CN106694035B - Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol - Google Patents

Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol Download PDF

Info

Publication number
CN106694035B
CN106694035B CN201610312860.8A CN201610312860A CN106694035B CN 106694035 B CN106694035 B CN 106694035B CN 201610312860 A CN201610312860 A CN 201610312860A CN 106694035 B CN106694035 B CN 106694035B
Authority
CN
China
Prior art keywords
ionic liquid
use according
catalyst
sugar alcohol
dehydration reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610312860.8A
Other languages
Chinese (zh)
Other versions
CN106694035A (en
Inventor
徐宝华
邓洁
郭亚菲
张锁江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Process Engineering of CAS
Original Assignee
Institute of Process Engineering of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Process Engineering of CAS filed Critical Institute of Process Engineering of CAS
Priority to CN201610312860.8A priority Critical patent/CN106694035B/en
Publication of CN106694035A publication Critical patent/CN106694035A/en
Application granted granted Critical
Publication of CN106694035B publication Critical patent/CN106694035B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
    • 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
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
    • 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
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
    • 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
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
    • B01J31/0288—Phosphorus
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

Use of a sulphonic acid functionalised ionic liquid catalyst of formula I wherein Y is Y for catalysing the intramolecular dehydration of a polyhydric sugar alcohol to produce the corresponding dehydrated compound+Is imidazole, quaternary amine, pyridine and pyrrole heterocyclic compound cation; n is 0 or a positive integer; x‑Is Cl‑、Br‑、I‑、BF4 ‑、PF6 ‑、SbF6 ‑、HSO4 ‑、CmH2m+1SO4 ‑、H2PO4 ‑、CF3SO3 ‑、C(CF3SO2)2 ‑、NTf2 ‑、N(C2F5SO2)2 ‑、NO3 ‑、CH3COO‑Or CF3COO‑And m is a positive integer between 1 and 8. Compared with the existing preparation method, the method for preparing the corresponding dehydrated compound of the polyhydric sugar alcohol by using the ionic liquid catalytic system has the advantages of high raw material conversion rate, easy product separation, good catalyst stability, low consumption, recyclable potential, low corrosion to equipment and the like.

Description

Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to an application of an acidic ionic liquid catalyst in catalyzing polyhydric sugar alcohol to prepare a corresponding dehydrated compound.
Background
Due to the special chiral structure of the dehydrated compound prepared by dehydrating the polyhydric sugar alcohol, the dehydrated compound is widely applied to the fields of medicines, foods, cosmetics, polymers and the like, wherein the dehydration of sorbitol to prepare isosorbide is particularly a focus of attention in the field. Isosorbide is a novel plant-based fine chemical intermediate, functional diol, and is widely applied to the fields of medicines, foods, cosmetics, polymers and the like due to the special chiral structure of isosorbide. Currently, isosorbide is primarily made by two-step dehydration of sorbitol.
The conventional route for the dehydration of sorbitol is to use inorganic acids as catalysts, for example, HCl, H, are described in U.S. Pat. No. 8, 6407266, WO 00/14081, U.S. Pat. No. 3, 4169152, DD 132266, WO 89/00162A, DE 3521809A1, DE 3229412A13PO4、HF、H2SO4And catalyzing the dehydration of the sorbitol by using liquid acid as a catalyst to prepare the isosorbide. In general, in the sorbitol dehydration process using a liquid acid as a catalyst, water continuously generated in the reaction system is removed by distillation under reduced pressure during the reaction, thereby causing the reaction to proceed in the direction of the formation of isosorbide. After the reaction is finished, neutralizing the catalyst liquid acid by using alkali liquor, and carrying out reduced pressure distillation and recrystallization to obtain the purified isosorbide. However, the isosorbide production process using inorganic acid as catalyst has the disadvantages of serious corrosion to equipment and reduced service life of equipment; the carbonization phenomenon is serious in the reaction; side reactions are more, and the product yield is low; the catalyst is not easy to separate and can not be recycled.
Since the use of liquid acid as a catalyst has many inconveniences in production, research into highly efficient solid acid catalysts has been gradually developed. Yellow and et al (CN 101691376a) use a heteropoly acid catalyst containing Mo, M, etc. elements prepared with a metal oxide, a molecular sieve, etc. as a carrier; high-rooted et al (CN 1425637A) use strongly acidic ion exchange resins as catalysts; CA 1178288A1 adopts sulfonated polystyrene resin as a catalyst for catalyzing the dehydration of sorbitol to prepare isosorbide. However, in the above method, the number of active sites of the solid catalyst is limited, and the contact of the active sites with the reactants is limited by the mass transfer process. Therefore, in heterogeneous reaction systems using solid acids as catalysts, the starting concentration of sorbitol is generally low, in the range of 5 to 20% aqueous solution, resulting in a low production capacity of dehydrated products per unit time.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a sulfonic acid functionalized ionic liquid catalyst which combines the advantages of both homogeneous and heterogeneous catalysts, and can efficiently and cleanly catalyze polyhydric sugar alcohols to prepare corresponding dehydrated compounds.
The invention combines the designability of ionic liquid structure effect and the extremely low saturated vapor pressure, and provides a method for preparing a corresponding dehydrated compound by catalyzing alditol by using acidic ionic liquid as a catalyst. Because the saturated vapor pressure of the ionic liquid is extremely low, the ionic liquid can not be lost in the rectification separation process of the product and can be recycled, the discharge of waste acid is reduced, and the production process in the preparation process is greatly improved.
In order to achieve the purpose, the invention adopts the following technical means:
use of a sulphonic acid functionalised ionic liquid catalyst of formula I for catalysing the intramolecular dehydration of a polyhydric sugar alcohol to produce the corresponding dehydrated compound,
Figure BDA0000988026110000021
wherein Y is+Can be imidazole, quaternary amine, pyridine, pyrrole and piperidine heterocyclic compound cations; n is 0 or a positive integer, e.g., 0, 3, 6, 9, 12, 15, 19, 23, 30, 50, etc.; x-Is Cl-、Br-、I-、BF4 -、PF6 -、SbF6 -、HSO4 -、CmH2m+1SO4 -、H2PO4 -、CF3SO3 -、C(CF3SO2)2 -，NTf2 -、N(C2F5SO2)2 -，NO3 -、CH3COO-Or CF3COO-And m is a positive integer between 1 and 8.
Preferably, in the use according to the invention, X is-Is Cl-、BF4 -、HSO4 -、H2PO4 -、CF3SO3 -、C(CF3SO2)2 -，NTf2 -、N(C2F5SO2)2 -Or CF3COO-。
Preferably, in the use according to the invention, the ionic liquid cation is:
Figure BDA0000988026110000031
Figure BDA0000988026110000032
wherein R is1，R2，R3，R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14Substituted or unsubstituted halogenated group and alkyl.
Preferably, the alkyl group is C1-C12Alkyl, optionally substituted by F, Cl, OH, NO2，NH2The groups are partially or fully substituted; r1，R2，R3，R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14May be the same or different.
Preferably, the ionic liquid is:
Figure BDA0000988026110000033
a combination of two or more thereof.
The sulfonic acid-functionalized ionic liquid catalysts of the present invention may be synthesized by prior art methods, such as disclosed in WO 2014063582a1, CN 1594280a, CN 101172949a, WO 2012037736A1, CN 102442951B.
We have found that this sulfonic acid functionalized ionic liquid catalyst system significantly improves the conversion of polyhydric sugar alcohols and the yield of the corresponding anhydro compounds when compared to other catalysts, with the same molar ratio of the catalyst of the invention being added to the dehydration reaction of the polyhydric sugar alcohol. The ionic liquid catalyst system has good stability and reaction activity, the saturated vapor pressure is extremely low, alkali is not required to be added in the subsequent dehydration compound purification process to neutralize the catalyst, the rectification and purification of the product are facilitated, and the discharge of waste acid can be reduced.
Preferably, in the use according to the invention, the polyhydric sugar alcohol is sorbitol and the corresponding anhydro compound is isosorbide. A
Preferably, in the application of the present invention, the temperature of the dehydration reaction is 100-300 ℃, for example, 102 ℃, 110 ℃, 130 ℃, 150 ℃, 190 ℃, 220 ℃, 250 ℃, 280 ℃, etc., preferably 100-200 ℃, more preferably 110-170 ℃. The invention adopts lower temperature to achieve high product yield at one time, and simultaneously improves the product quality.
Preferably, in the use of the present invention, the pressure of the dehydration reaction is 1 to 15kPa, for example, 2.5kPa, 3.6kPa, 4.5kPa, 6kPa, 8kPa, 10kPa, 12kPa, 14kPa, etc., preferably 1 to 10kPa, more preferably 3 to 5 kPa.
The selection of the temperature and pressure ranges of the present invention is interdependent, with the lowest temperature corresponding to the extreme low pressure. Therefore, the following conditions need to be satisfied in the selection: 1) the dehydration reaction is a bulk reaction, and the polyhydric sugar alcohol is required to be ensured to be carried out in a molten state; 2) higher temperatures favor dehydration, but also accelerate the occurrence of side reactions (such as coking) under acidic conditions; therefore, the temperature should not be theoretically higher than 300 ℃, preferably not higher than 200 ℃; 3) low pressures are advantageous for the choice of low temperatures, but it is not industrially possible to achieve pressures that are too low, so that currently 1 to 15kPa, preferably 3 to 5kPa, are used.
The reaction time is mainly determined by the conversion/selectivity of the reaction under certain temperature and pressure, and the product is beneficial to a certain extent by prolonging the time, but coking is easy to generate (the carbonization degree is high) in a longer time. Therefore, in the application of the present invention, the time of the dehydration reaction is preferably at least 5min, for example, 7min, 8.5min, 9.6min, 12min, 14min, 16min, 19min, 25min, 40min, 1.5h, 3h, 5h, 8h, 14h, 20h, 25h, 30h, etc., preferably at least 10min, and more preferably 0.5 to 24 h.
The catalyst system of the invention is preferably used in homogeneous phase.
Increasing the amount of catalyst within a certain range can improve the catalytic effect, but the amount of catalyst is too high to be beneficial to the product selectivity. Therefore, in the use of the present invention, the catalyst is preferably used in an amount of 0.1 mol% to 20 mol%, for example, 0.3 mol%, 0.6 mol%, 1.2 mol%, 1.5 mol%, 2 mol%, 5 mol%, 8 mol%, 11 mol%, 14 mol%, 16 mol%, 18 mol% or the like of the polyhydric sugar alcohol.
The reaction conditions of the invention can be one-time reaction in a batch reactor or continuous reaction, and the continuous reaction can improve the utilization efficiency of the catalyst (the continuous reaction can be carried out for a period of time at a lower temperature in the reactor and then the temperature is raised for reaction, and the method can reduce the generation of by-products and shorten the reaction time), and is more beneficial to the reaction. Thus, the method of the invention will increase the yield of dehydrated compounds and has the potential to improve the process route for the preparation of dehydrated compounds by catalytic dehydration of polyhydric sugar alcohols.
Compared with the existing preparation method, the method for preparing the isosorbide by using the ionic liquid and the catalytic system has the advantages of high raw material conversion rate, easy product separation, good catalyst stability, small using amount, recycling, low corrosion to equipment and the like.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows.
The conversion of the polyhydric sugar alcohol and the selectivity for the corresponding anhydro compound can be calculated with reference to the conversion of sorbitol and the selectivity for 1, 4-anhydrosorbitol and the selectivity for isosorbide as follows.
The conversion of sorbitol and the selectivity for 1, 4-sorbitan and the selectivity for isosorbide are determined by liquid chromatography, which is defined as follows:
Figure BDA0000988026110000051
Figure BDA0000988026110000061
example 1
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 130 ℃ to melt the sorbitol; then 0.0012mol of 1-sulfopropyl-3-methylimidazolium chloride ionic liquid is added, the reaction is carried out for 4 hours under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 2
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 130 ℃ to melt the sorbitol; then 0.0012mol of 1-sulfopropyl-2-hydroxymethyl 3-methylimidazolium tetrafluoroborate ionic liquid is added, the reaction is carried out for 4 hours under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 3
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 130 ℃ to melt the sorbitol; then 0.0012mol of 1-sulfopropyl pyridine hydrogen phosphate ionic liquid is added, the reaction is carried out for 4 hours under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 4
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 130 ℃ to melt the sorbitol; then 0.0012mol of triethylsulfopropyl hexafluorophosphate phosphonium ionic liquid is added, the reaction is carried out for 4 hours under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 5
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 130 ℃ to melt the sorbitol; then 0.0012mol of methylsulfonylpyrrole trifluoroacetate ionic liquid is added, the reaction is carried out for 4h under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 6
Adding 0.2mol of sorbitol with the mass fraction of 70% into a 100mL three-neck flask with magnetons, and heating to 130 ℃; then 0.0012mol of methylsulfonylpyrrole trifluoroacetate ionic liquid is added, the reaction is carried out for 4h under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 7
Adding 0.2mol of sorbitol with the mass fraction of 50% into a 100mL three-neck flask with magnetons, and heating to 130 ℃; then 0.0012mol of methylsulfonylpyrrole trifluoroacetate ionic liquid is added, the reaction is carried out for 4h under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 8
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 150 ℃ to melt the sorbitol; then 0.0012mol of methylsulfonylpyrrole trifluoroacetate ionic liquid is added, the reaction is carried out for 4h under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 9
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 110 ℃ to melt the sorbitol; then 0.0012mol of methylsulfonylpyrrole trifluoroacetate ionic liquid is added, the reaction is carried out for 4h under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 10
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 100 ℃ to melt the sorbitol; then 0.0012mol of triethylsulfopropyl hexafluorophosphate phosphonium ionic liquid is added, the reaction is carried out for 24 hours under the pressure of 10kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 11
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 300 ℃ to melt the sorbitol; then 0.0002mol of triethylsulfopropyl hexafluorophosphate phosphonium ionic liquid is added, the reaction is carried out for 0.5h under the pressure of 1kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Example 12
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 200 ℃ to melt the sorbitol; then 0.04mol of triethylsulfopropyl hexafluorophosphate phosphonium ionic liquid is added, the reaction is carried out for 10h under the pressure of 15kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Comparative example 1
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 130 ℃ to melt the sorbitol; then 0.0012mol of concentrated sulfuric acid is added, the reaction is carried out for 4 hours under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
Comparative example 2
Adding 0.2mol of sorbitol into a 100mL three-neck flask with magnetons, and heating to 130 ℃ to melt the sorbitol; then 0.0036mol of concentrated sulfuric acid (the dosage of the catalyst which is commonly used in industry and is 3 times of the dosage of the catalyst used in the invention) is added for reaction for 4 hours under the pressure of 4kPa, and the content of the components is analyzed by high performance liquid chromatography. The results are shown in Table 1.
TABLE 1
Figure BDA0000988026110000081
Figure BDA0000988026110000091
Comparison of the examples with the comparative examples shows:
1) the catalyst used in the invention has excellent catalytic effect, and reaches or exceeds the concentrated sulfuric acid catalyst used in the industry at present;
2) the catalyst used in the invention has the property of extremely low saturated vapor pressure, so that the reaction product can be directly distilled during purification, and the product purification scheme is simplified;
3) compared with a concentrated sulfuric acid catalyst, the catalyst used in the invention has more excellent recyclable potential.
Compared with the ionic liquid of the invention, the ionic liquid of the invention can achieve or exceed the catalytic effect of the strong acid as the catalyst under the same condition, which shows that the ionic liquid catalyst used by people has higher catalytic effect; and compared with concentrated sulfuric acid, the ionic liquid has the advantage of low saturated vapor pressure, and is favorable for product separation and catalyst circulation.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (14)

1. Use of a sulfonic acid functionalized ionic liquid catalyst of formula I for catalyzing an intramolecular dehydration reaction of a polyhydric sugar alcohol to produce a corresponding dehydrated compound,
Figure FDA0002197598150000011
n is 0 or a positive integer; x-Is BF4 -、PF6 -、SbF6 -、CmH2m+1SO4 -、H2PO4 -、CF3SO3 -、C(CF3SO2)2 -、NTf2 -、N(C2F5SO2)2 -、NO3 -Or CF3COO-M is a positive integer between 1 and 8;
the cation of the ionic liquid is:
Figure FDA0002197598150000012
wherein R is1，R2，R3，R4，R5，R6，R7，R8，R9，R10，R11，R12，R13，R14Is substituted or unsubstituted halogeno, alkyl, said alkyl being substituted by F, Cl, OH, NO2，NH2The groups are partially or fully substituted;
wherein the temperature of the dehydration reaction is 100-300 ℃, and the pressure of the dehydration reaction is 1-15 kPa.
2. Use according to claim 1, characterized in that X-Is BF4 -、H2PO4 -、CF3SO3 -、C(CF3SO2)2 -，NTf2 -、N(C2F5SO2)2 -Or CF3COO-。
3. Use according to claim 1, characterized in that the alkyl group is C1-C12An alkyl group.
4. Use according to claim 1, wherein the ionic liquid is:
Figure FDA0002197598150000014
Figure FDA0002197598150000021
or a combination of two or more thereof.
5. Use according to claim 1, characterized in that the polyhydric sugar alcohol is sorbitol and the corresponding anhydro compound is isosorbide.
6. Use according to claim 1, characterized in that the temperature of the dehydration reaction is 100-200 ℃.
7. Use according to claim 6, wherein the temperature of the dehydration reaction is 110-170 ℃.
8. Use according to claim 1, characterized in that the pressure of the dehydration reaction is 1-10 kPa.
9. Use according to claim 8, characterized in that the pressure of the dehydration reaction is 3-5 kPa.
10. Use according to claim 1, characterized in that the time of the dehydration reaction is at least 5 min.
11. Use according to claim 10, characterized in that the time of the dehydration reaction is at least 10 min.
12. Use according to claim 11, characterized in that the time of the dehydration reaction is between 0.5 and 24 h.
13. Use according to claim 1, characterized in that the catalyst is used in homogeneous phase.
14. Use according to claim 1, characterized in that the catalyst is used in an amount of 0.1-20 mol% of the polyhydric sugar alcohol.
CN201610312860.8A 2016-05-12 2016-05-12 Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol Active CN106694035B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610312860.8A CN106694035B (en) 2016-05-12 2016-05-12 Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610312860.8A CN106694035B (en) 2016-05-12 2016-05-12 Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol

Publications (2)

Publication Number Publication Date
CN106694035A CN106694035A (en) 2017-05-24
CN106694035B true CN106694035B (en) 2020-01-24

Family

ID=58939701

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610312860.8A Active CN106694035B (en) 2016-05-12 2016-05-12 Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol

Country Status (1)

Country Link
CN (1) CN106694035B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107722033B (en) * 2017-11-06 2020-06-02 上海纳米技术及应用国家工程研究中心有限公司 Method for separating sugar alcohol dehydration reaction product by adding hydrophobic ionic liquid and carrying out reduced pressure distillation
CN109320522A (en) * 2018-12-03 2019-02-12 山东天力药业有限公司 A method of preparing isobide
CN110090664B (en) * 2019-06-03 2020-08-21 中国科学院过程工程研究所 Acidic ionic liquid @ COF material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1594280A (en) * 2004-06-25 2005-03-16 清华大学 Pyridine sulfonic acid salt ion liquid and its preparing process and application
CN102199136A (en) * 2011-03-31 2011-09-28 中国科学院西双版纳热带植物园 Method for preparing 5-hydroxymethylfurfural from acidic iron liquids
CN102875301A (en) * 2011-07-12 2013-01-16 中国石油化工股份有限公司 Method for catalytic dehydration of ethanol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1594280A (en) * 2004-06-25 2005-03-16 清华大学 Pyridine sulfonic acid salt ion liquid and its preparing process and application
CN102199136A (en) * 2011-03-31 2011-09-28 中国科学院西双版纳热带植物园 Method for preparing 5-hydroxymethylfurfural from acidic iron liquids
CN102875301A (en) * 2011-07-12 2013-01-16 中国石油化工股份有限公司 Method for catalytic dehydration of ethanol

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Selective dehydration of sorbitol to 1,4-anhydro-D-sorbitol catalyzed by a polymer-supported acid catalyst;Yuhe Xiu, et al;《RSC Adv.》;20150316;第5卷;第28234页左栏第3段至右栏第3段及图2、表2实施例5 *
酸性离子液体中果糖脱水制备5-羟甲基糠醛;王福余，等;《应用化学》;20140430;第31卷(第4期);第425页倒数第1段至第426页第5段 *

Also Published As

Publication number Publication date
CN106694035A (en) 2017-05-24

Similar Documents

Publication Publication Date Title
CN106694035B (en) Application of acidic ionic liquid catalyst in preparation of corresponding dehydrated compound by catalyzing polyhydric sugar alcohol
CN104529707A (en) Method for one-step hydration synthesis of terpilenol by catalyzing turpentine through carbon-based solid acid
CN107311868B (en) Method for preparing p-tert-butyl methyl benzoate
CN102267882B (en) Method for preparing acrolein by catalyzing dehydration of glycerol with immobilized acidic ionic liquid
US10335774B2 (en) Carbonylation process and catalyst system therefor
CN102311360B (en) Method for preparing N-ethoxy oxalyl alanine ethyl ester
CN102146032A (en) Method for preparing methyl methacrylate
CN108863793B (en) Preparation method of isopropyl acetate
CN112194569B (en) Method for preparing cyclopentanol from cyclopentene through cyclopentyl formate
CN106673952A (en) Method for catalytic synthesis of benzyl toluene by activated clay-loaded ferric trichloride (FeCl3) solid acid catalyst
CN107663148B (en) Method for preparing C6-10 aryl C1-4 alkyl ether
CN109942358A (en) A kind of solid acid catalysis low-boiling point alcohol continuous esterification technique
US10087131B2 (en) Process for the production of glycolic acid
CN102976939B (en) Preparation method of propionate
CN106631651A (en) Preparation method of benzyl methylbenzene
CN112645815A (en) Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent
CN103288628A (en) Method for preparing 1,3-acetone dicarboxylic acid diester and intermediate thereof by oxidizing citric acid and hydrogen peroxide
CN110818538A (en) Na-NaOH/gamma-Al2O3Method for catalytic synthesis of anisole
CN104355976B (en) A kind of method of acetone through one-step method synthesis mesityl oxide
KR102086531B1 (en) A method for preparation of anhydrosugar alcohols usint a catalyst that is heteropoly aci salt substituted with cesium
CN103288634A (en) A method for catalytic synthesis of diisopropyl maleate
CN113461498B (en) Environment-friendly preparation method of acetal
CN109384642A (en) A kind of preparation method of sec-butyl alcohol
CN114292168B (en) Method for preparing acetone by using by-product in process of synthesizing triacetonamine
TWI435862B (en) Tetraacetylalkylenediamine

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant