CN104045610A - Method for preparing 1,4-sorbitan by dehydrating high-concentration sorbitol under catalytic action of formic acid - Google Patents
Method for preparing 1,4-sorbitan by dehydrating high-concentration sorbitol under catalytic action of formic acid Download PDFInfo
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- CN104045610A CN104045610A CN201410294984.9A CN201410294984A CN104045610A CN 104045610 A CN104045610 A CN 104045610A CN 201410294984 A CN201410294984 A CN 201410294984A CN 104045610 A CN104045610 A CN 104045610A
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention belongs to the technical field of industrial catalysis, and relates to a method for preparing 1,4-sorbitan by dehydrating high-concentration sorbitol under the catalytic action of formic acid. The method comprises the following steps: dissolving sorbitol in a formic acid water solution to obtain a reaction solution, wherein the mass ratio of the sorbitol to the formic acid water solution is 0.1-1, and the mass concentration of the formic acid water solution is 10-40%; and putting the reaction solution in a reaction kettle, reacting for some time, and cooling to room temperature; and adding a Pd-base catalyst into the cooled reaction solution, reacting at 95 DEG C for 4 hours, and filtering to obtain the 1,4-sorbitan. By using the sorbitol as the raw material and the formic acid as the dehydration reaction catalyst, the method has the advantages of mild reaction conditions and low raw material loss rate; the formic acid is decomposed into gas after the reaction; the pH value of the product system is approximate to 7; the product is easy to separate; the yield of the 1,4-sorbitan is up to 78%; the unit time production capacity is up to 3.3g.h<-1>.g[catal.]<-1>; and thus, the invention provides a novel method with high practicality.
Description
Technical field
The invention belongs to Industrial Catalysis technical field, relate to a kind of Catalyzed by Formic Acid high density sorbyl alcohol Dehydration for the method for Isosorbide-5-Nitrae-anhydro sorbitol.
Background technology
Sorbyl alcohol dehydration can generate two class products: (1) is sloughed 1 molecular water and generated anhydro sorbitol; (2) anhydro sorbitol is further sloughed 1 molecular water and is generated Isosorbide.Sorbyl alcohol has a plurality of dehydrations site, and this makes it have multiple primary dewatering product, i.e. multiple anhydro sorbitol.Wherein, Isosorbide-5-Nitrae-anhydro sorbitol is the most common and topmost primary dewatering product.Isosorbide-5-Nitrae-anhydro sorbitol is of many uses in industry, is the important source material of synthetic Span and Tween class tensio-active agent.Its fatty acid ester analog derivative can be used as natural tensio-active agent and nontoxic foodstuff additive.The traditional route of sorbyl alcohol dehydration is to adopt mineral acid as catalyzer, removes the water constantly generating in system, thereby dehydration reaction is carried out towards forward always in reaction process through underpressure distillation.Reaction finishes in rear use alkali lye and mineral acid, can obtain the sorbyl alcohol dewatered product of purifying by underpressure distillation recrystallization.But the dehydration of mineral acid catalyzing sorbitol exists many deficiencies, the method can produce corrosion to equipment, shortens service life of equipment; In reaction, carbonization phenomenon is serious, and side reaction is many, and product yield is low; Catalyzer is not easily separated and reclaim.Along with the inconvenience that inorganic acid catalyst brings aborning, little by little there is replacing with solid catalyst the synthesis technique of liquid acid catalyst.The people such as Huang He (CN101691376A) adopt usings the heteropolyacid catalyst that metal oxide, molecular sieve etc. contain Mo, elements such as w as supported carrier, in fixed-bed reactor, carry out dehydration reaction, the raw material using is the sorbitol aqueous solution that mass percent is 5-15%, and the primary product obtaining is Isosorbide; The people such as grade of coca discloses a kind of strong-acid ion exchange resin that uses and as dehydration catalyst, has prepared the method for Isosorbide in patent CN1425637A, the method is the band aqua that adds 10-50% weight percentage in sorbitol aqueous solution, at 100-120 ℃, carry out dehydration reaction, reaction finishes rear decoupled band aqua, obtains the sorbyl alcohol dewatered product of purifying through alcohol-ether recrystallization.Yet in above-mentioned method, the active centre quantity of solid catalyst is limited, active sites is limited to mass transfer process with contacting of reactant, therefore take in the heterogeneous catalytic reaction system that solid catalyst is dehydration catalyst, the initial concentration lower (mass percent is 5-20%) of sorbyl alcohol, this has caused the throughput of dewatered product in the unit time lower.The dehydration of mineral acid catalyzing sorbitol belongs to homogeneous catalytic reaction, and catalyzer can contact fully effectively with reactant, and catalytic efficiency is high.Yet because mineral acid is not consumed in reaction process, make product system be strongly-acid, under this condition, cannot directly carry out the separation of product, need generate corresponding salts solution through the acid of alkali lye neutralising fluid, and the separating difficulty of product in salts solution is large, running cost is high.Face these difficult problems, we need to find a suitable sorbyl alcohol dehydration route, can merge the advantage of heterogeneous catalyst and homogeneous catalysis, and the catalyzing sorbitol dehydration of high-efficiency cleaning ground generates object product.
Summary of the invention
The object of the present invention is to provide a kind of with biomass-based Catalyzed by Formic Acid sorbyl alcohol Dehydration the method for Isosorbide-5-Nitrae-anhydro sorbitol.The initial concentration of the method Raw is high, and formic acid can be decomposed after reaction finishes.The advantages such as it is high that the method has unit time throughput, and reaction conditions is gentle, and loss rate of raw materials is low, and product system is clean.
The invention provides a kind of Catalyzed by Formic Acid high density sorbyl alcohol Dehydration for the method for Isosorbide-5-Nitrae-anhydro sorbitol, technical scheme is as follows:
(1) sorbyl alcohol is dissolved in to aqueous formic acid, is reaction solution; Wherein, the mass ratio of sorbyl alcohol and aqueous formic acid is 0.1-1, and the mass concentration of aqueous formic acid is 10-40%.
(2) reaction solution of step (1) gained is placed in to reactor, after reaction certain hour, is cooled to room temperature; Wherein, temperature of reaction is 150-180 ℃, and the reaction times is 3-9h.
(3) join in the cooled reaction solution of step (2) Pd is catalyst based, react 4h at 95 ℃, after filtration, obtain product liquid, be Isosorbide-5-Nitrae-anhydro sorbitol.
The invention has the beneficial effects as follows: of the present invention 1, the preparation method of 4-anhydro sorbitol be take sorbyl alcohol as raw material, and formic acid is dehydration reaction catalyzer, and reaction conditions is gentle, loss rate of raw materials is low, formic acid usage quantity is 10% of sorbyl alcohol quality, and after reaction, formic acid is broken down into gas, and the pH of product system is close to 7, product is easily separated, the yield of Isosorbide-5-Nitrae-anhydro sorbitol is up to 72%, and the unit time, throughput was up to 3.3gh
-1g
catal. -1, be the novel method that a kind of practicality is very strong.
Embodiment
Below in conjunction with technical scheme, describe specific embodiments of the invention in detail.
Embodiment 1
1g sorbyl alcohol is dissolved in to 10g aqueous formic acid, and the mass concentration of aqueous formic acid is 40%.Liquid is added to 50mL Hastelloy autoclave, be warming up to 150 ℃, reaction 3h.Naturally cool to after room temperature, by 0.2g Pd-Au/SiO
2catalyzer adds in reacted liquid, and wherein, the loading of Pd is 3wt%, and the loading of Au is 1wt%, 95 ℃ of reaction 4h under opening-wide state, and filtration obtains liquid and is product, and product analysis the results are shown in Table one.
Embodiment 2
1g sorbyl alcohol is dissolved in to 10g aqueous formic acid, and the mass concentration of aqueous formic acid is 40%.Liquid is added to 50mL Hastelloy autoclave, be warming up to 150 ℃, reaction 9h.Naturally cool to after room temperature, by 0.2g Pd-Au/SiO
2catalyzer adds in reacted liquid, and wherein, the loading of Pd is 3wt%, and the loading of Au is 1wt%, 95 ℃ of reaction 4h under opening-wide state, and filtration obtains liquid and is product, and product analysis the results are shown in Table one.
Embodiment 3
1g sorbyl alcohol is dissolved in to 10g aqueous formic acid, and the mass concentration of aqueous formic acid is 10%.Liquid is added to 50mL Hastelloy autoclave, be warming up to 180 ℃, reaction 3h.Naturally cool to after room temperature, by 0.2g Pd-Au/SiO
2catalyzer adds in reacted liquid, and wherein, the loading of Pd is 3wt%, and the loading of Au is 1wt%, 95 ℃ of reaction 4h under opening-wide state, and filtration obtains liquid and is product, and product analysis the results are shown in Table one.
Embodiment 4
1g sorbyl alcohol is dissolved in to 10g aqueous formic acid, and the mass concentration of aqueous formic acid is 10%.Liquid is added to 50mL Hastelloy autoclave, be warming up to 180 ℃, reaction 9h.Naturally cool to after room temperature, by 0.2g Pd-Au/SiO
2catalyzer adds in reacted liquid, and wherein, the loading of Pd is 3wt%, and the loading of Au is 1wt%, 95 ℃ of reaction 4h under opening-wide state, and filtration obtains liquid and is product, and product analysis the results are shown in Table one.
Embodiment 5
5g sorbyl alcohol is dissolved in to 10g aqueous formic acid, and the mass concentration of aqueous formic acid is 10%.Liquid is added to 50mL Hastelloy autoclave, be warming up to 180 ℃, reaction 3h.Naturally cool to after room temperature, by 0.2g Pd-Au/SiO
2catalyzer adds in reacted liquid, and wherein, the loading of Pd is 3wt%, and the loading of Au is 1wt%, 95 ℃ of reaction 4h under opening-wide state, and filtration obtains liquid and is product, and product analysis the results are shown in Table one.
Embodiment 6
10g sorbyl alcohol is dissolved in to 10g aqueous formic acid, and the mass concentration of aqueous formic acid is 10%.Liquid is added to 50mL Hastelloy autoclave, be warming up to 180 ℃, reaction 3h.Naturally cool to after room temperature, by 0.2g Pd-Au/SiO
2catalyzer adds in reacted liquid, and wherein, the loading of Pd is 3wt%, and the loading of Au is 1wt%, 95 ℃ of reaction 4h under opening-wide state, and filtration obtains liquid and is product, and product analysis the results are shown in Table one.
Table one embodiment response analysis result
Claims (1)
1. Catalyzed by Formic Acid high density sorbyl alcohol Dehydration, for a method for Isosorbide-5-Nitrae-anhydro sorbitol, is characterized in that, comprises the steps:
(1) sorbyl alcohol is dissolved in to aqueous formic acid, is reaction solution; Wherein, the mass ratio of sorbyl alcohol and aqueous formic acid is 0.1-1, and the mass concentration of aqueous formic acid is 10-40%;
(2) reaction solution of step (1) gained is placed in to reactor, after reaction certain hour, is cooled to room temperature; Wherein, temperature of reaction is 150-180 ℃, and the reaction times is 3-9h;
(3) join in the cooled reaction solution of step (2) Pd is catalyst based, react 4h at 95 ℃, after filtration, obtain product liquid, be Isosorbide-5-Nitrae-anhydro sorbitol.
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| CN201410294984.9A CN104045610B (en) | 2014-06-26 | 2014-06-26 | Catalyzed by Formic Acid high-concentration sorbitol is dehydrated the method preparing 1,4-anhydro sorbitol |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690039A (en) * | 2018-06-26 | 2018-10-23 | 大连理工大学 | A kind of method that sorb dehydration of alcohols prepares isobide |
Citations (3)
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| CN1218805A (en) * | 1997-11-07 | 1999-06-09 | 底古萨股份公司 | Process for preparing penta or hexa cyclic ether, particularly dehydropolyol |
| US20070173654A1 (en) * | 2006-01-26 | 2007-07-26 | Holladay Johnathan E | Methods for dehydration of sugars |
| CN102757445A (en) * | 2012-07-27 | 2012-10-31 | 山东福田药业有限公司 | Preparation technique of isosorbide |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218805A (en) * | 1997-11-07 | 1999-06-09 | 底古萨股份公司 | Process for preparing penta or hexa cyclic ether, particularly dehydropolyol |
| US20070173654A1 (en) * | 2006-01-26 | 2007-07-26 | Holladay Johnathan E | Methods for dehydration of sugars |
| CN102757445A (en) * | 2012-07-27 | 2012-10-31 | 山东福田药业有限公司 | Preparation technique of isosorbide |
Non-Patent Citations (6)
| Title |
|---|
| MIN PANG ET AL: "An eco-friendly paradigm for the synthesis of sorbitan and isosorbide through dehydration of sorbitol catalyzed by bio-based and decomposable formic acid", 《2ND INTERNATIONAL CONGRESS ON CATALYSIS FOR BIOREFINERIES》, 22 September 2013 (2013-09-22) * |
| S. P. HILL ET AL: "The Conversion of Polysaccharides to Hydrogen Gas. Part I: The Palladium Catalysed Decomposition of Formic Acid Sodium Formate Solutions", 《J. CHEM. TECH. BIOTECHNOL.》, vol. 41, no. 2, 24 April 2007 (2007-04-24), pages 121 - 133 * |
| XIAOCHUN ZHOU ET AL: "High-quality hydrogen from the catalyzed decomposition of formic acid by Pd-Au/C and Pd-Ag/C", 《CHEM.COMMUN.》, vol. 2008, no. 30, 29 May 2008 (2008-05-29), pages 3540 - 3542 * |
| XIAOJUN GU ET AL: "Synergistic Catalysis of Metal-Organic Framework-Immobilized Au-Pd Nanoparticles in Dehydrogenation of Formic Acid for Chemical Hydrogen Storage", 《J. AM. CHEM. SOC.》, vol. 133, no. 31, 15 July 2011 (2011-07-15), pages 11822 - 11825, XP 055210206, DOI: doi:10.1021/ja200122f * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690039A (en) * | 2018-06-26 | 2018-10-23 | 大连理工大学 | A kind of method that sorb dehydration of alcohols prepares isobide |
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Effective date of registration: 20221102 Address after: No. 1-2-15, Technical Innovation Building, No. 2, East Section of Shihua North Road, Pengzhou, Chengdu, Sichuan, 611939 Patentee after: Chengdu Dayan Technology Industry Development Co.,Ltd. Address before: 124221 Panjin campus of Dalian University of technology, No. 2 Dagong Road, Liaodongwan new area, Panjin City, Liaoning Province Patentee before: DALIAN University OF TECHNOLOGY |
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