CN112625011A - Continuous catalytic preparation method of cyclic polyol - Google Patents
Continuous catalytic preparation method of cyclic polyol Download PDFInfo
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- CN112625011A CN112625011A CN201910905785.XA CN201910905785A CN112625011A CN 112625011 A CN112625011 A CN 112625011A CN 201910905785 A CN201910905785 A CN 201910905785A CN 112625011 A CN112625011 A CN 112625011A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
- C07D307/20—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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Abstract
The invention relates to a preparation method of cyclic polyol, which comprises the step of carrying out one-step or multi-step dehydration reaction on raw materials under the catalytic action of hydrotalcite-like compound to obtain the cyclic polyol. The invention uses hydrotalcite-like compound as catalyst, which has stable catalytic performance and solves the problem of limited catalytic life of the prior solid acid catalyst. And the product is easy to separate and purify, and is suitable for large-scale production of the isosorbide.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a continuous catalytic preparation method of cyclic polyol.
Background
The biomass has the characteristics of reproducibility, rich resources, high functionalization and environmental friendliness, and is a hotspot for research in the fields of fine chemistry industry and new materials. Cyclic polyols such as isosorbide and the like are important biomass-based derivative chemicals, are completely nontoxic green polyols, are widely applied to the fields of medicines, surfactants, plastic additives and the like, and have very important significance in the field of novel polymer materials. Isosorbide, for example, is an excellent antihypertensive and diuretic; isosorbide can be used to synthesize surfactants span and tween; the novel green plasticizer can be used for synthesizing a novel green plasticizer to replace a benzoic acid diester plasticizer; isosorbide can be used for modifying PET to replace ethylene glycol to obviously improve the high-temperature property and the impact resistance of the PET; in the new carbonate material technology, substitution of bisphenol a, which has health risks, as an important raw material also has been initiated to expose eosin, and the polycarbonate has improved environmentally friendly properties due to its degradability, so in recent years, the synthetic technology of isosorbide and its related applications have been attracting attention.
The synthesis technical route of the cyclic polyol reported in the literature at present mainly takes glucose, fructose and sorbitol as raw materials and takes solid acid or liquid acid as a catalyst, and the cyclic polyol is synthesized by a catalytic dehydration method; because the raw materials are solid, the kettle type batch method is mostly adopted in the process for production, and although the batch method has the advantages of flexible operation and simple equipment, the defects are obvious, such as unstable quality, small production scale, troublesome operation and the like, so that a continuous reactor is adopted as much as possible to realize large-scale production. The existing catalyst mainly comprises a liquid catalyst and a solid acid catalyst, and the liquid acid catalyst has strong corrosivity; the activity of the solid acid catalyst is easy to lose, and the catalytic life cannot meet the industrial requirement.
Disclosure of Invention
The invention aims to solve the technical problem that in the prior art, the catalytic life of a catalyst solid acid adopted for preparing isosorbide is limited due to the fact that acidity is easy to lose, and provides a continuous catalytic preparation method of cyclic polyol.
In order to solve the technical problems, the invention provides a continuous catalytic preparation method of cyclic polyol, which comprises the step of carrying out one-step or multi-step dehydration reaction on raw materials under the catalytic action of hydrotalcite-like compound to obtain the cyclic polyol.
The invention takes glucose, fructose or sorbitol as raw materials, takes hydrotalcite-like compound or solid acid as a catalytic dehydrating agent, and synthesizes the cyclic polyol through one-step or multi-step dehydration reaction, wherein the structure of the cyclic polyol is shown as follows:
these products have a wide range of applications in the fields of medicine, new materials and organic synthesis because they contain multiple functional groups and special steric structures and are green biomass-derived products.
According to some embodiments of the invention, hydrotalcite-like compounds are used as catalytic dehydration agents. Hydrotalcite-like compounds are substances with a layered structure, and have wide application in catalysis due to the fact that the specific structure causes the acid-base adjustability. The molecular composition of hydrotalcite is M1-x ⅡMx Ⅲ(OH)2(An-)x/n·yH2O, wherein MⅡ＝＝Mg2+、 Ni2+、Co2+、Zn2+、Cu2+Etc.; mⅢ＝Al3+、Cr3 +、Fe3+、Sc3+Etc.; a. then-For anions which are stable in alkaline solutions, e.g. CO3 2-、NO3-、Cl-、OH-、SO4 2-Etc.; x is 0.2-0.33; y is 0 to 6. Different MⅡAnd MⅢDifferent interstitial anions A-Thus different hydrotalcite-like compounds can be formed. Because different ion exchange can lead to the adjustability of acid and alkali, the dehydration reaction mainly utilizes the acid center of hydrotalcite-like compound.
According to some embodiments of the invention, the hydrotalcite-like compounds include, but are not limited to: such as ternary zinc-aluminum hydrotalcite, dodecyl sulfonic acid pillared magnesium-aluminum lanthanum hydrotalcite, binary magnesium-aluminum hydrotalcite and the like.
According to some embodiments of the invention, the solid acid is a modified ion exchange resin, the main components being c.h.o and s elements: such as sulfonic acid ion exchange resins, and the like.
The invention adopts a continuous preparation method, and reaction equipment comprises a raw material feeding pump, a reaction liquid vaporizer, a primary dehydration reactor, a secondary dehydration reactor, a product receiving tower, a solvent recovery tower, corresponding connecting pipelines, valves, a vacuum pump, instrument accessories and the like which are sequentially connected.
According to some embodiments of the invention, the reaction liquid vaporizer temperature is 120-300 ℃, preferably 150-180 ℃; the primary dehydration temperature is between 120-300 ℃, preferably 150-170 ℃; the secondary dehydration temperature is between 120-300 ℃, preferably 160-180 ℃; the reaction pressure is between 0 and 1atm, preferably between 0.04 and 0.1 atm; the liquid space velocity is 10-100min-1Preferably 20-30min-1(ii) a The loading of the catalyst is between 100 and 1000mL, preferably 100 and 200 mL.
According to some embodiments of the invention, the reaction feedstock is preferably sorbitol, and the corresponding product is isosorbide. Adding a certain amount of sorbitol into a solvent for dissolving, pumping into a reaction liquid vaporizer through a feed pump, sequentially entering a primary dehydration reactor and a secondary dehydration reactor, entering a product receiving tower, adding the solvent for treatment, and separating to obtain a product.
According to some embodiments of the invention, the first dehydration is a 1, 4-dehydration in sorbitol and the second further dehydration is a 3, 6-dehydration, the first dehydration being easier and at a lower temperature than the second dehydration due to steric hindrance
The invention has the beneficial effects that:
1. the hydrotalcite-like compound is used as the catalyst, so that the catalytic performance is stable, and the problem of limited catalytic life of the traditional solid acid catalyst is solved.
2. The product is easy to separate and purify, and is suitable for large-scale production of isosorbide.
Drawings
FIG. 1 is the NMR spectrum of isosorbide obtained in example 3;
FIG. 2 is an HPLC chromatogram of isosorbide obtained in example 3.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Pumping 1000mL of 15% sorbitol solution into a reaction liquid vaporizer at a liquid hourly space velocity of 100min-1The temperature of a vaporizer is 160 ℃, and then the mixture enters a primary dehydration reaction temperature device and hydrotalcite catalyst Mg4 Al2(OH)12[C10 H6(SO3)2]·4H2The loading of O is 100mL, the reaction temperature is 150 ℃, then the mixture enters a secondary dehydration reactor, the hydrotalcite catalyst is 100mL, the temperature is 160 ℃, and the product content can reach 85 percent after the product is collected.
Example 2
Pumping 1000mL of 15% sorbitol solution into a reaction liquid vaporizer at a liquid hourly space velocity of 100min-1The temperature of a vaporizer is 160 ℃, and then the mixture enters a primary dehydration reaction temperature device and hydrotalcite catalyst Mg4 Al2(OH)12[C10 H6(SO3)2]·4H2The loading of O is 100mL, the reaction temperature is 160 ℃, then the mixture enters a secondary dehydration reactor, the hydrotalcite catalyst is 100mL, the temperature is 165 ℃, and the product content can reach 86% after the product is collected.
Example 3
Pumping 1000mL of 15% sorbitol solution into a reaction liquid vaporizer at a liquid hourly space velocity of 100min-1The temperature of a vaporizer is 160 ℃, and then the mixture enters a primary dehydration reaction temperature device and hydrotalcite catalyst Mg4 Al2(OH)12[C10 H6(SO3)2]·4H2The loading of O is 100mL, the reaction temperature is 165 ℃, then the mixture enters a secondary dehydration reactor, the hydrotalcite catalyst is 100mL, the temperature is 170 ℃, and the product content can reach 88 percent after the product is collected.
Example 6
This example differs from example 1 in that: example 1 the catalyst after use was first recycled. The content of the product obtained was 84%.
Example 7
This example differs from example 6 in that: example 6 recycling of the used catalyst, i.e. the second recycling of the used catalyst of example 1. The content of the product obtained was 85%.
Example 8
This example differs from example 7 in that: example 7 recycling of the used catalyst, i.e. the third recycling of the used catalyst of example 1. The content of the product obtained was 83%.
Example 9
This example differs from example 8 in that: example 8 recycling of the used catalyst, i.e. the fourth recycling of the used catalyst of example 1. The content of the product obtained was 85%.
Example 10
This example differs from example 9 in that: example 9 recycling of the used catalyst, i.e. the fifth recycling of the used catalyst of example 1. The content of the product obtained was 86%.
Example 11
This example differs from example 1 in that: in this example, glucose was used as the starting material, and the content of the obtained product was 50%.
Example 12
This example differs from example 1 in that: the raw material used in this example was fructose, and the content of the product obtained was 65%.
Example 13
Adding 200g of sorbitol and 20g of hydrotalcite-like compound into a three-necked bottle, introducing nitrogen, stirring, vacuumizing to 30mba, heating to 140 ℃, reacting for 5 hours, neutralizing, vacuumizing, distilling, decoloring, filtering and drying to obtain 112g of a product, wherein the yield is 70%.
Comparative example 1
Adding 200g of sorbitol and 20g of concentrated sulfuric acid into a three-neck flask, introducing nitrogen, stirring, vacuumizing to 30mba, heating to 140 ℃, reacting for 5 hours, neutralizing, vacuumizing, distilling, decoloring, filtering and drying to obtain 80g of product, wherein the yield is 50%.
Comparative example 2
Pumping 1000mL of 15% sorbitol solution into a reaction liquid vaporizer at a liquid hourly space velocity of 110min-1The temperature of a vaporizer is 160 ℃, then the mixture enters a primary dehydration reaction temperature device, the filling amount of a solid acid catalyst, namely sulfonic acid ion resin, is 100mL, the reaction temperature is 160 ℃, then the mixture enters a secondary dehydration reactor, the temperature of a solid acid catalyst is 175 ℃, and the content of a product can reach 73 percent after the product is collected.
Comparative example 3
Pumping 1000mL of 15% sorbitol solution into a reaction liquid vaporizer at a liquid hourly space velocity of 120min-1The temperature of a vaporizer is 160 ℃, then the mixture enters a primary dehydration reaction temperature device, the filling amount of a solid acid catalyst sulfonic acid ion resin is 100mL, the reaction temperature is 170 ℃, then the mixture enters a secondary dehydration reactor, the temperature of a solid acid catalyst is 180 ℃, and the content of a product can reach 75% after the product is collected.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for preparing a cyclic polyol, comprising:
the raw material containing polysaccharide is subjected to one-step or multi-step dehydration reaction in the presence of hydrotalcite-like compound to obtain the cyclic polyol.
2. Application of hydrotalcite-like compound as catalytic dehydrating agent.
3. The use according to claim 2, characterized in that the cyclic polyol is prepared by dehydrating the polysaccharide using hydrotalcite-like compound as catalytic dehydrating agent.
4. The method or use according to any one of claims 1 to 3, wherein the polysaccharide is selected from the group consisting of polysaccharides comprising one or more of glucose, fructose and sorbitol; and/or
The cyclic polyol is selected from one or more of the following compounds:
5. the method or use according to any of claims 1-4, wherein the molecular composition of the hydrotalcite-like compound is M1-x ⅡMx Ⅲ(OH)2(An-)x/n·yH2O，
Wherein: mⅡIs a divalent metal cation, preferably selected from Mg2+、Ni2+、Co2+、Zn2+And Cu2+One or more of;
wherein: mⅢIs a trivalent metal cation, preferably selected from Al3+、Cr3+、Fe3+And Sc3+One or more of;
wherein: a. then-The anion is preferably selected from CO, which is stable in alkaline solution3 2-、NO3-、Cl-、OH-And SO4 2-One or more of;
wherein: x is 0.2-0.33; y is 0 to 6 and n is 1 to 3.
6. The preparation method or use according to any one of claims 1 to 5, wherein the dehydration reaction conditions comprise: the temperature is 120 ℃ and 300 ℃, and the liquid hourly space velocity is 10-100min-1The pressure is 0-1 atm.
7. The method or use according to any one of claims 1 to 6, wherein the loading of the hydrotalcite-like compound is 100-1000 mL; the raw material comprising polysaccharide is gasified in a gasifier in advance, preferably at a gasification temperature of 120-300 ℃.
8. The method or use according to any one of claims 1 to 7, wherein the dehydration reaction comprises a first dehydration reaction and a second dehydration reaction, the temperature of the first dehydration reaction being lower than the temperature of the second dehydration reaction, preferably by 5 to 20 ℃.
9. The preparation method or use according to any one of claims 1 to 8, wherein the dehydration is carried out in a continuous reaction apparatus.
10. The preparation method or use according to claim 9, wherein the continuous reaction apparatus comprises: a feed pump, a reaction liquid vaporizer, a primary dehydration reactor, a secondary dehydration reactor, a product receiving tower and a solvent recovery tower which are sequentially connected.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275442A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Waterlike talc solid catalyst for production of triethyl glycol monoethers |
| CN101691376A (en) * | 2009-09-22 | 2010-04-07 | 南京工业大学 | Method for preparing isosorbide taking supported heteropoly acid as catalyst |
| CN106478649A (en) * | 2015-08-26 | 2017-03-08 | Sk新技术株式会社 | The method that anhydrosugar alcohol is prepared by two-step reaction |
| CN108126699A (en) * | 2017-12-19 | 2018-06-08 | 广州科创新能源有限责任公司 | A kind of catalyst of aqueous catalysis sugar synthesis higher alcohol |
| CN110935435A (en) * | 2018-09-21 | 2020-03-31 | 中国石油化工股份有限公司 | Catalyst for preparing cyclic polyol and application thereof |
-
2019
- 2019-09-24 CN CN201910905785.XA patent/CN112625011A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275442A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Waterlike talc solid catalyst for production of triethyl glycol monoethers |
| CN101691376A (en) * | 2009-09-22 | 2010-04-07 | 南京工业大学 | Method for preparing isosorbide taking supported heteropoly acid as catalyst |
| CN106478649A (en) * | 2015-08-26 | 2017-03-08 | Sk新技术株式会社 | The method that anhydrosugar alcohol is prepared by two-step reaction |
| CN108126699A (en) * | 2017-12-19 | 2018-06-08 | 广州科创新能源有限责任公司 | A kind of catalyst of aqueous catalysis sugar synthesis higher alcohol |
| CN110935435A (en) * | 2018-09-21 | 2020-03-31 | 中国石油化工股份有限公司 | Catalyst for preparing cyclic polyol and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| SHUN NISHIMURA ET AL.: "Monodisperse Iron Oxide Nanoparticles Embedded in MgAl Hydrotalcite as a Highly Active, Magnetically Separable,and Recyclable Solid Base Catalyst", 《BULL. CHEM. SOC. JPN.》 * |
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