CN103785451A - Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst - Google Patents

Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst Download PDF

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CN103785451A
CN103785451A CN201410050168.3A CN201410050168A CN103785451A CN 103785451 A CN103785451 A CN 103785451A CN 201410050168 A CN201410050168 A CN 201410050168A CN 103785451 A CN103785451 A CN 103785451A
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catalyst
cyclohexene
hzsm
reaction
cyclohexanol
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魏东炜
朱璟
汪宝和
陈爽
殷金柱
田红兵
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Tianjin University
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Tianjin University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Abstract

The invention discloses a catalyst for preparing cyclohexanol through cyclohexene hydration. The catalyst consists of a carrier HZSM-5 and supported active ingredient niobium, the catalyst is subjected to surface modification by adopting a silylating reagent, and the oleophylic performance can be enhanced. Meanwhile, because the number of reaction sites containing activated hydrogen is reduced, the stability of the compound is enhanced. The application of the catalyst in preparation of the cyclohexanol through cyclohexene hydration comprises the following steps: adding the catalyst prepared by the reaction, cyclohexene and water into a reactor, wherein a mass ratio of the catalyst to the cyclohexene to the water is 1 to 2-20 to 2-20, the reaction temperature is 80 to 180 DEG C, and the reaction time is 0.5-3.0 hours. The prepared catalyst is easy to separate and recycle, the equipment is not corroded, and the catalyst is environmentally friendly. Compared with an original method for preparing cyclohexanol through heterogeneous catalysis cyclohexene hydration, the method is high in catalyst activity and high in selectivity.

Description

The catalyst of preparing cyclohexanol by cyclohexene hydration reaction and application
Technical field
Technical scheme of the present invention belongs to the synthetic of cyclohexanol, relates to a kind of technique of preparing cyclohexanol take cyclohexene as raw material hydration.Specifically relate to a kind of silylating reagent and niobic acid HZSM-5 surface is modified, obtain amphipathic catalyst and methods for making and using same thereof.
Background technology
Cyclohexanol can be used for preparing adipic acid, hexamethylene diamine, cyclohexanone, caprolactam, as good middle higher boiling Organic chemical products, is widely used in fields such as organic chemical industry, weaving and coating.Cyclohexanol, owing to possessing the good advantage such as dissolubility and low volatility, also can be used as the solvent of many high molecular polymers, alkyd resins, rubber, ethyl cellulose, acetate fiber and nitrocotton.
Cyclohexene hydration is produced cyclohexanol route, and safe, energy-conservation, carbon atom utilization rate 100%, without discarded object and environmental pollution, has the feature such as Atom economy and environmental friendliness.There is very large advantage industrial, be subject to showing great attention to and paying attention to of people.
Cyclohexene hydration is typical acid catalyzed reaction, and the acidic catalyst that can adopt is as inorganic acid, Ion exchange resins and solid acid molecular sieve etc.
Mineral acid and benzene sulfonic acid are the earliest for hydration reaction.20th century the forties, (the US2504517 of Phillip oil company, US2414646) report can make cyclohexene hydration generate cyclohexanol take sulfuric acid as catalyst, but due to the defect such as have product recovery process complexity in sulfur process, energy consumption is high, equipment corrosion is serious.In order to overcome the defect that adopts homogeneous catalyst, 1986, Dupont company applied for utilizing the patent (US4595786) of perfluorinated sulfonic resin catalysis cyclohexene hydration; Within 2008, woods delicate fragrance has proposed a kind of cyclohexene hydration patent (CN101284767) take sulfonic acid type strong acid salt ion exchange resin as catalyst, compare ion exchange resin has solved target product recovery, the problem such as has separated with mineral acid catalyst, but due to cyclohexene hydration reaction, need the reaction temperature of 100～130 ℃, the shortcomings such as the short and poor heat stability of ion exchange resin average life, price is higher has also limited its extensive use in hydration system; 1986, Asahi Chemical Industry discloses the patent (JP61180735 for preparing efficient hydration molecular sieve catalyst, JP61234945), more research shows, in cyclohexene, water, catalyst three-phase reaction system, the hydrophobicity of molecular sieve pore passage inwall plays an important role for the competitive Adsorption of cyclohexene and water, suitable hydrophobicity is conducive to the absorption of cyclohexene in catalyst duct, thereby raising catalytic activity, be that reaction rate and balance are subject to cyclohexene and the cyclohexanol adsorption capacity on catalyst, and the distribution coefficient control of profit phase.
Molecular sieve is the more solid acid catalyst of current industrial application, its preparation easily, stable in properties, be easy to and reactants separate, can repeatedly recycle, there is obvious advantage, but industrial in order to reach the catalyst that considerable reaction rate need to be a large amount of, be therefore necessary to develop more efficient hydration catalyst.
Summary of the invention
Technical problem to be solved by this invention is: niobium oxide (Nb is provided 2o 5) load HZSM-5 and silylating reagent it is carried out to finishing can be in water, oily two-phase interface place equally distributed boundary amphiphilic zeolite catalyst, preparation method and the application in preparing cyclohexanol by cyclohexene hydration reaction reaction thereof.The preparation method of catalyst that niobium load HZSM-5 of the present invention and silylating reagent carry out finishing to it is simple, easy operating, and repeatability is high; This catalyst is a kind of activity, selective high heterogeneous catalysis, for preparing cyclohexanol by cyclohexene hydration reaction reaction, overcome corrosion and the separation problem of homogeneous acid catalyst to equipment, and the shortcoming such as existing heterogeneous catalysis reaction rate is slow, the reaction time is long, cyclohexanol yield is low.
Technical scheme of the present invention is as follows:
A kind of preparing cyclohexanol by cyclohexene hydration reaction catalyst, preparation method is as follows:
A) first prepare niobium and be carried on the catalyst of HZSM-5;
B) silylating reagent is dissolved in to toluene;
C) a) solid catalyst is put into b) silylating reagent toluene solution, silylating reagent in toluene solution and solids weight ratio 0.1～1.0:1, at room temperature stir after 0.1～3 hour sand core funnel suction filtration, solid is dried 0.1～5 hour at 50～100 ℃, thereby obtains load Nb 2o 5amphipathic HZSM-5 catalyst.
Utilize catalyst of the present invention to be applied to the method for preparing cyclohexanol by cyclohexene hydration reaction, step is as follows:
Amphipathic HZSM-5 catalyst, cyclohexene and the water of step c) are joined in reactor, its consumption is quality than catalyst: cyclohexene: water=1:(2～20): (2～20), reaction temperature is risen to 80～180 ℃, and the reaction time is 0.5～3.0 hour, obtains cyclohexanol.
Described silylating reagent is selected from HMDS, n-octyl trichlorine azane, or has the compound of following general formula:
(R 1) x(R 2) ySiCl z
R in formula 1and R 2for alkyl or aryl, R 1and R 2can be the same or different; X+y+z=4, and z>=1.
The silylating reagent of the compound of described general formula is trim,ethylchlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl vinyl chlorosilane, dimethyl isopropyl chloride silane, tert-butyl chloro-silicane, dimethyl octyl group chlorosilane, octadecyl trichlorosilane alkane or cyclohexyl trichlorosilane.
Catalyst of the present invention is made up of the active component niobium of carrier HZSM-5 and load, afterwards, silylation is incorporated in molecule, generally to replace reactive hydrogen, reactive hydrogen has reduced the polarity of compound after being replaced by silylation, reduced hydrogen bond constraint, the Silylation thing that therefore formed can strengthen oleophylic performance.Meanwhile, due to the reaction site decreased number containing reactive hydrogen, the stability of compound is also strengthened.
After preparing cyclohexanol by cyclohexene hydration reaction reaction finishes, by filtering to isolate catalyst, with ethanol washing, then 50～80 ℃ of vacuum drying to constant weight, catalyst can be again for cyclohexene hydration reaction.
The invention has the beneficial effects as follows: in the present invention, adopt silylating reagent to carry out finishing to the HZSM-5 of load niobium, preparing can be at water, the equally distributed boundary amphiphilic zeolite in oily two-phase interface place, make it to become the amphipathic catalyst of water oil, the resistance to mass tranfer of cyclohexene at catalyst surface be can reduce, the activity of original catalyst, selective and life-span improved.In addition, used catalyst good stability of the present invention, easily regenerates and reuses.(seeing embodiment 17)
The specific embodiment
Comparative example 1
80 milliliters of the ammonium niobium oxalate aqueous solution preparing 0.15 mol/L concentration, impregnated in 50 grams of carrier HZSM-5, at 100 ℃, stir, heating until water volatilize completely; Then be placed in 150 ℃, baking oven and be dried 3 hours; Finally be placed in 400 ℃ of roastings of Muffle furnace 2 hours, thereby obtain Nb 2o 5the catalyst of load capacity 6 % by weight, is designated as Nb/HZSM-5.
By 45 grams of the HZSM-5 catalyst of load niobium, 100 grams of 110 grams of cyclohexene, water join in 0.5 liter of autoclave, still is sealed, be filled with high pure nitrogen displacement, be heated to 120 ℃, react 1.5 hours, by reactant liquor filtration under diminished pressure, catalyst and reactant liquor are separated, with the composition of gas chromatographic analysis organic phase, and ring hexanol yield and selective.The results are shown in Table 1.
Embodiment 1
50 grams of Nb that comparative example 1 is made 2o 5load HZSM-5 catalyst, put into trim,ethylchlorosilane-toluene solution that 300 ml concns are 0.1 grams per milliliter, at room temperature stir after 3 hours, sand core funnel suction filtration, and with 100 milliliters of carbon tetrachloride and each point of three washing of 100 milliliters of ethanol, finally at 50 ℃, dry 5 hours, thereby obtain load Nb 2o 5amphipathic HZSM-5 catalyst, be designated as TMCS-Nb/HZSM-5.
Embodiment 2～11
Identical with the preparation method of embodiment 6, just changing silylating reagent is (OTCSZ) such as HMDS (HMDSZ), chlorotriethyl silane (TECS), tri isopropyl chlorosilane (TIPCS), cyclohexyl trichlorosilane (CHTCS), dimethyl vinyl chlorosilane (DMVCS), dimethyl isopropyl chloride silane (TMCS), tert-butyl chloro-silicane (TBDMCS), dimethyl octyl group chlorosilane (DMOCS), octadecyl trichlorosilane alkane (OTCS), n-octyl trichlorine azane.Make load Nb 2o 5amphipathic HZSM-5 catalyst, be designated as respectively HMDSZ-Nb/HZSM-5, TECS-Nb/HZSM-5, TIPCS-Nb/HZSM-5, CHTCS-Nb/HZSM-5, DMVCS-Nb/HZSM-5, TMCS-Nb/HZSM-5, TBDMCS-Nb/HZSM-5, DMOCS-Nb/HZSM-5, OTCS-Nb/HZSM-5 and OTCSZ-Nb/HZSM-5.
Embodiment 12
The amphipathic load niobium HZSM-5 catalyst that embodiment 1～11 is made is applied in preparing cyclohexanol by cyclohexene hydration reaction reaction, and reaction result is compared, in order to evaluate the performance of catalyst prepared by each embodiment.Evaluation method is identical with comparative example 1.The activity rating of embodiment 1～11 prepared catalyst the results are shown in Table 1.
Table 1 adopts the impact on hydration reaction of catalyst that different silylating reagents modify
Figure BDA0000465662560000041
Embodiment 13
50 grams of Nb that comparative example 1 is made 2o 5load HZSM-5 catalyst, put into trim,ethylchlorosilane-toluene solution that 100 ml concns are 0.5 grams per milliliter, at room temperature stir after 0.1 hour, sand core funnel suction filtration, and with 100 milliliters of carbon tetrachloride and each point of three washing of 100 milliliters of ethanol, finally at 100 ℃, dry 0.1 hour, thereby obtain load Nb 2o 5amphipathic HZSM-5 catalyst.Press 45 grams of catalyst, 100 grams of 110 grams of cyclohexene, water join in 0.5 liter of autoclave, at 120 ℃, react 1.5 hours, by reactant liquor filtration under diminished pressure, catalyst and reactant liquor are separated, with the composition of gas chromatographic analysis organic phase, and ring hexanol yield and selective.Cyclohexene conversion rate is 15.2%, and cyclohexanol is selectively 99.6%.
Embodiment 14
5 grams of load Nb that embodiment 1 is made 2o 5amphipathic HZSM-5 catalyst (TMCS-Nb/HZSM-5), join in 0.5 liter of autoclave with 100 grams of 100 grams of cyclohexene, water, at 120 ℃, react 1.5 hours, by reactant liquor filtration under diminished pressure, catalyst and reactant liquor are separated, with the composition of gas chromatographic analysis organic phase, and ring hexanol yield and selective.Cyclohexene conversion rate is 15.3%, and cyclohexanol is selectively 99.6%.
Embodiment 15
The load Nb that uses embodiment 1 to make 2o 5amphipathic HZSM-5 catalyst (TMCS-Nb/HZSM-5), chemical reagent consumption is identical with embodiment 12 with reactions steps, but change reaction temperature, its reaction result is in table 2.
The impact of table 2 reaction temperature on cyclohexene hydration reaction
Figure BDA0000465662560000051
Embodiment 16
The load Nb that uses embodiment 1 to make 2o 5amphipathic HZSM-5 catalyst (TMCS-Nb/HZSM-5), chemical reagent consumption is identical with embodiment 12 with reactions steps, but change the reaction time, its reaction result is in table 3.
The impact of table 3 reaction time on cyclohexene hydration reaction
Figure BDA0000465662560000052
Embodiment 17
The load Nb that uses embodiment 1 to make 2o 5amphipathic HZSM-5 catalyst (TMCS-Nb/HZSM-5), press catalyst, chemical reagent consumption is identical with embodiment 12 with reactions steps, after reaction finishes, by filtering to isolate catalyst, with ethanol washing, then 80 ℃ of vacuum drying to constant weight, gained catalyst is applied to cyclohexene hydration reaction again, and its reaction result is in table 4.As catalyst has loss in removal process, use fresh catalyst to supply weight.
Table 4 catalyst access times are on the impact by cyclohexene hydration reaction
Figure BDA0000465662560000061

Claims (4)

1. a preparing cyclohexanol by cyclohexene hydration reaction catalyst, is characterized in that niobium to be carried on the amphipathic catalyst of profit that HZSM-5 obtains through silanization, and preparation method is as follows:
A) first prepare niobium and be carried on the catalyst of HZSM-5;
B) silylating reagent is dissolved in to toluene;
C) a) solid catalyst is put into b) silylating reagent toluene solution, silylating reagent in toluene solution and solids weight ratio 0.1～1.0:1, at room temperature stir after 0.1～3 hour, sand core funnel suction filtration, solid is dried 0.1～5 hour at 50～100 ℃, thereby obtains the amphipathic HZSM-5 catalyst of load Nb2O5.
2. the catalyst of claim 1 is applied to the method for preparing cyclohexanol by cyclohexene hydration reaction, it is characterized in that step is as follows:
Amphipathic HZSM-5 catalyst, cyclohexene and the water of step c) are joined in reactor, its consumption is quality than catalyst: cyclohexene: water=1:(2～20): (2～20), reaction temperature is risen to 80～180 ℃, and the reaction time is 0.5～3.0 hour, obtains cyclohexanol.
3. the method for claim 1, is characterized in that described silylating reagent is selected from HMDS, n-octyl trichlorine azane, or has the compound of following general formula:
(R 1) x(R 2) ySiCl z
R in formula 1and R 2for alkyl or aryl, R 1and R 2can be the same or different; X+y+z=4, and z>=1.
4. method as claimed in claim 3, is characterized in that the silylating reagent of the compound of described general formula is trim,ethylchlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl vinyl chlorosilane, dimethyl isopropyl chloride silane, tert-butyl chloro-silicane, dimethyl octyl group chlorosilane, octadecyl trichlorosilane alkane or cyclohexyl trichlorosilane.
CN201410050168.3A 2014-02-13 2014-02-13 Catalyst for preparing cyclohexanol through cyclohexene hydration and application of catalyst Pending CN103785451A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106000450A (en) * 2016-05-20 2016-10-12 中国天辰工程有限公司 Preparation method of catalyst for hydrating cyclohexene
CN108212205A (en) * 2018-01-23 2018-06-29 山东亚科环保科技有限公司 A kind of cyclohexene prepares the preparation method and applications of cyclohexanol catalyst
CN111450875A (en) * 2020-04-29 2020-07-28 烟台大学 Preparation method of cyclohexene hydration liquid-liquid amphiphilic catalyst
CN113559931A (en) * 2021-06-18 2021-10-29 烟台大学 Preparation method of hydrophobization heteropoly acid catalyst and application of catalyst in cyclohexene hydration
CN115591571A (en) * 2022-09-29 2023-01-13 神马实业股份有限公司（Cn） Modification method for preparing cyclohexanol HZSM-5catalyst by direct hydration of cyclohexene
CN115591539A (en) * 2022-10-21 2023-01-13 神马实业股份有限公司（Cn） Catalyst for direct hydration reaction of cyclohexene and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106000450A (en) * 2016-05-20 2016-10-12 中国天辰工程有限公司 Preparation method of catalyst for hydrating cyclohexene
CN108212205A (en) * 2018-01-23 2018-06-29 山东亚科环保科技有限公司 A kind of cyclohexene prepares the preparation method and applications of cyclohexanol catalyst
CN111450875A (en) * 2020-04-29 2020-07-28 烟台大学 Preparation method of cyclohexene hydration liquid-liquid amphiphilic catalyst
CN113559931A (en) * 2021-06-18 2021-10-29 烟台大学 Preparation method of hydrophobization heteropoly acid catalyst and application of catalyst in cyclohexene hydration
CN115591571A (en) * 2022-09-29 2023-01-13 神马实业股份有限公司（Cn） Modification method for preparing cyclohexanol HZSM-5catalyst by direct hydration of cyclohexene
CN115591539A (en) * 2022-10-21 2023-01-13 神马实业股份有限公司（Cn） Catalyst for direct hydration reaction of cyclohexene and preparation method thereof
CN115591539B (en) * 2022-10-21 2024-02-02 神马实业股份有限公司 Catalyst for cyclohexene direct hydration reaction and preparation method thereof

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