CN102584532A - Method for improving selectivity of 1,2-propanediol prepared by reforming and hydrogenating glycerol - Google Patents
Method for improving selectivity of 1,2-propanediol prepared by reforming and hydrogenating glycerol Download PDFInfo
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- CN102584532A CN102584532A CN2011103995380A CN201110399538A CN102584532A CN 102584532 A CN102584532 A CN 102584532A CN 2011103995380 A CN2011103995380 A CN 2011103995380A CN 201110399538 A CN201110399538 A CN 201110399538A CN 102584532 A CN102584532 A CN 102584532A
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Abstract
The invention belongs to the technical field of chemical industry, and in particular relates to a method for improving the selectivity of 1,2-propanediol prepared by reforming and hydrogenating glycerol. On the basis of the original method, oxide serving as a cocatalyst is added while a quenching skeletal nickel molybdenum catalyst is used, so that the selectivity of a target product, namely the 1,2-propanediol is improved, wherein one part of glycerol is subjected to liquid-phase reforming reaction to form hydrogen in the presence of the metal catalyst, and the other part of glycerol is hydrogenated to form the 1,2-propanediol in the presence of the hydrogen; the oxide is used for adjusting the reforming hydrogen production activity of the glycerol on the metal catalyst and the hydrogenolysis performance of the glycerol; and by adjusting the weight ratio of the metal catalyst to the oxide, the 1,2-propanediol can be highly selectively prepared from the glycerol without an external hydrogen source. By the method, the problem that high-pressure hydrogen is inconvenient to transport and store is solved, operation safety can be increased, and equipment cost is greatly reduced.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of raising USP Kosher reformation-hydrogenation preparing 1, the optionally method of 2-Ucar 35.
Background technology
1, the 2-Ucar 35 is widely used in numerous areas such as daily life and chemical industry be synthetic.For example, it is frostproofer, deicing agent and the lubricant of using always, also is widely used in the food and medicine field.In processes such as industrial preparation polyester and urethane, 1, the 2-Ucar 35 is a kind of important material.At present, main method preparation 1 in the industry through the propylene oxide hydration, the 2-Ucar 35, this process is a cost to consume non-renewable fossil energy.Under the background of global fossil resource scarcity, it is traditional 1 that investigators are just making great efforts to attempt to change, the 2-Ucar 35 produce route (Angew. Chem. Int. Ed., 2007,
46, 4434).
USP Kosher is produced the main by product of biofuel as biomass, and supply is in superfluous state at present.Therefore, the trans-utilization of USP Kosher becomes an important research project.Recently, the investigator has proposed to prepare 1 through hydrogenolysis of glycyl alcohol, the method for 2-Ucar 35.But; This preparation method need carry out under higher relatively added hydrogen pressure (about 5 –, 8 MPa), just can obtain comparatively ideal target product selectivity, on economy and processing safety, all is unfavorable for industrial application (the Green Chem. of this method; 2010
12, 290).
Recently, some investigators have proposed USP Kosher reformation-hydrogenation preparing 1, the variation route of 2-Ucar 35; Promptly on the heterogeneous catalyst that possesses certain reformation hydrogen production ability, make the part USP Kosher liquid phase reforming reaction at first take place, utilize the hydrogen that is somebody's turn to do " original position " generation to make rest part USP Kosher generation hydrogenolysis again to obtain hydrogen; To obtain 1; 2-Ucar 35 (J. Catal., 2010
269, 411).This method is more green, safety, if can successfully realize, will make USP Kosher preparation 1, and 2-Ucar 35 route has more prospects for commercial application.Yet, how easily the ratio of USP Kosher reformation, hydrogenation effectively to be regulated and control the enough hydrogenolysis of glycyl alcohol of hydrogen that reforming reaction is produced; But do not consume USP Kosher excessively; Thereby highly selective and obtain 1 with high yield, the 2-Ucar 35 is the key issue that this route needs to be resolved hurrily.
Summary of the invention
The objective of the invention is to propose simple, the easy to operate raising USP Kosher reformation-hydrogenation preparing 1 of a kind of technology, the 2-Ucar 35 is method optionally.
The raising USP Kosher reformation-hydrogenation preparing 1 that the present invention proposes; The 2-Ucar 35 is method optionally; Be to be the basis, when using chilling skeleton nickel molybdenum catalyst (metal catalyst), add a certain amount of oxide compound as co-catalyst with original method; Improve title product 1, the selectivity of 2-Ucar 35.
Among the present invention, said oxide compound can be selected from a kind of in Natural manganese dioxide, titanium oxide, aluminum oxide, silicon oxide, zirconium white, HZSM-5 molecular sieve, cerium oxide, the zinc oxide.
Among the present invention, the part by weight of metal catalyst and oxide compound is generally 0.1 – 10.
Among the present invention, said oxide compound is preferred zinc oxide, and the weight ratio of metal catalyst and zinc oxide is 0.1 – 10, preferred 0.5 – 2.
Among the present invention, USP Kosher reformation-hydrogenation preparing 1, the reaction of 2-Ucar 35 is carried out in continuous fixed bed reactor.In reaction tubes, not only loaded chilling skeleton nickel molybdenum catalyst, also loaded oxide compound and be used for this reaction of catalysis as co-catalyst.Chilling skeleton nickel molybdenum and oxide compound are placed in the reaction tubes, but do not have chemical action each other, neither load or the relation of parcel.The two type of feed in reaction tubes can be segmentation filling, and promptly the reactant USP Kosher is earlier through the superoxide section, and then through the metal catalyst section, or reactant is earlier through the metal catalyst section, and then through the superoxide section; It also can be the two even physical mixed.
Among the present invention, metal catalyst makes part USP Kosher generation liquid phase reforming reaction to produce hydrogen, and these hydrogen are used to make another part USP Kosher hydrogenation to generate 1, the 2-Ucar 35; The USP Kosher reformation hydrogen production that oxide compound is used to regulate on the metal catalyst is active, and the hydrogenolysis performance of regulating USP Kosher.Through regulating the part by weight of metal catalyst and oxide compound, can regulate this two reactions, make USP Kosher preparation 1, the 2-Ucar 35 is in that need not to add can the highly selective generation under the situation of hydrogen source.
The present invention utilizes the synergy between metal catalyst and the oxide compound, and through regulating the ratio of the two, realizes from USP Kosher preparation 1 continuously, the purpose of 2-Ucar 35.Because hydrogen directly provides through the USP Kosher reforming reaction, so need not the plus high-pressure hydrogen source, has not only avoided the problem that transports and store of high pressure hydrogen, and can increase the security of operation, and greatly reduced equipment cost.
USP Kosher reformation-hydrogenation preparing 1 provided by the invention, the active available following method evaluation of 2-Ucar 35 technology:
At internal diameter is in the stainless steel fixed-bed reactor of 6 mm, with silica sand 0.5 g chilling skeleton nickel molybdenum and a certain amount of oxide compound is limited in the constant temperature zone of reaction tubes, and using constant-flux pump is that the glycerin solution of 10 wt% is thrown reaction tubes into from the lower end with concentration.The mass space velocity of USP Kosher is 1.2 h
– 1, temperature of reaction is 508 K, with pressure to 3.1 MPa of argon gas conditioned reaction system.Gas phase is separated in gas-liquid separator with liquid product, and gas-phase product is used the gc on-line analysis.In the reaction process, emit the liquid in the gas-liquid separator at set intervals, with the composition of gas chromatographic analysis liquid product.
Description of drawings
Fig. 1 is the synoptic diagram of zinc oxide and chilling skeleton nickel molybdenum catalyst different types of feed in tubular reactor.Wherein, A. zinc oxide is placed earlier, places after the chilling skeleton nickel molybdenum catalyst; B. chilling skeleton nickel molybdenum catalyst is placed earlier, places behind the zinc oxide; C. place behind zinc oxide and the chilling skeleton nickel molybdenum catalyst uniform mixing.
Embodiment
The invention is further illustrated by the following examples:
Embodiment 1: the catalytic performance of chilling skeleton nickel molybdenum catalyst
At room temperature, 1.0 g chilling skeleton nickel molybdenum duraluminums (mass ratio of nickel, molybdenum, aluminium is 40%:10%:50%) are slowly joined in the NaOH aqueous solution (10 mL, 5 M).After interpolation finished, this mixture stirred extracting 60 min under 363 K, and the Dark grey solid water that obtains is washed till neutrality, promptly obtains chilling skeleton nickel molybdenum catalyst, and is stored in the zero(ppm) water for use.
USP Kosher reformation-hydrogenation conditions is: 0.5 g chilling skeleton nickel molybdenum catalyst, and concentration is the glycerin solution of 10 wt%, USP Kosher is 1.2 h with respect to the mass space velocity of chilling skeleton nickel molybdenum catalyst
– 1, temperature of reaction 508 K are with argon gas conditioned reaction system pressure to 3.1 MPa.USP Kosher reaction result on this catalyzer is listed in
Table one
Embodiment 2: the catalytic performance during the even physical mixed of different oxide compounds and chilling skeleton nickel molybdenum catalyst
0.5 g chilling skeleton nickel molybdenum catalyst, 0.25 g oxide compound, both are even physical mixed in reaction tubes.The concentration of glycerin solution is 10 wt%, and USP Kosher is 1.2 h with respect to the mass space velocity of chilling skeleton nickel molybdenum catalyst
– 1, temperature of reaction 508 K, reaction system pressure is adjusted to 3.1 MPa with argon gas.The USP Kosher reaction result that this catalyst body is fastened is also listed in
Table one
Embodiment 3: the influence of oxide compound and chilling skeleton nickel molybdenum catalyst filling order
0.5 g chilling skeleton nickel molybdenum catalyst, 1.0 g zinc oxide are seated in the reaction tubes with three kinds of different modes: (1) zinc oxide prior to chilling skeleton nickel molybdenum catalyst filling (
Fig. 1 (A)); (2) behind the zinc oxide in chilling skeleton nickel molybdenum catalyst filling (
Fig. 1 (B)); (3) both even mechanically mixing (
Fig. 1 (C)).Other reaction conditionss are: glycerin solution concentration 10 wt%, USP Kosher is with respect to mass space velocity 1.2 h of chilling skeleton nickel molybdenum catalyst
– 1, temperature of reaction 508 K are with argon gas conditioned reaction system pressure to 3.1 MPa.Reaction result under different catalysts filling is in proper order listed in
Table two
Embodiment 4: the evenly influence of oxide compound and chilling skeleton nickel molybdenum catalyst weight ratio under the physical mixed condition
0.5 g chilling skeleton nickel molybdenum catalyst and zinc oxide is even physical mixed in reaction tubes.The concentration of glycerin solution is 10 wt%, and USP Kosher is 1.2 h with respect to the mass space velocity of chilling skeleton nickel molybdenum catalyst
– 1, temperature of reaction 508 K, reaction system pressure is adjusted to 3.1 MPa with argon gas, and the weight ratio of zinc oxide and chilling skeleton nickel molybdenum catalyst is respectively 0,0.5,1.0,2.0, and reaction result is listed in
Table three
Comparative Examples:The catalytic performance of the platinum/aluminum oxide-ruthenium/aluminium oxide catalyst of even physical mixed
According to document Catal. Today, 2010,
156, 31 have prepared platinum/aluminium oxide catalyst and ruthenium/aluminium oxide catalyst, and the charge capacity of platinum and ruthenium is 5 wt%.0.25 g platinum/aluminium oxide catalyst and 0.25 g ruthenium/aluminium oxide catalyst be even physical mixed in reaction tubes, the concentration of glycerin solution is 10 wt%, and USP Kosher is 1.2 h with respect to the mass space velocity of catalyzer
– 1, temperature of reaction 508 K, reaction system pressure is adjusted to 3.1 MPa with argon gas.The USP Kosher reaction result that this catalyst body is fastened is listed in
Table two
Visible from table one, after different oxide compounds and the even physical mixed of chilling skeleton nickel molybdenum catalyst, except that Natural manganese dioxide, zirconium white, all can improve 1, the selectivity of 2-Ucar 35.But except that zinc oxide, the adding of other oxide compounds has all reduced the transformation efficiency of USP Kosher to some extent.When zinc oxide and the coexistence of chilling skeleton nickel molybdenum catalyst, not only can keep the activity of chilling skeleton nickel molybdenum catalyst, and can significantly improve 1, the selectivity of 2-Ucar 35.It is the cocatalyst system optimum that zinc oxide and chilling skeleton nickel molybdenum catalyst are formed.
From
Table twoIt is thus clear that, in tubular fixed-bed reactor, if chilling skeleton nickel molybdenum catalyst and zinc oxide are not to mix equably, but with the two with tandem mode separate filling (
Figure 1AWith
Figure 1B), the mode of these two kinds of separate filling is little to the optimization function of products distribution, the result during the approaching use separately of catalytic performance chilling skeleton nickel molybdenum catalyst.Zinc oxide have only with chilling skeleton nickel molybdenum catalyst uniform mixing together, just can embody zinc oxide to 1, the 2-Ucar 35 is castering action optionally.
From
Table threeIn visible, under the reaction conditions that is adopted, chilling skeleton nickel molybdenum catalyst can make USP Kosher transform (transformation efficiency fully; 99%), wherein the selectivity of gas-phase product is 40.9%, 1, and the selectivity of 2-Ucar 35 is 32.0%.When zinc oxide and the even physical mixed of chilling skeleton nickel molybdenum catalyst; Along with the weight ratio of zinc oxide and chilling skeleton nickel molybdenum is increased to 2.0 from 0; The selectivity of gas-phase product progressively reduces to 16.5%, 1 from 40.9%, and the selectivity of 2-Ucar 35 increases to 50.2% gradually from 32.0%; And in the process that zinc oxide dosage increases, the transformation efficiency of USP Kosher remains at about 99%.The existence that zinc oxide is described is to 1, and 2-Ucar 35 optionally castering action is to be not cost to sacrifice activity.Greater than 0.5 o'clock, from active and angle optionally, catalytic performance was all more superior in both weight ratios for platinum/aluminum oxide that documents is reported-ruthenium/aluminium oxide catalyst, the co-catalyst that zinc oxide and chilling skeleton nickel molybdenum are formed.
In sum; In USP Kosher reformation-hydrogenation system 1; In the process of 2-Ucar 35, when the weight ratio of zinc oxide and chilling skeleton nickel molybdenum catalyst is 2.0, and both even physical mixed and the cocatalyst system that forms; Can obtain USP Kosher and add under the hydrogen source 1 in nothing, 2-Ucar 35 yield surpasses 50% good result.
USP Kosher reformation-hydrogenation result during the even physical mixed of table one, different oxide compound and chilling skeleton nickel molybdenum catalyst
The different types of feed of table two, zinc oxide and chilling skeleton nickel molybdenum catalyst are to the influence of selectivity of product
Table three, zinc oxide and chilling skeleton nickel molybdenum catalyst weight ratio are to the influence of USP Kosher transformation efficiency and selectivity of product
Claims (3)
1. one kind is improved USP Kosher reformation-hydrogenation preparing 1, and the optionally method of 2-Ucar 35 is characterized in that being the basis with original method; When using chilling skeleton nickel molybdenum catalyst; Add oxide compound as co-catalyst, improve title product 1, the selectivity of 2-Ucar 35; Wherein, said oxide compound is a kind of in Natural manganese dioxide, titanium oxide, aluminum oxide, silicon oxide, zirconium white, HZSM-5 molecular sieve, cerium oxide, the zinc oxide; The weight ratio of chilling skeleton nickel molybdenum catalyst and oxide compound is 0.1 – 10.
2. method according to claim 1 is characterized in that said oxide compound is a zinc oxide, and the weight ratio of chilling skeleton nickel molybdenum catalyst and oxide compound is 0.5 – 2.
3. method according to claim 1; It is characterized in that the two type of feed in reaction tubes of said chilling skeleton nickel molybdenum catalyst and oxide compound is the segmentation filling; Be that the reactant USP Kosher is earlier through the superoxide section; And then through over-quenching skeleton nickel molybdenum catalyst section, or reactant is first through over-quenching skeleton nickel molybdenum catalyst section, and then through the superoxide section; Or the two even physical mixed.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547095A (en) * | 2020-11-12 | 2021-03-26 | 复旦大学 | Catalyst for preparing cis-pinane by alpha-pinene hydrogenation and preparation method and application thereof |
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| EP0523015A2 (en) * | 1991-07-10 | 1993-01-13 | NOVAMONT S.p.A. | A method of hydrogenating glycerol |
| CN101372444A (en) * | 2007-08-24 | 2009-02-25 | 中国科学院大连化学物理研究所 | Method for hydrocracking glycyl alcohol |
| CN101497047A (en) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | Application of X-type molecular sieve supported Ni-based catalyst in hydrogenolysis of glycyl alcohol |
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Patent Citations (3)
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|---|---|---|---|---|
| EP0523015A2 (en) * | 1991-07-10 | 1993-01-13 | NOVAMONT S.p.A. | A method of hydrogenating glycerol |
| CN101372444A (en) * | 2007-08-24 | 2009-02-25 | 中国科学院大连化学物理研究所 | Method for hydrocracking glycyl alcohol |
| CN101497047A (en) * | 2008-02-03 | 2009-08-05 | 中国科学院大连化学物理研究所 | Application of X-type molecular sieve supported Ni-based catalyst in hydrogenolysis of glycyl alcohol |
Non-Patent Citations (6)
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| 《中国博士学位论文全文数据库 工程科技I辑》 20101115 褚娴文 多元醇液相重整反应的催化剂研究 B016-2 1-3 , 第11期 * |
| HU JIYE ET AL.: "Physically mixed ZnO and skeletal NiMo for one-pot reforming-hydrogenolysis of glycerol to 1,2-propanediol", 《CHINESE JOURNAL OF CATALYSIS》 * |
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| 褚娴文: "多元醇液相重整反应的催化剂研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547095A (en) * | 2020-11-12 | 2021-03-26 | 复旦大学 | Catalyst for preparing cis-pinane by alpha-pinene hydrogenation and preparation method and application thereof |
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Application publication date: 20120718 |