CN105566068B - A kind of method for beta-diketon Hydrogenation for beta-diol - Google Patents
A kind of method for beta-diketon Hydrogenation for beta-diol Download PDFInfo
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- CN105566068B CN105566068B CN201410614504.2A CN201410614504A CN105566068B CN 105566068 B CN105566068 B CN 105566068B CN 201410614504 A CN201410614504 A CN 201410614504A CN 105566068 B CN105566068 B CN 105566068B
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Abstract
The present invention relates to a kind of method for beta diketone Hydrogenation for β glycol, including catalyst exist and fixed bed hydrogenation reaction condition under, beta diketone is contacted with hydrogen to obtain β glycol；Wherein described catalyst contains CuO and ZnO, preferably also contains Al2O3, more preferably also contain alkali metal oxide.The present invention realizes the technique using fixed bed device continuous production β glycol, and the technological operation is easy, can improve the utilization rate of raw material and the production efficiency of product；And reaction is avoided and carried out under high pressure, reduces potential security risk.
Description
Technical field
The present invention relates to a kind of beta-diketon Hydrogenation that is used for for the method for beta-diol, belong to aldehyde ketone catalytic hydrogenation field.
Background technology
Catalyst is the key technology in polyolefin industry evolution.At present, Ziegler-Natta catalyst is poly- third
Absolutely essential status is still accounted in alkene industrial production.In Z-N catalyst evolutions, the application of internal electron donor and develop
Conclusive effect, it has also become its core technology.
Sinopec Beijing Research Institute of Chemical Industry is developed in a kind of new 1,3- diol-lipids
Electron donor, such as patent CN1453298A, CN1580034A etc..The characteristics of such internal electron donor, is lived with higher catalysis
Property, preferable stereoselectivity, while species that can be by varying substituent and position, obtain the catalysis of different hydrogen responses
Agent, gained polymerizate have wider relative molecular mass distribution.Continuous development and need with China's polypropylene art
The continuous rising for the amount of asking, such internal electron donor can progressively be applied in production, and market prospects are considerable.
Beta-diol is the important source material for synthesizing 1,3- diol-lipid internal electron donors.The current synthesis in relation to beta-diol, state
Inside and outside report is using beta-diketon as raw material, in a manner of intermittently synthesizing, is reduced through catalytic hydrogenation or reducing agent and obtains phase
The beta-diol answered.
Document J.Am.Chem.Soc.1988,110,629-631 report BINAP-Ru (II) series compounds as β-
The catalyst of diketone asymmetric hydrogenation beta-diol, it is hereafter this kind of that catalysts are used as using precious metals complex such as ruthenium, platinum
Report more, its research hotspot is concentrated mainly in the design and synthesis of ligand, it is therefore intended that improves ee (the enantiomer mistakes of product
Amount) value is to obtain the higher beta-diol with optical activation of purity, such as document Organometallics, 32 (4), 1075-
1084；2013, Organometallics 2000,19,2450-2461, Organometallics 2008,27,1119-
1127, J.of Organometallic Chem., 624 (1-2), 162-166；2001, Tetrahedron:Asymmetry 15
(2004) 2299-2306 etc..Catalyst that such method is related to because having used precious metal chemical complex, and ligand is not easily-synthesized,
Therefore production cost is higher；In addition, reaction condition is harsher, it usually needs carries out under high pressure.
Document Chemistry Letters, 1979,1049-1050, J.Chem.Soc., Chem.Commun., (12),
795-6；1991 report catalyst of the Raney Ni of tartaric acid cooperation as beta-diketon asymmetric hydrogenation beta-diol, activity
Preferably, the conversion ratio of beta-diketon is up to more than 90%.But because having used Raney Ni, operating process exists certain the method
Danger, meanwhile, catalyst reuse it is difficult, the preparation of catalyst and the processing of dead catalyst there are problem of environmental pollution,
Be not suitable for industrialized production.
Beta-diketon can also be through NaBH4、LiAlH4Obtained beta-diol is reduced Deng reducing agent.As CN102432701 is reported
NaBH4With NaOH mixed solution and drippings 2, the methanol solution of 4- pentanediones can generate product 2 in a short time, 4- pentanediols,
Yield is 90%.Such a method is because used more active reducing agent, and reaction can carry out generally under low temperature, normal pressure, instead
It should take shorter, but product separating-purifying process is cumbersome, and time-consuming, and needs to consume substantial amounts of organic solvent and water, so as to produce
Raw a large amount of waste liquids, it is impossible to meet the requirement of environmental protection.
The content of the invention
The object of the present invention is to provide a kind of method for beta-diketon Hydrogenation for beta-diol, the method is using fixation
Bed hydroprocessing technique simultaneously uses CuO/ZnO or CuO/ZnO/Al2O3O composite metallic oxide catalyst, reaction without under high pressure into
OK.Environmentally safe, operating condition is gentle, suitable for continuous production.
To achieve the above object, technical scheme is as follows：
According to the present invention, the method for beta-diketon Hydrogenation for beta-diol, including catalyst exists and fixed bed
Under hydrogenation conditions, beta-diketon is contacted with hydrogen to obtain beta-diol.Wherein, CuO and ZnO is contained in the catalyst.
Specifically, the method for being prepared beta-diol for beta-diketon using fixed bed hydrogenation technique is included：
(1) catalyst is subjected to reduction pretreatment under reducing atmosphere before reaction；
(2) after question response device and preheater temperature reach certain reaction temperature and pressure, the reaction after solvent dilutes
Enter reactor reaction after thing beta-diketon and the preheated device vaporization mixing of hydrogen, you can generation beta-diol.
The method of beta-diol is prepared above-mentioned, fixed bed hydrogenation reactor is made of three sections of temperature control areas, including flat-temperature zone
Section and upper and lower packing section.The measure of real reaction temperature is carried out inside hydrogenation reactor equipped with casing.Catalyst packing is reacting
Device constant temperature section, upper-lower section load effigurate inert filler.
The method of beta-diol is prepared above-mentioned, the reducing atmosphere described in step (1) is hydrogen or hydrogen and indifferent gas
The gaseous mixture of body (such as nitrogen, argon gas), the percentage by volume of hydrogen can be 10~100% in the reducing atmosphere.Reduction is pre-
The temperature of processing is 200~300 DEG C, preferably 230 DEG C.The time of reduction pretreatment is 3~30h, preferably 4~6h.
The method of beta-diol is prepared above-mentioned, the reaction temperature in step (2) is 100~180 DEG C, preferably 125~150
℃.Reaction pressure is 3~10bar, preferably 4~7bar.
According to the present invention, the reactant beta-diketon structural formula in step (2) isWherein R1And R2
The alkyl for being 1~5 for carbon number, can be 2,4- pentanediones (acac), 2,4- acetyl butyryls, 2,4- heptadione, 3,5- heptan two
Ketone etc., preferably 2,4- pentanediones.
The structural formula of the product beta-diol isR therein1、R2With the R in beta-diketon1、R2
It is identical.
The method of beta-diol is prepared above-mentioned, the beta-diketon in step (2) can be with solvent mixed feeding, the β-two
The volume content of ketone can be 10~100%, preferably 20~60%.The solvent can be methanol, ethanol, normal propyl alcohol, isopropyl
One or more in alcohol, isobutanol, sec-butyl alcohol and the tert-butyl alcohol, are preferably the tert-butyl alcohol and/or sec-butyl alcohol.
The method of beta-diol is prepared above-mentioned, the mass space velocity of the beta-diketon in step (2) is 0.1~2h-1, preferably
0.1~0.5h-1.The molar ratio of hydrogen and beta-diketon is 10~100:1, preferably 20~90:1.
In one embodiment of the invention, Al is also contained in the catalyst2O3, also contain in more preferably described catalyst
There is alkali metal oxide.
In one embodiment of the invention, each component content is calculated as with parts by weight in the catalyst：
In one embodiment of the invention, the specific surface area of the catalyst is generally 10~90 meters squared per grams, hole body
Generally 0.05~0.4 ml/g of product, most probable pore size is generally 15~19nm；Wherein, preferably specific surface area is flat for 80~90
Square rice/gram, pore volume is 0.3~0.4 ml/g, and most probable pore size is 16~19nm.
Present invention also offers the preparation method of above-mentioned catalyst, including：In 50~60 DEG C of temperature ranges and 7~7.5
PH value condition under, the mixed solution of soluble copper salt and zinc salt and precipitating reagent cocurrent are added, in the Al that may be optionally added2O3
Upper to be co-precipitated, warm aging, filtering, drying and roasting obtain the catalyst.
Wherein, " in optional Al2O3It is upper to be co-precipitated " it is meant that：When there are Al in the catalyst2O3When, it is
Under the action of precipitating reagent, soluble copper salt and zinc salt are in Al2O3It is upper to be co-precipitated.When Al is not present in the catalyst2O3
When, soluble copper salt and zinc salt are co-precipitated under the action of precipitating reagent.
In one embodiment of the invention, the soluble copper salt and zinc salt are selected from nitrate, the sulfuric acid of copper and zinc
At least one of salt and chloride.
In one embodiment of the invention, the precipitating reagent is selected from Na2CO3、K2CO3, in NaOH, KOH and ammonium hydroxide
It is at least one.
In one embodiment of the invention, when the ageing time is 0.5~2 small；Calcination temperature is 350~500
DEG C, preferably 400~450 DEG C, when roasting time is 4~6 small.
, according to the invention it is preferred to impregnate alkali metal compound on the above-mentioned catalyst being prepared, then dry again
And roasting, obtain finished catalyst.
In one embodiment of the invention, the alkali metal compound is selected from alkali metal lithium, sodium, potassium, rubidium, the nitre of caesium
At least one of hydrochlorate or carbonate；The calcination temperature is 350~500 DEG C, when roasting time is 4~6 small.
In a preferred embodiment of the invention, the preparation method of above-mentioned catalyst includes：In 50~60 DEG C of temperature
Under scope and 7~7.5 pH value condition, the mixed solution of soluble copper salt and zinc salt and precipitating reagent cocurrent are added, in Al2O3
It is upper to be co-precipitated, after warm aging, filtering, drying and roasting, alkali metal compound is impregnated, then dry again and roasting
Burn, obtain finished catalyst.
The present invention realizes the technique using fixed bed device continuous production beta-diol, and the technological operation is easy, can improve
The utilization rate of raw material and the production efficiency of product；And reaction is avoided and carried out under high pressure, reduces potential security risk.
Catalyst used in the prior art is only applicable to prepare beta-diol with intermittent reaction.The present invention is using above-mentioned work
While skill, a kind of beta-diketon Hydrogenation that is used for is additionally provided for the catalyst of beta-diol, there is higher specific surface area and hole
Hold.Its preparation method is simple, and raw material is easy to get, cheap, reduces production cost.
Embodiment
Embodiment 1
By 121g Cu (NO3)2·3H2O and 147g Zn (NO3)2·6H2O, which is dissolved in deionized water, is made mixing salt solution,
106gNaCO3It is dissolved in water and precipitant solution is made.A small amount of water is added in four-hole boiling flask, is heated to 50 DEG C, will be upper under stirring
State mixing salt solution and the uniform cocurrent of precipitant solution be added dropwise in four-hole boiling flask, keep 50 DEG C of constant temperature and constant pH 7~
7.5.Sediment is filtered and is washed with water, 120 DEG C of dryings, then grind when stirring 2 is small under the conditions of 50 DEG C of constant temperature after dripping off
Into fine powder, tabletting, when 450 DEG C of roastings 5 are small, is made finished catalyst.Using MICROMERITICS companies of the U.S.
The specific surface area 15.2m of the full-automatic materialization Sorption Analyzer measure gained catalyst of ASAP2020-M+C2/ g, pore volume 0.06cm3/
G, average pore size
Embodiment 2
By 121g Cu (NO3)2·3H2O and 147g Zn (NO3)2·6H2O, which is dissolved in deionized water, is made mixing salt solution,
106gNaCO3It is dissolved in water and precipitant solution is made.A small amount of water and γ-Al is added in four-hole boiling flask2O3Powder, is heated to 50 DEG C, stirs
Mix and above-mentioned mixing salt solution and the uniform cocurrent of precipitant solution are added dropwise in four-hole boiling flask under state, keep 50 DEG C of constant temperature and perseverance
Determine pH value 7~7.5.Sediment is filtered and is washed with water when stirring 2 is small under the conditions of 50 DEG C of constant temperature after dripping off, 120 DEG C dry
It is dry, fine powder is then ground to, tabletting, when 450 DEG C of roastings 5 are small, is made finished catalyst.The specific surface area of gained catalyst
81.4m2/ g, pore volume 0.39cm3/ g, average pore size
Embodiment 3
Catalyst made from embodiment 2 is immersed into KNO3In solution, magnetic stirrer over night is dry, when 450 DEG C of roastings 5 are small,
Finished product catalyst.
Catalyst prepared by embodiment 1~3 is packed into small fixed hydrogenation reaction device respectively, loadings are
1g, reactor inside diameter 1cm, long 23cm, are mixed in 200~300 DEG C of temperature ranges with the hydrogen that hydrogen volume content is 10%-nitrogen
Gas carries out reduction pretreatment.The preheated device gasification of 2,4- pentanediones-sec-butyl alcohol solution containing 20% volume fraction 2,4- pentanediones
Reactor is mixed into hydrogen afterwards and carries out hydrogenation reaction, passes through 2,4- pentanediones in gas chromatographic analysis efflux and 2,4- penta
The content of glycol, and calculate the conversion ratio of 2,4- pentanediones and the selectivity of 2,4- pentanediol.
In the present invention, the definition of 2,4- pentanediols selectivity is the ratio shared by 2, the 4- pentanediols generated in product, is counted
Calculating formula is：The 2,4- pentanediones of reaction are converted into the amount of the 2,4- pentanediones for the amount of 2,4-PD/reacted.2,4- penta 2
The definition of ketone conversion ratio is the ratio of shared 2, the 4- pentanediones fed of 2,4- pentanediones reacted, and calculation formula is：Conversion
2,4- pentanediones amount/flow through 2,4- pentanediones in catalyst bed charging amount.Obtain result such as table 1.
Table 1
As known from Table 1, catalyst provided by the invention has higher specific surface area and pore volume.Use it for 2,4- penta 2
Ketone is hydrogenated with, and the conversion ratio of 2,4- pentanediones reaches more than 70%, and hydrogenation reaction up to the selectivity of 100%, 2,4- pentanediol
It can be carried out continuously.High catalytic efficiency, suitable for continuous production.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (20)
1. a kind of method for beta-diketon Hydrogenation for beta-diol, including catalyst exists and fixed bed hydrogenation reaction condition
Under, beta-diketon is contacted with hydrogen to obtain beta-diol；Wherein described catalyst contains CuO and ZnO；
In terms of parts by weight, CuO is 20~80 parts, and ZnO is 30~40 parts；
The beta-diketon structural formula isWherein R1 and R2 is the alkyl of C1~C5；
The specific surface area of the catalyst is 10~90 meters squared per grams, and pore volume is 0.05~0.4 ml/g, most probable pore size
For 15~19nm；
The pressure of the reaction is 3~10bar.
2. according to the method described in claim 1, it is characterized in that, also contain Al in the catalyst2O3。
3. the according to the method described in claim 2, it is characterized in that, catalyst also oxide containing alkali metal.
4. according to the method described in claim 3, it is characterized in that, each component content is in terms of parts by weight in the catalyst
For：
5. according to the method described in claim 4, it is characterized in that, the CuO is 30~60 parts；The Al2O3For 10~40
Part；The alkali metal oxide is 3~7 parts.
6. the according to the method described in claim 5, it is characterized in that, Al2O3For 15~30 parts.
7. method according to any one of claims 1 to 6, it is characterised in that hydrogenation reaction temperature is 100~180 DEG C.
8. the method according to the description of claim 7 is characterized in that hydrogenation reaction temperature is 125~150 DEG C；Reaction pressure is 4
~7bar.
9. method according to any one of claims 1 to 6, it is characterised in that the mass space velocity of the beta-diketon for 0.1~
2h-1；The molar ratio of hydrogen and beta-diketon is 10~100:1.
10. according to the method described in claim 9, it is characterized in that, the mass space velocity of the beta-diketon is 0.1~0.5h-1；Hydrogen
The molar ratio of gas and beta-diketon is 20~90:1.
11. method according to any one of claims 1 to 6, it is characterised in that the beta-diketon is with 10~100% body
Product content and solvent mixed feeding, the solvent are selected from methanol, ethanol, normal propyl alcohol, isopropanol, isobutanol, sec-butyl alcohol and tertiary fourth
One or more in alcohol.
12. according to the method for claim 11, it is characterised in that the beta-diketon with 40~60% volume content with it is molten
Agent mixed feeding.
13. according to the method for claim 11, it is characterised in that the solvent tertiary butanol and/or sec-butyl alcohol.
14. method according to any one of claims 1 to 6, it is characterised in that the beta-diketon be selected from 2,4- pentanediones,
2,4- acetyl butyryls, 2,4- heptadione or 3,5- heptadione.
15. according to the method for claim 14, it is characterised in that the beta-diketon is 2,4- pentanediones.
16. method according to any one of claims 1 to 6, it is characterised in that by hydrogenation catalyst in also Primordial Qi before reaction
Pre-processed under atmosphere.
17. according to the method for claim 16, it is characterised in that the reducing atmosphere is hydrogen or hydrogen and indifferent gas
The gaseous mixture of body.
18. according to the method for claim 17, it is characterised in that the percentage by volume of the hydrogen is 10~100%.
19. according to the method for claim 16, it is characterised in that pretreatment temperature is 200~300 DEG C；Pretreatment time
For 3~30h.
20. according to the method for claim 19, it is characterised in that pretreatment temperature is 230 DEG C, pretreatment time for 4~
6h。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279127A (en) * | 2000-05-12 | 2001-01-10 | 石油大学(华东) | Process for preparing paraoctanol by hydrogenction of paraoctanone and its catalyst |
| US20080132742A1 (en) * | 2006-12-02 | 2008-06-05 | Eastman Chemical Company | Process for the preparation of a tetraalkycyclobutane-1,3-diol using a promoted-copper catalyst |
| US20080154012A1 (en) * | 2006-12-02 | 2008-06-26 | Eastman Chemical Company | Process for the simultaneous co-production of 2,2,4,4-tetramethycyclobutane-1,3-diol and 1,4-cyclohexanedimethanol |
| WO2014135605A1 (en) * | 2013-03-06 | 2014-09-12 | Sonja Jost | Water-insoluble ruthenium catalyst composition for use in aqueous hydrogenation reactions |
-
2014
- 2014-11-04 CN CN201410614504.2A patent/CN105566068B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279127A (en) * | 2000-05-12 | 2001-01-10 | 石油大学(华东) | Process for preparing paraoctanol by hydrogenction of paraoctanone and its catalyst |
| US20080132742A1 (en) * | 2006-12-02 | 2008-06-05 | Eastman Chemical Company | Process for the preparation of a tetraalkycyclobutane-1,3-diol using a promoted-copper catalyst |
| US20080154012A1 (en) * | 2006-12-02 | 2008-06-26 | Eastman Chemical Company | Process for the simultaneous co-production of 2,2,4,4-tetramethycyclobutane-1,3-diol and 1,4-cyclohexanedimethanol |
| WO2014135605A1 (en) * | 2013-03-06 | 2014-09-12 | Sonja Jost | Water-insoluble ruthenium catalyst composition for use in aqueous hydrogenation reactions |
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