventionally more expensive, and poor heat stability, life-span are short.And, in this reaction, except obtaining hexalin, the butylacetate of amount of substance such as also can generate, Atom economy is poor.
Summary of the invention
Technical problem to be solved by this invention is: in synthetic for current hexalin, separation difficulty, corrosion phenomenon, the catalyst activity of the catalyzer of appearance are low, speed of reaction is slow, easy inactivation, operation, control complex steps, and the problem such as regenerative process is complicated, energy consumption is high, provide a kind of catalytic activity high, the high and catalyzer raw materials wide material sources of selectivity, cost are low, in reaction, easily reclaim afterwards, the method for repeatable high synthesizing cyclohexanol.
Technical solution of the present invention is as follows:
A method by tetrahydrobenzene, carboxylic acid and water reaction synthesizing cyclohexanol, comprises the steps:
Tetrahydrobenzene, carboxylic acid and water are joined in tank reactor, and its consumption mol ratio is tetrahydrobenzene: carboxylic acid: water=1:0.5~6:5~40; In reactor, add catalyzer again, its consumption is 0.01~0.2 gram of catalyzer of every milliliter of tetrahydrobenzene; Be filled with N 2, its dividing potential drop is 0.3~1.5MPa; Temperature of reaction is risen to 70~150 ℃, react 0.5~5 hour, obtain hexalin;
Described catalyzer is Pericarppium arachidis hypogaeae carbon-based solid acid catalyst.
Described carboxylic acid is formic acid, acetic acid or propionic acid.
The described method by tetrahydrobenzene, carboxylic acid and water reaction synthesizing cyclohexanol, after also comprising the steps: that reaction finishes, by filtering to isolate catalyzer, use again deionized water wash, then at 50~100 ℃, be dried to constant weight, catalyzer is renewable, again for being reacted by tetrahydrobenzene, carboxylic acid and water synthesizing cyclohexanol.
Described Pericarppium arachidis hypogaeae carbon-based solid acid catalyst, is made by following methods, comprises the following steps:
(1) Pericarppium arachidis hypogaeae is cleaned, 50~100 ℃ of oven dry, then pulverize; Get Pericarppium arachidis hypogaeae fragment, put into tube furnace, under N2 protection, Pericarppium arachidis hypogaeae, 350~650 ℃ of heating 6~15 hours, is obtained to partially carbonized Pericarppium arachidis hypogaeae, and is ground to Powdered;
(2) get partially carbonized Pericarppium arachidis hypogaeae powder and sulfonated reagent, be placed in reactor, at N 2under protection, 85~200 ℃ are heated sulfonation 4~15 hours, are then cooled to room temperature, and wherein, material proportion is that every gram of partially carbonized Pericarppium arachidis hypogaeae powder adds 5~50 milliliters of sulfonated reagents;
(3) sulfonated products is filtered, reclaim sulfonated reagent, the deionized water of reusable heat (80 ℃ of >) washing and filtering product, until can't detect remaining sulfonated reagent in washing lotion; At 50~100 ℃, be dried, make required Pericarppium arachidis hypogaeae carbon-based solid acid catalyst.
Described sulfonated reagent is the vitriol oil, oleum, chlorsulfonic acid or Witco 1298 Soft Acid.
The invention has the beneficial effects as follows: in the present invention, take Pericarppium arachidis hypogaeae carbon-based solid acid as catalyzer is applied in this reaction system, obtained good effect; With respect to liquid acid catalyst, the Pericarppium arachidis hypogaeae carbon-based solid acid catalyst using in the present invention is etching apparatus not, and Separation and Recovery is easy, environmentally friendly, and cost is low; With respect to solid acid catalysts such as ion exchange resin and zeolite molecular sieves, the Pericarppium arachidis hypogaeae carbon-based solid acid catalyst cost that the present invention uses is low, active high, and not only oleophylic, but also hydrophilic, and for water, oily two phase reaction, speed of reaction is fast, and the time is short.Use Pericarppium arachidis hypogaeae carbon-based solid acid catalyst catalysis tetrahydrobenzene, carboxylic acid and the reaction of water synthesizing cyclohexanol, cyclohexene conversion rate is 88.0%, hexalin yield is that 82.0%(is shown in embodiment 2).Compare (seeing embodiment 3) with HZSM-5 catalyzer, cyclohexene conversion rate and hexalin yield all improve greatly.In addition, used catalyst good stability of the present invention, is easy to reuse (seeing embodiment 25).
Embodiment
Embodiment 1
(1) Pericarppium arachidis hypogaeae is cleaned, 80 ℃ of oven dry, pulverize.Take 20 grams of Pericarppium arachidis hypogaeae fragments, put into tube furnace, at N 2under protection, Pericarppium arachidis hypogaeae, 550 ℃ of heating 10 hours, is obtained to partially carbonized Pericarppium arachidis hypogaeae, and be ground to Powdered (cross 100 mesh sieves);
(2) get 6 grams of partially carbonized Pericarppium arachidis hypogaeae powder and 150 milliliters of vitriol oils that mass concentration is 98%, be placed in glass flask, at N 2under protection, 160 ℃ are heated sulfonation 10 hours, are then cooled to room temperature;
(3) sulfonated products is filtered, reclaim the vitriol oil; The deionized water of reusable heat (80 ℃ of >) washing and filtering product, until can't detect sulfuric acid in washing lotion; At 80 ℃, be dried, make required Pericarppium arachidis hypogaeae carbon-based solid acid catalyst.
Embodiment 2
By the Pericarppium arachidis hypogaeae carbon-based solid acid catalyst making in embodiment 1 for being reacted by tetrahydrobenzene, formic acid and water synthesizing cyclohexanol.
8 milliliters of tetrahydrobenzene (79 mmole), formic acid 9 milliliters (238 mmole) and water 50 milliliters (2778 mmoles) are joined in tank reactor, then add 0.56 gram of Pericarppium arachidis hypogaeae carbon-based solid acid catalyst, closed reactor; Be filled with 0.6MPa N 2, 110 ℃ of reactions 4 hours.By reaction solution filtration under diminished pressure, make catalyzer separated with reaction solution, with chromatogram ration analysis reaction solution, form.Calculating cyclohexene conversion rate is 88.0%, and hexalin yield is 82.0%, and cyclohexyl formate yield is 5.5%.
Embodiment 3
Use HZSM-5 catalyzer (purchased from Catalyst Factory, Nankai Univ, mol ratio SiO 2/ Al 2o 3=25), consumption is 0.56 gram, and all the other chemical reagent consumptions and reactions steps are identical with embodiment 2, investigates the catalytic performance of HZSM-5 to tetrahydrobenzene, formic acid and the reaction of water synthesizing cyclohexanol.Reaction finishes the rear chromatogram ration analysis reaction solution of using and forms, and obtaining cyclohexene conversion rate is 63.3%, and hexalin yield is 40.0%, and cyclohexyl formate yield is 12.6%.
Embodiment 4~6
Identical with the preparation method of embodiment 1, the sulfonated reagent that just changes step (2) is respectively oleum, chlorsulfonic acid and Witco 1298 Soft Acid, makes respectively required separately Pericarppium arachidis hypogaeae carbon-based solid acid catalyst of the present invention.
Embodiment 7~9
The Pericarppium arachidis hypogaeae carbon-based solid acid catalyst making in embodiment 4~6, for being reacted by tetrahydrobenzene, formic acid and water synthesizing cyclohexanol, is corresponded respectively to embodiment 7~9, and all the other chemical reagent consumptions and reactions steps are identical with embodiment 2, and reaction result is in Table 1.
The impact of the different sulfonated reagents of table 1 on Pericarppium arachidis hypogaeae carbon-based solid acid catalytic property
Embodiment 10~12
Identical with the preparation method of embodiment 1, just change carbonization temperature in step (1) and be respectively 350 ℃, 450 ℃ and 650 ℃, make required Pericarppium arachidis hypogaeae carbon-based solid acid catalyst.
Embodiment 13~15
The Pericarppium arachidis hypogaeae carbon-based solid acid catalyst making in embodiment 10~12, for being reacted by tetrahydrobenzene, formic acid and water synthesizing cyclohexanol, is corresponded respectively to embodiment 13~15, and all the other chemical reagent consumptions and reactions steps are identical with embodiment 2, and reaction result is in Table 2.
The impact of table 2 carbonization temperature on Pericarppium arachidis hypogaeae carbon-based solid acid catalytic property
Embodiment 16~18
Identical with the preparation method of embodiment 1, just change sulfonation temperature in step (2) and be respectively 85 ℃, 120 ℃ and 200 ℃, make required Pericarppium arachidis hypogaeae carbon-based solid acid catalyst.
Embodiment 19~21
The Pericarppium arachidis hypogaeae carbon-based solid acid catalyst making in embodiment 16~18, for being reacted by tetrahydrobenzene, formic acid and water synthesizing cyclohexanol, is corresponded respectively to embodiment 19~21, and all the other chemical reagent consumptions and reactions steps are identical with embodiment 2, and reaction result is in Table 3.
The impact of table 3 sulfonation temperature on Pericarppium arachidis hypogaeae carbon-based solid acid catalytic property
Embodiment 22
Adopt the Pericarppium arachidis hypogaeae carbon-based solid acid catalyst making in embodiment 1, adopt respectively acetic acid and the propionic acid of the amount of same substance to replace formic acid, all the other chemical reagent consumptions and reactions steps are identical with embodiment 2, investigate the impact of different carboxylic acids on reactivity worth, and reaction result is in Table 4.
Table 4 Pericarppium arachidis hypogaeae carbon-based solid acid catalysis tetrahydrobenzene, carboxylic acid and water synthesizing cyclohexanol reactivity worth
Embodiment 23
Adopt the Pericarppium arachidis hypogaeae carbon-based solid acid catalyst making in embodiment 1, change formic acid consumption and be respectively 3 milliliters (79 mmoles), 6 milliliters (159 mmole), 12 milliliters (318 mmole) and 15 milliliters (398 mmole), all the other chemical reagent consumptions and reactions steps are identical with embodiment 2, investigate the impact of formic acid consumption on reaction, the results are shown in Table 5.
The impact of table 5 formic acid consumption on Pericarppium arachidis hypogaeae carbon-based solid acid catalysis tetrahydrobenzene, formic acid and the reaction of water synthesizing cyclohexanol
Embodiment 24
Adopt the Pericarppium arachidis hypogaeae carbon-based solid acid catalyst making in embodiment 1, change temperature of reaction and be respectively 70 ℃, 90 ℃, 130 ℃ and 150 ℃, all the other chemical reagent consumptions and reactions steps are identical with embodiment 2, and reaction result is in Table 6.
The impact of table 6 temperature of reaction on Pericarppium arachidis hypogaeae carbon-based solid acid catalysis tetrahydrobenzene, formic acid and the reaction of water synthesizing cyclohexanol
Embodiment 25
The Pericarppium arachidis hypogaeae carbon-based solid acid catalyst that uses embodiment 1 to make, chemical reagent consumption and reactions steps are identical with embodiment 2.After reaction finishes, by filtering to isolate catalyzer, with deionized water wash, then at 80 ℃, be dried to constant weight, gained catalyzer is again for this reaction of catalysis, and its reaction result is in Table 7.As catalyzer has loss in removal process, use live catalyst to supply weight.
The repeat performance of table 7 Pericarppium arachidis hypogaeae carbon-based solid acid catalyst

Claims (5)

1. by a method for tetrahydrobenzene, carboxylic acid and water reaction synthesizing cyclohexanol, it is characterized by and comprise the steps:
Tetrahydrobenzene, carboxylic acid and water are joined in tank reactor, and its consumption mol ratio is tetrahydrobenzene: carboxylic acid: water=1:0.5~6:5 ~ 40; In reactor, add catalyzer again, its consumption is 0.01~0.2 gram of catalyzer of every milliliter of tetrahydrobenzene; Be filled with N 2, its dividing potential drop is 0.3 ~ 1.5 MPa; Temperature of reaction is risen to 70~150 ℃, react 0.5~5 hour, obtain hexalin;
Described catalyzer is Pericarppium arachidis hypogaeae carbon-based solid acid catalyst.
2. the method by tetrahydrobenzene, carboxylic acid and water reaction synthesizing cyclohexanol as claimed in claim 1, it is characterized by described carboxylic acid is formic acid, acetic acid or propionic acid.
3. the method by tetrahydrobenzene, carboxylic acid and water reaction synthesizing cyclohexanol as claimed in claim 1, it is characterized by also comprise the steps: reaction finish after, by filtering to isolate catalyzer, use again deionized water wash, then at 50 ~ 100 ℃, be dried to constant weight, catalyzer is renewable, again for being reacted by tetrahydrobenzene, carboxylic acid and water synthesizing cyclohexanol.
4. Pericarppium arachidis hypogaeae carbon-based solid acid catalyst as claimed in claim 1, is characterized by by following methods and makes, and comprises the following steps:
(1) Pericarppium arachidis hypogaeae is cleaned, 50 ~ 100 ℃ of oven dry, then pulverize; Get Pericarppium arachidis hypogaeae fragment, put into tube furnace, at N 2under protection, Pericarppium arachidis hypogaeae, 350~650 ℃ of heating 6~15 hours, is obtained to partially carbonized Pericarppium arachidis hypogaeae, and is ground to Powdered;
(2) get partially carbonized Pericarppium arachidis hypogaeae powder and sulfonated reagent, be placed in reactor, at N 2under protection, 85~200 ℃ are heated sulfonation 4~15 hours, are then cooled to room temperature, and wherein, material proportion is that every gram of partially carbonized Pericarppium arachidis hypogaeae powder adds 5 ~ 50 milliliters of sulfonated reagents;
(3) sulfonated products is filtered, reclaim sulfonated reagent, the deionized water of reusable heat (80 ℃ of >) washing and filtering product, until can't detect remaining sulfonated reagent in washing lotion; At 50 ~ 100 ℃, be dried, make required Pericarppium arachidis hypogaeae carbon-based solid acid catalyst.
5. Pericarppium arachidis hypogaeae carbon-based solid acid catalyst as claimed in claim 4, it is characterized by described sulfonated reagent is the vitriol oil, oleum, chlorsulfonic acid or Witco 1298 Soft Acid.
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CN109603905A (en) * 2018-12-05 2019-04-12 福州大学 A kind of Jujun grasses porous charcoal base solid catalyst and preparation method thereof
CN110327678A (en) * 2019-07-30 2019-10-15 河南永新科技有限公司 A kind of separating and reclaiming device and technique of the hydration catalyst of cyclohexene hydration cyclohexanol technique
CN110354531A (en) * 2019-07-30 2019-10-22 河南永新科技有限公司 Cyclohexene hydration produces the separating and reclaiming device and technique of the hydration catalyst of cyclohexanol technique

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CN109603905A (en) * 2018-12-05 2019-04-12 福州大学 A kind of Jujun grasses porous charcoal base solid catalyst and preparation method thereof
CN110327678A (en) * 2019-07-30 2019-10-15 河南永新科技有限公司 A kind of separating and reclaiming device and technique of the hydration catalyst of cyclohexene hydration cyclohexanol technique
CN110354531A (en) * 2019-07-30 2019-10-22 河南永新科技有限公司 Cyclohexene hydration produces the separating and reclaiming device and technique of the hydration catalyst of cyclohexanol technique
CN110327678B (en) * 2019-07-30 2020-09-18 河南永新科技有限公司 Separation and recovery device and process for hydration catalyst of cyclohexene hydration cyclohexanol process

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