CN104069875B - A kind of dehydrogenation and preparation method thereof and a kind of method of dehydrogenating - Google Patents
A kind of dehydrogenation and preparation method thereof and a kind of method of dehydrogenating Download PDFInfo
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- CN104069875B CN104069875B CN201310104478.4A CN201310104478A CN104069875B CN 104069875 B CN104069875 B CN 104069875B CN 201310104478 A CN201310104478 A CN 201310104478A CN 104069875 B CN104069875 B CN 104069875B
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Abstract
The invention provides a kind of dehydrogenation and preparation method thereof, wherein, the method includes: water solublity nickel compound containing and acidic sol are mixed with ethanol, and the pH value of mixture obtained with alkaline matter regulation is 59, and stand aging under this pH value condition, then wash, be dried to obtain solid；Roasting after described solid and dehydrogenation adjuvant component are mixed.The invention provides a kind of method of dehydrogenating, wherein, the method includes: under the conditions of catalytic dehydrogenation, cyclohexanediol and/or the Cyclohexanediole derivatives containing ehter bond are contacted with dehydrogenation, wherein, described dehydrogenation is the dehydrogenation prepared according to preparation method of the present invention.The dehydrogenation prepared according to the method for the present invention is for cyclohexanediol and/or the Cyclohexanediole derivatives dehydrogenation containing ehter bond, and dehydrogenation activity is high, and the stability height i.e. life-span is long.
Description
Technical field
The preparation method that the present invention relates to a kind of dehydrogenation and the dehydrogenation prepared by the method, with
And one method of dehydrogenating.
Background technology
The existing dehydrogenation kind for cyclohexanediol dehydrogenation is more, however existing dehydrogenation activity with
And the stability i.e. life-span still needs to be improved further.
Meanwhile, the derivant of cyclohexanediol is numerous, wherein, is much important chemical intermediate.By cyclohexanediol
Derivant is the important reaction of a class as the derivant of intermediate dehydrogenation synthesis diphenol, spreading out of existing method synthesizing o-dihydroxybenzene
Biological being typically synthesizes with catechol for raw material, and the condition of such reaction is harsh, and side reaction is many, selectivity
Difference, yield are the highest.Especially with the method for dehydrogenating of derivant of the cyclohexanediol of ehter bond, have no report.
Summary of the invention
It is an object of the invention to provide the preparation side of a kind of dehydrogenation activity preferable dehydrogenation of relatively high and stable property
Method.
For realizing object defined above, according to the first aspect of the invention, the invention provides the preparation of a kind of dehydrogenation
Method, wherein, the method includes: water solublity nickel compound containing and acidic sol is mixed with ethanol, and regulates with alkaline matter
The pH value of the mixture obtained is 5-9, and stands aging under this pH value condition, then washes, is dried to obtain solid；By described
Roasting after solid and the mixing of dehydrogenation adjuvant component.
According to the second aspect of the invention, the invention provides a kind of according to the preparation method of the present invention prepare de-
Hydrogen catalyst.
According to the third aspect of the invention we, the invention provides a kind of method of dehydrogenating, wherein, the method includes: in catalysis
Under dehydrogenation condition, cyclohexanediol and/or the Cyclohexanediole derivatives containing ehter bond are contacted with dehydrogenation, wherein, described
Dehydrogenation is the dehydrogenation prepared according to preparation method of the present invention.
The dehydrogenation prepared according to the method for the present invention is for cyclohexanediol and/or the hexamethylene two containing ehter bond
01 derivatives dehydrogenation, dehydrogenation activity is high, and the stability height i.e. life-span is long.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of dehydrogenation, wherein, the method includes: by nickeliferous for water solublity chemical combination
Thing and acidic sol mix with ethanol, and the pH value of mixture obtained with alkaline matter regulation is 5-9, and in this pH value condition
Lower standing is aging, then washes, is dried to obtain solid；Roasting after described solid and dehydrogenation adjuvant component are mixed.
In the present invention, so that dehydrogenation adjuvant component and described solids mixing is uniform as far as possible, so that preparation
Each component on the dehydrogenation obtained is uniformly distributed, preferably by the solution of described solid and dehydrogenation adjuvant component (for example,
The aqueous solution of dehydrogenation adjuvant component) mixing after roasting.
The dehydrogenation prepared according to preceding method is urged for dehydrogenation of the present invention, dehydrogenation activity height, and dehydrogenation
Agent good stability.
With the method for the invention it is preferred to described water solublity nickel compound containing, acidic sol and the consumption weight ratio of ethanol
For 0.01-10:0.5-20:1, more preferably 0.1-2:1-5:1, more preferably 0.62:1.3:1；The most described acidity
The solid content of colloidal sol is 10-30 weight %, more preferably 20 weight %.Dehydrogenation is prepared according to this consumption weight ratio,
The catalyst dehydrogenation activity prepared can be made to improve further.
With the method for the invention it is preferred to the aging temperature of described standing is 30-70 DEG C, more preferably 50 DEG C.Aforementioned
At a temperature of stand aging, the catalyst dehydrogenation activity prepared improves further.
With the method for the invention it is preferred to described standing aging time is 0.1-10h, more preferably 1-6h.According to front
State standing ageing time and prepare dehydrogenation, it is possible to make the catalyst dehydrogenation activity prepared improve further.
With the method for the invention it is preferred to the condition being dried includes: temperature is 100-120 DEG C, and the time is 10-20 hour.
Under aforementioned drying condition, it is possible to improve dehydrogenation activity and the life-span of catalyst further.
With the method for the invention it is preferred to the condition of described roasting includes: temperature is 300-500 DEG C, the time is that 2-5 is little
Time.Under aforementioned roasting condition, it is possible to improve dehydrogenation activity and the life-span of catalyst further.
With the method for the invention it is preferred to optional wider range of consumption of described water solublity nickel compound containing, adjuvant component,
Specifically can be adjusted according to needs, the present invention to this without particular/special requirement.
With the method for the invention it is preferred to described water solublity nickel compound containing is in nickel sulfate, nickel nitrate and Nickel dichloride.
One or more, the most specifically used for nickel nitrate.Use the aforementioned nickeliferous chemical combination of preferred water solublity
Thing, it is possible to improve activity and the life-span of dehydrogenation further.
The method according to the invention, optional wider range of the kind of described acidic sol, can be such as siliceous and/or
One or more in the colloidal sol of aluminum, preferably acidic silicasol, acidic aluminum sol and acid silicon-aluminum sol, more preferably pH value
For one or more in acidic silicasol, acidic aluminum sol and the acid silicon-aluminum sol of 3-6.Use aforementioned preferred acidity molten
Dehydrogenation prepared by glue, it is possible to improve activity and the life-span of dehydrogenation further.
With the method for the invention it is preferred to described alkaline matter is in sodium carbonate, sodium bicarbonate, ammonia and ammonium carbonate
Kind or multiple, the most specifically used for sodium carbonate.
The method according to the invention, optional wider range of described dehydrogenation adjuvant component, commonly used in the art for conduct
The adjuvant component of dehydrogenation is used equally to the present invention, and for the present invention, the most described dehydrogenation adjuvant component is sodium sulfate, sulfur
One or more in acid potassium, lithium sulfate, magnesium sulfate, calcium sulfate and sodium carbonate, more preferably sodium sulfate.
According to the second aspect of the invention, the present invention provides a kind of dehydrogenation prepared according to the preparation method of the present invention
Catalyst.
The dehydrogenation dehydrogenation activity of the present invention is high, and good stability.
According to the third aspect of the invention we, the invention provides a kind of method of dehydrogenating, the method includes: at catalytic dehydrogenation bar
Under part, cyclohexanediol and/or the Cyclohexanediole derivatives containing ehter bond being contacted with dehydrogenation, wherein, described dehydrogenation is urged
Agent is the dehydrogenation prepared according to the preparation method of the present invention.
In the present invention, optional wider range of described catalytic dehydrogenation condition, for the present invention, the most described catalytic dehydrogenation bar
Part includes: temperature is 180-350 DEG C, preferably 240-320 DEG C；Dehydrogenation and cyclohexanediol and/or the ring containing ehter bond
The mass ratio of hexane diol derivatives is 1:5-50.
In the present invention, the most described contact is carried out in the presence of solvent, optional wider range of the kind of described solvent,
Can be such as one or more in alcohol, ester, nitrile, ketone and water；The most described solvent is methanol, ethanol, propanol, second two
Alcohol, propylene glycol, Hexalin, butanediol, capryl alcohol, ethyl acetate, cyclohexyl acetate, glycol dicaproate, ethylene glycol bisthioglycolate acetic acid
Ester, butanediol diacetate esters, diethylene adipate, butyl phthalate, octyl phthalate, acetonitrile, adiponitrile, hexamethylene
One or more in ketone, acetone, isophorone, Ketohexamethylene and water.Further preferred described solvent is ester, preferably acetic acid second
Ester, glycol dicaproate, ethylene acetate, butanediol diacetate esters, diethylene adipate and butyl phthalate
In one or more.
In the present invention, preferred solvent with the mass ratio of cyclohexanediol and/or the Cyclohexanediole derivatives containing ehter bond is
0.1-100:1, more preferably 0.5-10:1.
According to the method for the present invention, the cyclohexanediol of various structural formulas all can use the method dehydrogenation of the present invention, and it is permissible
For 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol.
According to the method for the present invention, every Cyclohexanediole derivatives containing ehter bond all can use the method for the present invention to take off
Hydrogen, for the present invention, the preferably described Cyclohexanediole derivatives containing ehter bond is cyclohexanediol monoalky lether and/or cyclohexanediol
Dialkyl ether, the most described alkyl is the straight or branched alkyl of C1-C10, and the most described alkyl is the straight chain of C1-C6 or props up
Alkyl group, wherein, described cyclohexanediol monoalky lether is the one in following structural formula:
OrWherein, R is the straight chain of C1-C10 or props up
The straight or branched alkyl of alkyl group, preferably C1-C6；
Wherein, described cyclohexanediol dialkyl ether is the one in following structural formula:
OrWherein R1And R2
It is respectively the straight or branched alkyl of C1-C10, preferably R1And R2It is respectively the straight or branched alkyl of C1-C6.
The method according to the invention, the most described Cyclohexanediole derivatives containing ehter bond is cyclohexanediol list first
Ether, cyclohexanediol list ether, cyclohexanediol list propyl ether, cyclohexanediol monobutyl ether, cyclohexanediol dimethyl ether, cyclohexanediol diethyl ether
With one or more in cyclohexanediol dipropyl ether；The most described Cyclohexanediole derivatives containing ehter bond is O-methoxy
HexalinAdjacent ethyoxyl HexalinAdjacent propoxyl group HexalinAdjacent butoxy HexalinAdjacent amoxy HexalinAdjacent hexyloxy HexalinAdjacent cyclohexyloxy HexalinAdjacent dimethoxycyclohexaneAdjacent diethoxy hexamethyleneWith adjacent dipropoxy hexamethyleneIn one or more.Before
Stating the Cyclohexanediole derivatives method dehydrogenation according to the present invention preferably containing ehter bond, its conversion ratio is high, and target product
The selectivity of aromatic compound is high.
Hereinafter will be described the present invention by embodiment, but the present invention will be not limited to this.
In the present invention, use gas chromatogram to carry out the analysis of each composition in system, carry out quantitatively, all by correction normalization method
Can refer to prior art carry out, calculate the evaluation indexes such as the conversion ratio of reactant, the yield of product and selectivity on this basis.
In the present invention, the time of staying refers to cyclohexanediol and/or the Cyclohexanediole derivatives containing ehter bond is urged with dehydrogenation
The time of agent contact catalytic time, i.e. dehydrogenation.
In the present invention, the conversion ratio of reactant (cyclohexanediol and/or the Cyclohexanediole derivatives containing ehter bond) calculates public affairs
Formula is as follows:
The computing formula of target product selectivity is as follows:
The computing formula of target product yield is as follows:
YTarget product=STarget product×XReactant
Wherein, X is conversion ratio；S is selectivity；Y is yield；M is the quality of component；N is the amount of the material of component；Wherein
m0And n0Represent the quality before reaction and mole respectively.
Catalyst Preparation Example 1
The 39 grams of Ni (NO that will weigh3)2·6H2O and 390 grams of solid contents are the acidic silicasol (pH value is 4) of 30 mass %,
Miscible in the dehydrated alcohol of 500ml, obtain mixture, add aqueous sodium carbonate (concentration is 1.5mol/L) regulation mixture
PH value be 7-7.2, at 50 DEG C, continue stand aging 1 hour, be then filtrated to get solid sediment, by solid sediment
Through deionized water wash to after without sodium, then with 500ml absolute ethanol washing one time, finally dry at 110 DEG C within 20 hours, obtain
Solid；
Weigh 50 grams size-reduced to the 300 above-mentioned solids of purpose, and the aqueous sodium persulfate solution (concentration 20 mass %) of 9 grams, so
Rear kneading, then at 500 DEG C, roasting 2h obtains catalyst C1.
Catalyst Preparation Example 2
The 780 grams of Ni (NO that will weigh3)2·6H2O and 1950 grams of solid contents are the acid silicon-aluminum sol (pH value of 10 mass %
It is 6), miscible in the dehydrated alcohol of 500ml, obtain mixture, add aqueous sodium carbonate (concentration is 1.5mol/L) regulation
The pH value of mixture is 8-9, at 50 DEG C, continues to stand aging 6 hours, is then filtrated to get solid sediment, is sunk by solid
Shallow lake thing through deionized water wash to after without sodium, then with 500ml absolute ethanol washing one time, finally at 100 DEG C dry 15 hours
Obtain solid；
Weigh 50 grams and size-reduced add the aqueous sodium persulfate solution (concentration 20 mass %) of 20 grams to the 300 above-mentioned solids of purpose,
Then mediating, then at 300 DEG C, roasting 5h obtains catalyst C2.
Catalyst Preparation Example 3
The 246.3 grams of Ni (NO that will weigh3)2·6H2O and 510 grams of solid contents are that (pH value is for the acidic aluminum sol of 20 mass %
3), miscible in the dehydrated alcohol of 500ml, obtain mixture, add aqueous sodium carbonate (concentration is 1.5mol/L) regulation mixed
The pH value of compound is 8-9, at 50 DEG C, continues to stand aging 6 hours, is then filtrated to get solid sediment, by solid precipitation
Thing through deionized water wash to after without sodium, then with 500ml absolute ethanol washing one time, finally dry 10 hours at 120 DEG C must
To solid；
Weigh 50 grams and size-reduced add the aqueous sodium persulfate solution (concentration 20 mass %) of 20 grams to the 300 above-mentioned solids of purpose,
Then mediating, then at 400 DEG C, roasting 4h obtains catalyst C3.
Catalyst Preparation Example 4
Catalyst is prepared according to the method for Catalyst Preparation Example 3, except for the difference that, Ni (NO3)2·6H2O, acid silicon are molten
Glue, the consumption of dehydrated alcohol are respectively 1560g, 2340g, 500ml, obtain catalyst C4.
Catalyst Preparation Example 5
Preparing catalyst according to the method for Catalyst Preparation Example 3, except for the difference that, standing aging temperature is 70 DEG C,
Time is 7h, obtains catalyst C5.
Catalyst Preparation Example 6
Preparing catalyst according to the method for Catalyst Preparation Example 3, except for the difference that, the temperature being dried is 130 DEG C, the time
For 9h；The temperature of roasting is 600 DEG C, and the time is 6h, obtains catalyst C6.
Catalyst Preparation Example 7
Preparing catalyst according to the method for Catalyst Preparation Example 3, except for the difference that, the acidic aluminum using pH value to be 2 is molten
The acidic aluminum sol (pH value is 3) that glue (solid content is 20 mass %) replaces solid content to be 20 mass %, obtains catalyst C7.
Embodiment 1-7
The catalyst C1-C7 prepared is carried out dehydrogenation according to the method for the present invention, actual conditions and the results are shown in Table 1.
Table 1
By the data of table 1 it can be seen that the catalyst activity height prepared according to the method for the present invention, target is produced
Thing selectivity is high.
Embodiment 8-18
Dehydrogenation is carried out according to the method for embodiment 1-7, except for the difference that, catalytic dehydrogenation condition and the results are shown in Table 2.
Table 2
By the result of table 2 it can be seen that the dehydrogenation catalysis activity prepared according to the method for the present invention is high, mesh
Mark selectivity of product is high, and catalyst life is long.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the technology concept of the present invention, technical scheme can be carried out multiple simple variant, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. the preparation method of a dehydrogenation, it is characterised in that the method includes: by water solublity nickel compound containing and acidity
Colloidal sol mixes with ethanol, and the pH value of mixture obtained with alkaline matter regulation is 5-9, and stands old under this pH value condition
Change, then wash, be dried to obtain solid；Roasting after described solid and dehydrogenation adjuvant component are mixed, described water solublity nickeliferousization
Compound, acidic sol are 0.01-10:0.5-20:1 with the consumption weight ratio of ethanol.
Preparation method the most according to claim 1, wherein, the condition that described standing is aging includes: temperature is 30-70 DEG C,
Time is 0.1-10h；Described dry condition includes: temperature is 100-120 DEG C, and the time is 10-20 hour；The bar of described roasting
Part includes: temperature is 300-500 DEG C, and the time is 2-5 hour.
Preparation method the most according to claim 1, wherein,
Described water solublity nickel compound containing is one or more in nickel sulfate, nickel nitrate and Nickel dichloride.；
Described acidic sol is one or more in acidic silicasol, acidic aluminum sol and acid silicon-aluminum sol；
Described alkaline matter is one or more in sodium carbonate, sodium bicarbonate, ammonia and ammonium carbonate；
Described dehydrogenation adjuvant component is the one in sodium sulfate, potassium sulfate, lithium sulfate, magnesium sulfate, calcium sulfate and sodium carbonate or many
Kind.
Preparation method the most according to claim 3, wherein, described dehydrogenation adjuvant component is sodium sulfate.
5. the dehydrogenation that in claim 1-4, preparation method described in any one prepares.
6. a method of dehydrogenating, the method includes: under the conditions of catalytic dehydrogenation, by cyclohexanediol and/or the hexamethylene containing ehter bond
Diol, derivatives contacts with dehydrogenation, it is characterised in that described dehydrogenation is according to any one in claim 1-4
The dehydrogenation that preparation method described in Xiang prepares.
Method of dehydrogenating the most according to claim 6, wherein, described catalytic dehydrogenation condition includes: temperature is 180-350 DEG C；
Dehydrogenation is 1:5-50 with the mass ratio of cyclohexanediol and/or the Cyclohexanediole derivatives containing ehter bond.
Method of dehydrogenating the most according to claim 7, wherein, described catalytic dehydrogenation condition includes: temperature is 240-320 DEG C.
9. according to the method for dehydrogenating described in any one in claim 6-8, wherein, described catalytic dehydrogenation is entered in the presence of solvent
OK.
Method of dehydrogenating the most according to claim 9, wherein, described solvent and cyclohexanediol and/or the hexamethylene containing ehter bond
The mass ratio of diol, derivatives is 0.1-100:1.
11. method of dehydrogenating according to claim 10, wherein, described solvent and cyclohexanediol and/or the ring containing ehter bond
The mass ratio of hexane diol derivatives is 0.5-10:1.
12. method of dehydrogenating according to claim 9, wherein, described solvent is the one in alcohol, ester, nitrile, ketone and water or many
Kind.
13. method of dehydrogenating according to claim 12, wherein, described solvent be methanol, ethanol, propanol, ethylene glycol, the third two
Alcohol, Hexalin, butanediol, capryl alcohol, ethyl acetate, cyclohexyl acetate, glycol dicaproate, ethylene acetate, fourth two
Alcohol diacetate esters, diethylene adipate, butyl phthalate, octyl phthalate, acetonitrile, adiponitrile, Ketohexamethylene, third
One or more in ketone, isophorone, Ketohexamethylene and water.
14. according to the method for dehydrogenating described in any one in claim 6-8, and wherein, the described cyclohexanediol containing ehter bond spreads out
Biology is cyclohexanediol monoalky lether and/or cyclohexanediol dialkyl ether.
15. method of dehydrogenating according to claim 14, wherein, described alkyl is the straight or branched alkyl of C1-C10.
16. method of dehydrogenating according to claim 15, wherein, described alkyl is the straight or branched alkyl of C1-C6.
17. method of dehydrogenating according to claim 14, wherein, the described Cyclohexanediole derivatives containing ehter bond is hexamethylene two
Alcohol monomethyl ether, cyclohexanediol list ether, cyclohexanediol list propyl ether, cyclohexanediol monobutyl ether, cyclohexanediol dimethyl ether, cyclohexanediol
One or more in diethyl ether and cyclohexanediol dipropyl ether.
18. method of dehydrogenating according to claim 17, wherein, the described Cyclohexanediole derivatives containing ehter bond is adjacent methoxy
Cyclohexanol, adjacent ethyoxyl Hexalin, adjacent propoxyl group Hexalin, adjacent butoxy Hexalin, adjacent amoxy Hexalin, adjacent hexyloxy
In Hexalin, adjacent cyclohexyloxy Hexalin, adjacent dimethoxycyclohexane, adjacent diethoxy hexamethylene and adjacent dipropoxy hexamethylene
One or more.
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Citations (3)
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|---|---|---|---|---|
| US4415477A (en) * | 1979-12-27 | 1983-11-15 | Rozovsky Alexandr Y | Catalyst for dehydrogenation oxygen-containing derivatives of the cyclohexane series into the corresponding cyclic ketones and/or phenols |
| CN1160703A (en) * | 1996-03-27 | 1997-10-01 | 化学工业部大连化工研究设计院 | Production of catechol |
| CN101912781A (en) * | 2010-07-08 | 2010-12-15 | 南京工业大学 | Preparation method of dehydrogenation nickel-based/diatomite catalyst |
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2013
- 2013-03-28 CN CN201310104478.4A patent/CN104069875B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4415477A (en) * | 1979-12-27 | 1983-11-15 | Rozovsky Alexandr Y | Catalyst for dehydrogenation oxygen-containing derivatives of the cyclohexane series into the corresponding cyclic ketones and/or phenols |
| CN1160703A (en) * | 1996-03-27 | 1997-10-01 | 化学工业部大连化工研究设计院 | Production of catechol |
| CN101912781A (en) * | 2010-07-08 | 2010-12-15 | 南京工业大学 | Preparation method of dehydrogenation nickel-based/diatomite catalyst |
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| "1,2-环己二醇脱氢镍基催化剂制备方法";裴松鹏 等;《化学工程》;20101130;第38卷(第11期);第78页的1.2节 * |
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Effective date of registration: 20181129 Address after: Room 209, 111 Yingpanling Road, Yueyang Economic and Technological Development Zone, Hunan 414000 Patentee after: Yueyang Changde Environmental Technology Co., Ltd. Address before: 414007 Yueyang Building, Yueyang City, Hunan Province, Office Building of Caprolactam Division, Wangyue Road Baling Petrochemical Company Patentee before: Changde Chemical Industry Co., Ltd., Yueyang |
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| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 414000 room 217, No. 111, yingpanling Road, Yueyang Economic and Technological Development Zone, Yueyang City, Hunan Province Patentee after: Changde Xincai Technology Co.,Ltd. Address before: Room 209, 111 Yingpanling Road, Yueyang Economic and Technological Development Zone, Hunan 414000 Patentee before: Yueyang Changde Environmental Technology Co.,Ltd. |