CN106278826B - A kind of method of comprehensive utilization of ketone alcohol mixture by utilizing - Google Patents
A kind of method of comprehensive utilization of ketone alcohol mixture by utilizing Download PDFInfo
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- CN106278826B CN106278826B CN201610640884.6A CN201610640884A CN106278826B CN 106278826 B CN106278826 B CN 106278826B CN 201610640884 A CN201610640884 A CN 201610640884A CN 106278826 B CN106278826 B CN 106278826B
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- cyclohexanol
- cyclohexanone
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- benzoquinone
- hydroquinone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention provides a kind of method that cyclohexanol/cyclohexanone mixture prepares hydroquinone for raw material, this method is using cyclohexanol/cyclohexanone mixture as raw material, not using hydrogen as hydrogen source but the hydrogen partial on cyclohexanol and cyclohexanone is transferred to 1,4-benzoquinone using catalyst and synthesizes hydroquinone, cyclohexanol and cyclohexanone portions turn are phenol simultaneously, isolated phenol obtains 1,4-benzoquinone as raw material through peroxidization, 1,4-benzoquinone occurs hydrogen transfer reaction with unreacted cyclohexanol and cyclohexanone again and synthesizes hydroquinone, to realize the cycle of phenol and 1,4-benzoquinone in whole process, the final comprehensive utilization for realizing cyclohexanol/cyclohexanone mixture, the hydroquinone of high added value is prepared using relatively inexpensive cyclohexanol/cyclohexanone mixture as raw material.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of cyclohexanol/cyclohexanone mixture.
Background technology
Cyclohexanone and cyclohexanol are important Organic Chemicals, are widely used in industrial circle general, are prepared in oneself
The main intermediate of amide and adipic acid, is also important industrial solvent, can be used for medicine, paint, coating, rubber and pesticide etc.
Industry also has application in terms of printing the recycling with plastics.At present the monomer caprolactam of synthetic fibers nylon 6 and nylon66 fiber and
Adipic acid is mainly produced using cyclohexanone as raw material, and it is to use cyclohexane oxidation technique to produce 90% or more cyclohexanone, should
The oxidation product that technique obtains is the mixture of cyclohexanol and cyclohexanone, it is therefore desirable to carry out separating-purifying.
It, can not be by it effectively point using conventional distillation technique since cyclohexanol and cyclohexanone dissolve each other and boiling point is close
From needing to find other methods.High-efficient spiral-screen column is industrially used, rectification under vacuum, ability are carried out under the pressure of about 4KPa
So that cyclohexanone content in rectifying product is reached 98~99%, needed for theoretical cam curve be 15 pieces, this method high energy consumption, operation
Complexity, it is of high cost.
WO2014159508, CN105164095 provide a kind of separation method of cyclohexanol and cyclohexanone, which uses hydroxyl
Amine and cyclohexanone occur oximation reaction and obtain cyclohexanol and cyclohexanone oxime, using cyclohexanone oxime in cyclohexanol the low spy of solubility
Property, cyclohexanol and cyclohexanone oxime are separated.But this method can only obtain cyclohexanol and cyclohexanone oxime, therefore be only applicable to close
At caprolactam, it is unable to get cyclohexanone.
Document《Cyclohexanol is studied with cyclohexanone binary system separation of extractive distillation》Using separation of extractive distillation method, by adding
It is extractant to enter diethylene glycol (DEG), changes the relative volatility of tower domestic demand separation component, to detach cyclohexanol and cyclohexanone.
But its theoretical cam curve is 39 pieces, and the number of plates needed for later separation is 11 pieces, operates more complex, high energy consumption, of high cost.
Invention content
The object of the present invention is to provide a kind of method of comprehensive utilization of cyclohexanol/cyclohexanone mixture, i.e., with relatively inexpensive
Cyclohexanol/cyclohexanone mixture be raw material prepare high added value hydroquinone.
In order to realize that the technical purpose of the present invention, a kind of cyclohexanol/cyclohexanone mixture of present invention offer are prepared by raw material
The method of hydroquinone, this method not using hydrogen as hydrogen source, but are utilized and are urged using cyclohexanol/cyclohexanone mixture as raw material
Hydrogen partial on cyclohexanol and cyclohexanone is transferred to 1,4-benzoquinone and synthesizes hydroquinone, while cyclohexanol and cyclohexanone part by agent
Be changed into phenol, isolated phenol obtains 1,4-benzoquinone as raw material through peroxidization, 1,4-benzoquinone again with unreacted ring
Hexanol and cyclohexanone occur hydrogen migration and synthesize hydroquinone, to realize the cycle of phenol and 1,4-benzoquinone in whole process, most
The technique for realizing cyclohexanol/cyclohexanone mixture synthesis hydroquinone eventually.
The technical solution for completing foregoing invention is as follows：1,4-benzoquinone, cyclohexanol/cyclohexanone mixture and catalyst are added and burnt
In bottle, hydrogen transfer reaction occurs under certain temperature and nitrogen protection, isolates catalyst after reaction, obtained mixture
Unreacted cyclohexanol and cyclohexanone, phenol and hydroquinone are isolated by simple distillation.Wherein phenol passes through as raw material
Oxidation reaction generates 1,4-benzoquinone, 1,4-benzoquinone and unreacted cyclohexanol/cyclohexanone mixture, recycling catalyst that the reaction was continued is raw
At hydroquinone, the final purpose for realizing cyclohexanol/cyclohexanone mixture synthesis hydroquinone.
The temperature of hydrogen transfer reaction of the present invention is 80~150 DEG C, preferably 100~140 DEG C；Reaction time be 2~
12h, preferably 4~8h；Cyclohexanone and 1,4-benzoquinone molar ratio are 0~8 in cyclohexanol/cyclohexanone mixture:1, preferably 0.5~3:1；
Catalyst accounts for 1~5wt% of benzoquinones quality, preferably 1~3.5wt%.
Hydrogen-transfer catalyst of the present invention is composition metal loaded catalyst, and active component is three kinds of metals, packet
Include noble metal, transition metal and rare earth metal.Noble metal is platinum, palladium, rhodium, ruthenium, iridium etc.；Transition metal be iron, nickel, cobalt, vanadium,
Copper, manganese etc.；Rare earth metal is yttrium, lanthanum, cerium etc..Combination can be platinum, cobalt, lanthanum；Palladium, vanadium, cerium；Platinum, nickel, yttrium；Rhodium, copper,
Cerium；Ruthenium, manganese, lanthanum；Iridium, iron, cerium etc..Catalyst carrier is activated carbon, silica, aluminium oxide, titanium dioxide etc., preferably dioxy
Change titanium and activated carbon；The load capacity of active component is 3~10wt%, preferably 5~8wt%；Noble metal, transition metal, rare earth gold
The mass ratio for belonging to three is 70~75:15~20:5~15, preferably 70~73:16~18:9~14.
The process of oxidation of phenol synthesis 1,4-benzoquinone involved in the present invention can refer to CN104557487；The system of catalyst
Standby process refers to CN100591416, CN102614868；The method that phenol is detached with benzoquinones refers to CN104761440.Above three
A process is not in the protection domain of this patent.
Relatively inexpensive cyclohexanol/cyclohexanone mixture is changed into the hydroquinone of high added value by the present invention, in the process
The intermediate (phenol, benzoquinones etc.) of generation recycles in system, does not go out system, does not generate other three wastes, open hydroquinone
The new approaches of synthesis；Under the action of ternary composite metal loaded catalyst, instead of traditional by the way of hydrogen migration
Iron powder reducing (generate iron cement and pollute environment) and catalytic hydrogenation (using hydrogen, band press operation, there are security risks), it is existing good
Good plus hydrogen effect is again without security risk；It provides a kind of without separation, the side of integrated treatment cyclohexanol/cyclohexanone mixture
Method.
Specific implementation mode
Following example is intended to explain the protrusion effect of the present invention, rather than limitation of the invention further.
The composite metal catalyst used in order to illustrate this patent preparation method (can specifically refer to CN100591416,
CN102614868), its preparation process is introduced by taking platinum cobalt cerium catalyst for titanium dioxide loaded as an example, and (activity component load quantity is
5wt%, wherein platinum：Cobalt：Cerium mass ratio is 72:18:10).
It is prepared by titanium dioxide precursor：10ml water and 170ml acetone are mixed to get solution A.20ml butyl titanates are added
Enter in 250ml ethylene glycol, poured into solution A after 8h is stirred at room temperature, continues to wash obtained precipitation with ethyl alcohol after stirring 1h
It washs repeatedly and dry to get titanium dioxide precursor at 60 DEG C.
Active component solution is prepared：80mg platinum chlorides, 20mg cobalt chlorides and 10mg cerium chlorides are dissolved in 2ml water, matched
Active component solution processed.
Catalyst preparation：1g titanium dioxide precursors are distributed in 150ml deionized waters, active component is added under stiring
Solution adds the sodium formate solution of 10ml a concentration of 5% after 5min.After being further continued for stirring 5hr, the centrifugation of obtained precipitation is washed
It washs and dries, you can obtain the platinum cobalt cerium catalyst for titanium dioxide loaded that load capacity is 5wt%.
Embodiment 1
Weigh 10.8g 1,4-benzoquinone, 30g cyclohexanol/cyclohexanone mixtures (cyclohexanone content 80wt%) and 0.32g5wt%
Platinum cobalt cerium catalyst for titanium dioxide loaded (platinum：Cobalt：Cerium mass ratio is 72:18:10) enter in 500ml flasks, under nitrogen protection
120 DEG C of insulation reaction 8h, are down to room temperature after reaction, and catalyst sinks to drag, pour out reaction solution and are taken out with Buchner funnel
Filter, isolates catalyst, and obtained filtrate isolates the unreacted cyclohexanol/cyclohexanone mixing of 25g successively by vacuum distillation
Object, 4.2g phenol and 9.9g hydroquinones.Yclohexanone conversion ratio 20.1%, in terms of 1,4-benzoquinone, hydroquinone yield 90%.4.2g
Phenol, 70g ethyl alcohol and 0.2g copper chlorides react 3h under 80 DEG C, 2.5MPa oxygen, and about 10g benzenesulfonamide trifluoroacetate first is added after reaction
Alkane is stood overnight, 1,4-benzoquinone is precipitated with precipitation form, and 1,4-benzoquinone is obtained by filtration after stirring 30 minutes.1,4-benzoquinone again with unreacted
Cyclohexanol/cyclohexanone mixture and recycling catalyst continue occur hydrogen transfer reaction can obtain hydroquinone again, realization
Cyclohexanol/cyclohexanone mixture synthesizes the purpose of hydroquinone.
Embodiment 2
Weigh 10.8g 1,4-benzoquinone, 30g cyclohexanol/cyclohexanone mixtures (cyclohexanone content 65wt%) and 0.28g6wt%
Palladium copper lanthanum supported active Pd/carbon catalyst (palladium：Copper：Lanthanum mass ratio is 71:18:11) enter in 500ml flasks, under nitrogen protection 130
DEG C insulation reaction 7h, is down to room temperature after reaction, and catalyst sinks to drag, pours out reaction solution and is filtered with Buchner funnel,
Isolate catalyst, obtained filtrate by vacuum distillation isolate successively the unreacted cyclohexanol/cyclohexanone mixtures of 24g,
4.1g phenol and 9.6g hydroquinones.Yclohexanone conversion ratio 23.4%, in terms of 1,4-benzoquinone, hydroquinone yield 87.3%.4.1g
Phenol, 70g ethyl alcohol and 0.2g copper chlorides react 3h under 80 DEG C, 2.5MPa oxygen, and about 12g benzenesulfonamide trifluoroacetate first is added after reaction
Alkane is stood overnight, 1,4-benzoquinone is precipitated with precipitation form, and 1,4-benzoquinone is obtained by filtration after stirring 30 minutes.1,4-benzoquinone again with unreacted
Cyclohexanol/cyclohexanone mixture and recycling catalyst continue occur hydrogen transfer reaction can obtain hydroquinone again, realization
Cyclohexanol/cyclohexanone mixture synthesizes the purpose of hydroquinone.
Embodiment 3
Weigh 10.6g 1,4-benzoquinone, 35g cyclohexanol/cyclohexanone mixtures (cyclohexanone content 50wt%) and 0.3g5wt% rhodiums
Nickel lanthanum supported active Pd/carbon catalyst (rhodium：Nickel：Lanthanum mass ratio is 73:17:10) enter in 500ml flasks, 125 DEG C under nitrogen protection
Insulation reaction 6.5h is down to room temperature after reaction, and catalyst sinks to drag, pours out reaction solution and is filtered with Buchner funnel,
Isolate catalyst, obtained filtrate by vacuum distillation isolate successively the unreacted cyclohexanol/cyclohexanone mixtures of 28g,
4.2g phenol and 9.8g hydroquinones.Yclohexanone conversion ratio 27.6%, in terms of 1,4-benzoquinone, hydroquinone yield 89.1%.4.2g
Phenol, 70g ethyl alcohol and 0.2g copper chlorides react 3h under 80 DEG C, 2.5MPa oxygen, and about 15g benzenesulfonamide trifluoroacetate first is added after reaction
Alkane is stood overnight, 1,4-benzoquinone is precipitated with precipitation form, and 1,4-benzoquinone is obtained by filtration after stirring 30 minutes.1,4-benzoquinone again with unreacted
Cyclohexanol/cyclohexanone mixture and the catalyst of recycling continue hydrogen transfer reaction occurs can to obtain hydroquinone, realize ring
The purpose of hexanol/cyclohexanone mixture synthesis hydroquinone.
Embodiment 4
Weigh 11g 1,4-benzoquinone, 40g cyclohexanol/cyclohexanones mixture (cyclohexanone content 40%) and 0.35g 4wt% iridium cobalts
Cerium supported active Pd/carbon catalyst (iridium：Cobalt：Cerium mass ratio is 72:16:12) enter in 500ml flasks, under nitrogen protection 115 DEG C of guarantors
Temperature reaction 9h, is down to room temperature after reaction, and catalyst sinks to drag, pours out reaction solution and is filtered with Buchner funnel, separation
Go out catalyst, obtained filtrate isolates the unreacted cyclohexanol/cyclohexanone mixtures of 33g, 4.3g successively by vacuum distillation
Phenol and 9.9g hydroquinones.Yclohexanone conversion ratio 29.6%, in terms of 1,4-benzoquinone, hydroquinone yield 90%.4.3g phenol,
70g ethyl alcohol and 0.2g copper chlorides react 3h under 80 DEG C, 2.5MPa oxygen, and about 18g benzenesulfonamide trifluoroacetate methane is added after reaction, stirs
It after mixing 30 minutes, stands overnight, 1,4-benzoquinone is precipitated with precipitation form, and 1,4-benzoquinone is obtained by filtration.1,4-benzoquinone again with unreacted ring
Hexanol/cyclohexanone mixture and the catalyst of recycling continue hydrogen transfer reaction occurs can to obtain hydroquinone, realize cyclohexanol/
Cyclohexanone mixture synthesizes the purpose of hydroquinone.
Embodiment 5-10
Inventory and reaction process are with embodiment 1, the difference is that carrying out hydrogen transfer reaction using different loads type catalyst.
Claims (6)
1. a kind of cyclohexanol/cyclohexanone mixture is the method that raw material prepares hydroquinone, which is characterized in that by 1,4-benzoquinone, ring
Hexanol/cyclohexanone mixture and catalyst are added in flask, and hydrogen transfer reaction occurs under certain temperature and nitrogen protection, react
After isolate catalyst, obtained mixture isolates unreacted cyclohexanol and cyclohexanone, phenol by simple distillation
And hydroquinone, the catalyst are composition metal loaded catalyst, including active component and catalyst carrier；Activearm
It is divided into three kinds of metals, including noble metal, transition metal and rare earth metal；Noble metal is platinum, palladium, rhodium, ruthenium, iridium, and transition metal is
Iron, nickel, cobalt, vanadium, copper, manganese, rare earth metal are yttrium, lanthanum, cerium；Catalyst carrier is activated carbon, silica, aluminium oxide, dioxy
Change titanium.
2. cyclohexanol/cyclohexanone mixture is the method that raw material prepares hydroquinone according to claim 1, feature exists
In the temperature of the hydrogen transfer reaction is 80~150 DEG C；Reaction time is 2~12h；Hexamethylene in cyclohexanol/cyclohexanone mixture
Ketone is 0~8 with 1,4-benzoquinone molar ratio:1；Catalyst accounts for 1~5wt% of 1,4-benzoquinone quality.
3. cyclohexanol/cyclohexanone mixture is the method that raw material prepares hydroquinone according to claim 2, feature exists
In the temperature of the hydrogen transfer reaction is 100~140 DEG C；Reaction time is 4~8h；Hexamethylene in cyclohexanol/cyclohexanone mixture
Ketone is 0.5~3 with 1,4-benzoquinone molar ratio:1；Catalyst accounts for 1~3.5wt% of benzoquinones quality.
4. cyclohexanol/cyclohexanone mixture is the method that raw material prepares hydroquinone according to claim 1, feature exists
In active component combination is platinum, cobalt, lanthanum；Palladium, vanadium, cerium；Platinum, nickel, yttrium；Rhodium, copper, cerium；Ruthenium, manganese, lanthanum；Iridium, iron, cerium.
5. cyclohexanol/cyclohexanone mixture is the method that raw material prepares hydroquinone according to claim 1, feature exists
In the load capacity of active component is 3~10wt%；Noble metal, transition metal, rare earth metal three mass ratio be 70~75:
15~20:5~15.
6. cyclohexanol/cyclohexanone mixture is the method that raw material prepares hydroquinone according to claim 5, feature exists
In the load capacity of active component is 5~8wt%；Noble metal, transition metal, rare earth metal three mass ratio be 70~73:16
~18:9~14.
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| CN1918101A (en) * | 2003-12-18 | 2007-02-21 | 通用电气公司 | Processes for preparing benzoquinones and hydroquinones |
| JP4288030B2 (en) * | 1999-07-30 | 2009-07-01 | パナソニック株式会社 | Semiconductor structure using group III nitride quaternary material system |
| CN102718633A (en) * | 2012-02-21 | 2012-10-10 | 湖北开元化工科技股份有限公司 | Hydroquinone preparation method |
| JP5064233B2 (en) * | 2004-11-24 | 2012-10-31 | ゼネラル・モーターズ・コーポレーション | Membrane processing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5760325B2 (en) * | 1973-10-19 | 1982-12-18 | Teijin Ltd | |
| JPH04288030A (en) * | 1991-03-15 | 1992-10-13 | Daicel Chem Ind Ltd | Production of 1-methyltetrahydrobenzyl alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4288030B2 (en) * | 1999-07-30 | 2009-07-01 | パナソニック株式会社 | Semiconductor structure using group III nitride quaternary material system |
| CN1918101A (en) * | 2003-12-18 | 2007-02-21 | 通用电气公司 | Processes for preparing benzoquinones and hydroquinones |
| JP5064233B2 (en) * | 2004-11-24 | 2012-10-31 | ゼネラル・モーターズ・コーポレーション | Membrane processing method |
| CN102718633A (en) * | 2012-02-21 | 2012-10-10 | 湖北开元化工科技股份有限公司 | Hydroquinone preparation method |
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| Title |
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| Mesoporous zirconosilicate doughnuts with high performance in liquid oxidative dehydrogenation of hydroquinone to quinone;Arnaud Lemaire等;《Journal of Colloid and Interface Science》;20110526;第361卷;第25-32页 * |
| MgZrAlO 复合氧化物催化酮氢转移还原反应;石能富等;《高效化学工程学报》;20110228;第25卷(第1期);第61-66页 * |
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