CN105566068A - Method for preparing beta-diol from beta-diketone by hydrogenation - Google Patents
Method for preparing beta-diol from beta-diketone by hydrogenation Download PDFInfo
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- CN105566068A CN105566068A CN201410614504.2A CN201410614504A CN105566068A CN 105566068 A CN105566068 A CN 105566068A CN 201410614504 A CN201410614504 A CN 201410614504A CN 105566068 A CN105566068 A CN 105566068A
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- diol
- diketon
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Abstract
The invention relates to a method for preparing beta-diol from beta-diketone by hydrogenation. The method comprises the following steps: in the presence of a catalyst and under the fixed-bed hydrotreating reaction condition, enabling beta-diketone to be in contact with hydrogen, so as to obtain beta-diol, wherein the catalyst contains CuO and ZnO, preferably also contains Al2O3, and more preferably also contains alkali metal oxides. According to the method for preparing beta-diol from beta-diketone by hydrogenation, provided by the invention, the technology of continuously producing beta-diol by adopting a fixed bed device is realized, the technology is simple and convenient to operate, the utilization ratio of raw materials and the production efficiency of products are improved, the reaction does not need to be carried out under high pressure, and potential safety hazards are reduced.
Description
Technical field
The present invention relates to a kind of for the method for beta-diketon Hydrogenation for beta-diol, belong to aldehyde ketone shortening field.
Background technology
Catalyzer is the gordian technique in polyolefin industry evolution.At present, Ziegler-Natta catalyst still accounts for absolute consequence in polypropylene industrial is produced.In the evolution of Z-N catalyzer, the application of internal electron donor and exploitation play conclusive effect, have become its core technology.
Sinopec Beijing Research Institute of Chemical Industry develops a kind of 1,3-novel diol-lipid internal electron donor, as patent CN1453298A, CN1580034A etc.The feature of such internal electron donor has higher catalytic activity, good stereospecificity, and simultaneously by changing substituent kind and position, obtain the catalyzer of different hydrogen response, gained polymerisate has wider relative molecular mass distribution.Along with the development of China's polypropylene art and the continuous rising of demand, this type of internal electron donor can progressively be applied aborning, and market outlook are considerable.
Beta-diol is the important source material of synthesis 1,3-diol-lipid internal electron donor.At present about the synthesis of beta-diol, report is all take beta-diketon as raw material both at home and abroad, in the mode of interval synthesis, obtains corresponding beta-diol through catalytic hydrogenation or reductive agent reduction.
Document J.Am.Chem.Soc.1988,110,629-631 reports the catalyzer of BINAP-Ru (II) series compound as beta-diketon asymmetric hydrogenation beta-diol, after this this kind of report using the precious metals complex such as ruthenium, platinum as catalysts is more, its study hotspot mainly concentrates on the design of part and synthesizes, object be improve product ee (enantiomeric excess) value with obtain purity higher there is optically active beta-diol, as document Organometallics, 32 (4), 1075-1084; 2013, Organometallics2000,19,2450-2461, Organometallics2008,27,1119-1127, J.ofOrganometallicChem., 624 (1-2), 162-166; 2001, Tetrahedron:Asymmetry15 (2004) 2299-2306 etc.The catalyzer that these class methods relate to is because employ precious metal chemical complex, and part not easily synthesizes, therefore production cost is higher; In addition, reaction conditions is harsher, usually needs under high pressure to carry out.
Document ChemistryLetters, 1979,1049-1050, J.Chem.Soc., Chem.Commun., (12), 795-6; 1991 report RaneyNi that tartrate coordinates as the catalyzer of beta-diketon asymmetric hydrogenation beta-diol, and active better, the transformation efficiency of beta-diketon can reach more than 90%.But this method is because employ RaneyNi, and operating process exists certain danger, and meanwhile, difficulty reused by catalyzer, and the preparation of catalyzer and the process of spent catalyst exist problem of environmental pollution, are not suitable for suitability for industrialized production.
Beta-diketon also can through NaBH
4, LiAlH
4deng the obtained beta-diol of reductive agent reduction.As CN102432701 reports NaBH
4with the methanol solution of NaOH mixed solution and dripping 2,4-diacetylmethane, can generate product 2,4-pentanediol at short notice, yield is 90%.This kind of method is because employ more active reductive agent, and reaction generally can be carried out under low temperature, normal pressure, and reaction time consumption is shorter, but product separation purification process is loaded down with trivial details, length consuming time, and need to consume a large amount of organic solvents and water, thus produce a large amount of waste liquid, can not meet the requirement of environmental protection.
Summary of the invention
The object of this invention is to provide a kind of for the method for beta-diketon Hydrogenation for beta-diol, described method adopts fixed bed hydrogenation technique and uses CuO/ZnO or CuO/ZnO/Al
2o
3o composite metallic oxide catalyst, reacts without the need under high pressure carrying out.Environmentally safe, operational condition is gentle, is suitable for continuous prodution.
For achieving the above object, technical scheme of the present invention is as follows:
According to the present invention, described for the method for beta-diketon Hydrogenation for beta-diol, comprise catalyzer and exist and under fixed bed hydrogenation reaction conditions, beta-diketon contacted with hydrogen and obtains beta-diol.Wherein, CuO and ZnO is contained in described catalyzer.
Particularly, the method that described employing fixed bed hydrogenation technique prepares beta-diol for beta-diketon comprises:
(1) before reaction, catalyzer is carried out reduction pretreatment under reducing atmosphere;
(2), after question response device and preheater temperature reach certain temperature of reaction and pressure, the reactant beta-diketon after solvent cut and hydrogen enter reactor reaction after preheater vaporization mixing, can generate beta-diol.
Prepare in the method for beta-diol above-mentioned, fixed bed hydrogenation reactor is made up of three sections of temperature control districts, comprises constant temperature section and upper and lower packing section.The mensuration that sleeve pipe carries out real reaction temperature is equipped with in hydrogenator inside.Catalyst loading is at reactor constant temperature section, and upper-lower section all loads effigurate inert filler.
Prepare in the method for beta-diol above-mentioned, the reducing atmosphere described in step (1) is the gas mixture of hydrogen or hydrogen and rare gas element (as nitrogen, argon gas), and in described reducing atmosphere, the percent by volume of hydrogen can be 10 ~ 100%.The temperature of reduction pretreatment is 200 ~ 300 DEG C, preferably 230 DEG C.The time of reduction pretreatment is 3 ~ 30h, preferably 4 ~ 6h.
Prepare in the method for beta-diol above-mentioned, the temperature of reaction in step (2) is 100 ~ 180 DEG C, preferably 125 ~ 150 DEG C.Reaction pressure is 3 ~ 10bar, preferably 4 ~ 7bar.
According to the present invention, the reactant beta-diketon structural formula in step (2) is
wherein R
1and R
2for carbonatoms is the alkyl of 1 ~ 5, can be 2,4-diacetylmethane (acac), 2,4-hexanediones, 2,4-heptadione, 3,5-heptadione etc., preferably 2,4-diacetylmethanes.
The structural formula of described product beta-diol is
r wherein
1, R
2with the R in beta-diketon
1, R
2identical.
Prepare in the method for beta-diol above-mentioned, the beta-diketon in step (2) can with solvent charging, the volume content of described beta-diketon can be 10 ~ 100%, preferably 20 ~ 60%.Described solvent can be one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, isopropylcarbinol, sec-butyl alcohol and the trimethyl carbinol, is preferably the trimethyl carbinol and/or sec-butyl alcohol.
Prepare in the method for beta-diol 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 mol ratio of hydrogen and beta-diketon is 10 ~ 100:1, preferably 20 ~ 90:1.
In one embodiment of the invention, also Al is contained in described catalyzer
2o
3, more preferably also contain alkalimetal oxide in described catalyzer.
In one embodiment of the invention, in described catalyzer, each component concentration is counted with parts by weight:
In one embodiment of the invention, the specific surface area of described catalyzer is generally 10 ~ 90 meters squared per gram, and pore volume is generally 0.05 ~ 0.4 ml/g, and most probable pore size is generally 15 ~ 19nm; Wherein, preferred specific surface area is 80 ~ 90 meters squared per gram, and 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 catalyzer, comprising: the temperature ranges of 50 ~ 60 DEG C and 7 ~ 7.5 pH value condition under, the mixing solutions of soluble copper salt and zinc salt is added with precipitation agent stream, at the Al that can select to add
2o
3upper generation co-precipitation, through be incubated aging, filter, dry and roasting obtains described catalyzer.
Wherein, " at optional Al
2o
3upper generation co-precipitation " implication be: when there is Al in described catalyzer
2o
3time, be under the effect of precipitation agent, soluble copper salt and zinc salt are at Al
2o
3upper generation co-precipitation.When there is not Al in described catalyzer
2o
3time, under the effect of precipitation agent, there is co-precipitation in soluble copper salt and zinc salt.
In one embodiment of the invention, described soluble copper salt and zinc salt are selected from least one in the nitrate of copper and zinc, vitriol and muriate.
In one embodiment of the invention, described precipitation agent is selected from Na
2cO
3, K
2cO
3, at least one in NaOH, KOH and ammoniacal liquor.
In one embodiment of the invention, described digestion time is 0.5 ~ 2 hour; Maturing temperature is 350 ~ 500 DEG C, preferably 400 ~ 450 DEG C, and roasting time is 4 ~ 6 hours.
According to the present invention, preferably on the above-mentioned catalyzer prepared, flood alkali metal compound, and then dry and roasting, obtain finished catalyst.
In one embodiment of the invention, described alkali metal compound is selected from least one in alkali metal lithium, sodium, potassium, rubidium, the nitrate of caesium or carbonate; Described maturing temperature is 350 ~ 500 DEG C, and roasting time is 4 ~ 6 hours.
In a preferred embodiment of the invention, the preparation method of above-mentioned catalyzer comprises: the temperature ranges of 50 ~ 60 DEG C and 7 ~ 7.5 pH value condition under, the mixing solutions of soluble copper salt and zinc salt is added, at Al with precipitation agent stream
2o
3upper generation co-precipitation, through be incubated aging, filter, after dry and roasting, dipping alkali metal compound, and then dry and roasting, obtain finished catalyst.
Present invention achieves the technique adopting fixed bed device continuous seepage beta-diol, this technological operation is easy, can improve the utilization ratio of raw material and the production efficiency of product; And reaction avoids and under high pressure carries out, and reduces potential potential safety hazard.
The catalyzer that prior art uses is only applicable to prepare beta-diol with rhythmic reaction.The present invention, while the above-mentioned technique of employing, additionally provides a kind of for the catalyzer of beta-diketon Hydrogenation for beta-diol, has higher specific surface area and pore volume.Its preparation method is simple, and raw material is easy to get, cheap, reduces production cost.
Embodiment
Embodiment 1
By 121gCu (NO
3)
23H
2o and 147gZn (NO
3)
26H
2o is dissolved in deionized water and makes mixing salt solution, 106gNaCO
3water-solublely make precipitant solution.Add a small amount of water in four-hole boiling flask, be heated to 50 DEG C, under whipped state, above-mentioned mixing salt solution and the even also drip of precipitant solution are added in four-hole boiling flask, keep constant temperature 50 DEG C and constant pH 7 ~ 7.5.Stirred 2 hours under constant temperature 50 DEG C of conditions by throw out after dripping off, filter and wash with water, 120 DEG C of dryings, then grind to form fine powder, compressing tablet, 450 DEG C of roastings 5 hours, obtained finished catalyst.The full-automatic materialization Sorption Analyzer of the ASAP2020-M+C of MICROMERITICS company of the U.S. is adopted to measure the specific surface area 15.2m of gained catalyzer
2/ g, pore volume 0.06cm
3/ g, mean pore size
Embodiment 2
By 121gCu (NO
3)
23H
2o and 147gZn (NO
3)
26H
2o is dissolved in deionized water and makes mixing salt solution, 106gNaCO
3water-solublely make precipitant solution.A small amount of water and γ-Al is added in four-hole boiling flask
2o
3powder, is heated to 50 DEG C, adds in four-hole boiling flask, keep constant temperature 50 DEG C and constant pH 7 ~ 7.5 under whipped state by above-mentioned mixing salt solution and the even also drip of precipitant solution.Stirred 2 hours under constant temperature 50 DEG C of conditions by throw out after dripping off, filter and wash with water, 120 DEG C of dryings, then grind to form fine powder, compressing tablet, 450 DEG C of roastings 5 hours, obtained finished catalyst.The specific surface area 81.4m of gained catalyzer
2/ g, pore volume 0.39cm
3/ g, mean pore size
Embodiment 3
Catalyzer obtained for embodiment 2 is immersed KNO
3in solution, magnetic stirrer over night, dry, 450 DEG C of roastings 5 hours, obtained finished catalyst.
Catalyzer prepared by embodiment 1 ~ 3 is packed in small fixed hydrogenation reaction device respectively, loadings is 1g, reactor inside diameter 1cm, long 23cm, carry out reduction pretreatment with hydrogen-nitrogen mixed gas that hydrogen volume content is 10% in 200 ~ 300 DEG C of temperature ranges.Containing 20% volume fraction 2,2 of 4-diacetylmethane, 4-diacetylmethane-sec-butyl alcohol solution is mixed into reactor with hydrogen and carries out hydrogenation reaction after preheater gasification, by in gas chromatographic analysis effluent liquid 2, the content of 4-diacetylmethane and 2,4-pentanediol, and calculate 2, the transformation efficiency of 4-diacetylmethane and the selectivity of 2,4-pentanediol.
In the present invention, 2,4-pentanediol is optionally defined as the ratio shared by 2,4-pentanediols generated in product, and calculation formula is: 2,4-diacetylmethanes of reaction are converted into the amount of 2,4-diacetylmethanes of the amount of 2,4-pentanediol/reacted.2,4-diacetylmethane transformation efficiency is defined as the ratio of 2,4-diacetylmethanes of charging shared by 2, the 4-diacetylmethanes that reacted, and calculation formula is: the amount of the amount of 2, the 4-diacetylmethanes transformed/flow through 2,4-diacetylmethanes in beds charging.Obtain result as table 1.
Table 1
As known from Table 1, catalyzer provided by the invention has higher specific surface area and pore volume.Use it for 2,4-diacetylmethane hydrogenation, the selectivity that the transformation efficiency of 2,4-diacetylmethane can reach 100%, 2,4-pentanediol reaches more than 70%, and hydrogenation reaction can be carried out continuously.Catalytic efficiency is high, is suitable for continuous prodution.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.
Claims (10)
1., for the method for beta-diketon Hydrogenation for beta-diol, comprise catalyzer and exist and under fixed bed hydrogenation reaction conditions, beta-diketon contacted with hydrogen and obtains beta-diol; Wherein said catalyzer contains CuO and ZnO.
2. method according to claim 1, is characterized in that, also containing Al in described catalyzer
2o
3, preferably also containing alkalimetal oxide.
3. method according to claim 2, is characterized in that, in described catalyzer, each component concentration is counted with parts by weight:
4. the method according to any one of claims 1 to 3, is characterized in that, hydrogenation reaction temperature is 100 ~ 180 DEG C, preferably 125 ~ 150 DEG C; Reaction pressure is 3 ~ 10bar, preferably 4 ~ 7bar.
5. the method according to any one of Claims 1-4, is characterized in that, the mass space velocity of described beta-diketon is 0.1 ~ 2h
-1, preferably 0.1 ~ 0.5h
-1; The mol ratio of hydrogen and beta-diketon is 10 ~ 100:1, preferably 20 ~ 90:1.
6. the method according to any one of claim 1 to 5, it is characterized in that, described beta-diketon is with 10 ~ 100%, preferably 20 ~ 60% volume content and solvent charging, one or more in described solvent particular methanol, ethanol, n-propyl alcohol, Virahol, isopropylcarbinol, sec-butyl alcohol and the trimethyl carbinol, are more preferably the trimethyl carbinol and/or sec-butyl alcohol.
7. the method according to any one of claim 1 to 6, is characterized in that, described beta-diketon structural formula is
wherein R
1and R
2for carbonatoms is the alkyl of 1 ~ 5, preferably from 2,4-diacetylmethane, 2,4-hexanediones, 2,4-heptadione or 3,5-heptadione, more preferably 2,4-diacetylmethanes.
8. the method according to any one of claim 1 to 7, is characterized in that, before reaction, hydrogenation catalyst is carried out pre-treatment under reducing atmosphere.
9. method according to claim 8, is characterized in that, described reducing atmosphere is the gas mixture of hydrogen or hydrogen and rare gas element, and the percent by volume of preferred hydrogen is 10 ~ 100%.
10. method according to claim 8, is characterized in that, pretreatment temperature is 200 ~ 300 DEG C, preferably 230 DEG C; Pretreatment time is 3 ~ 30h, preferably 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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