CN111744553A - Zirconium dodecylbenzene sulfonate catalyst and application thereof in furfuryl alcohol alcoholysis reaction - Google Patents
Zirconium dodecylbenzene sulfonate catalyst and application thereof in furfuryl alcohol alcoholysis reaction Download PDFInfo
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims abstract description 270
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 20
- VFWYTFYWLOJBKA-UHFFFAOYSA-N dodecyl benzenesulfonate;zirconium Chemical compound [Zr].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 VFWYTFYWLOJBKA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- 238000000034 method Methods 0.000 claims abstract description 25
- -1 alkyl levulinates Chemical class 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 30
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 20
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 20
- 229940058352 levulinate Drugs 0.000 claims description 17
- 150000003754 zirconium Chemical class 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000000796 flavoring agent Substances 0.000 claims 1
- 235000019634 flavors Nutrition 0.000 claims 1
- 230000002431 foraging effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002028 Biomass Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 2
- 239000007848 Bronsted acid Substances 0.000 abstract 1
- 239000002841 Lewis acid Substances 0.000 abstract 1
- 150000007517 lewis acids Chemical class 0.000 abstract 1
- GMEONFUTDYJSNV-UHFFFAOYSA-N Ethyl levulinate Chemical compound CCOC(=O)CCC(C)=O GMEONFUTDYJSNV-UHFFFAOYSA-N 0.000 description 39
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UAGJVSRUFNSIHR-UHFFFAOYSA-N Methyl levulinate Chemical compound COC(=O)CCC(C)=O UAGJVSRUFNSIHR-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- ISBWNEKJSSLXOD-UHFFFAOYSA-N Butyl levulinate Chemical compound CCCCOC(=O)CCC(C)=O ISBWNEKJSSLXOD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 238000010792 warming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000012830 cancer therapeutic Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a zirconium dodecyl benzene sulfonate catalyst and application thereof in furfuryl alcohol alcoholysis reaction, belonging to the technical field of biomass catalytic conversion. The catalyst prepared by the invention has simple synthesis steps, the used raw materials are cheap and easy to obtain, and the obtained catalyst carries a large amount of Bronsted acid sites and Lewis acid sites and can efficiently catalyze furfuryl alcohol to be converted into different alkyl levulinates. Meanwhile, the catalyst prepared by the method disclosed by the invention is easy to separate after reaction, can be repeatedly used, and meets the requirement of green sustainable development.
Description
Technical Field
The invention relates to a zirconium dodecyl benzene sulfonate catalyst and application thereof in furfuryl alcohol alcoholysis reaction, belonging to the technical field of biomass catalytic conversion.
Background
Due to the reduction of fossil energy and the increase of energy demand, we will face a serious challenge in the future with global warming and the energy and environmental problems caused by global warming. In recent years, therefore, much research has been devoted to the search for new renewable energy sources that can be efficiently converted and utilized. From current research, biomass appears to be a good alternative to fossil energy sources, and because it is cheap, abundant in raw materials and readily available, the conversion of lignocellulosic biomass to specialty chemical products, including biofuels, has attracted widespread attention globally.
Among the various high value organic chemicals derived from biomass, alkyl levulinates are a series of short chain compounds and biomass platform chemicals, mainly including methyl, ethyl, isopropyl and n-butyl levulinates with ester and carbonyl groups. Alkyl levulinates have many applications in industry, including diesel fuels, resins, cancer therapeutics, herbicides, fragrances, and the like. The alkyl levulinate, which has functional groups such as an ester group and a carbonyl group, can be converted into various high value-added chemicals by reactions such as substitution, addition, condensation, and hydrolysis.
There are three major routes to produce alkyl levulinates today: (1) synthesized from levulinate; (2) direct alcoholysis of biomass; (3) and (3) carrying out alcoholysis on furfuryl alcohol. Among the catalysts generally used for catalyzing the reaction of converting furfuryl alcohol into alkyl levulinate are ion exchange resins, ionic liquids, supported heteropolyacids, metal oxides, organic-inorganic hybrid solid acids and catalysts using various zeolites as raw materials. For example, songdian jade and the like synthesize a series of aryl sulfonic acid functionalized hollow mesoporous carbon sphere catalysts, the yield of ethyl levulinate of the catalysts under the optimal reaction conditions is about 80%, but the defects of complicated catalyst preparation exist at the same time; ZahraMohammadbagheri and the like synthesize a series of modified dendritic fiber nano-silica catalysts, the yield of n-hexyl levulinate of the catalysts under the optimal reaction conditions is about 93 percent, but the defects of complicated catalyst preparation exist; ShyamSunder R.Gupta et al synthesized sulfonic acid functionalized UiO-66(Hf) catalyst with isopropyl acetoacetate yield of about 88% under optimal reaction conditions, which suffered from the disadvantages of cumbersome catalyst preparation and expensive raw material metals used in the preparation process.
It can be seen that although some catalysts have been developed for the alcoholysis of furfuryl alcohol to produce alkyl levulinates, there are still some disadvantages to be overcome, such as cumbersome synthesis processes, expensive precious metal raw materials, etc. In particular, the reaction of alcoholysis of furfuryl alcohol also has disadvantages such as excessive reaction temperature, long reaction time, low selectivity and yield of the desired product.
Disclosure of Invention
[ problem ] to
Some catalysts have been developed for preparing alkyl levulinate by furfuryl alcohol alcoholysis, but the catalysts have the problems of complicated synthesis process, need of using expensive noble metal raw materials and the like. Particularly, in the furfuryl alcohol alcoholysis reaction, the disadvantages of overhigh reaction temperature, longer reaction time, lower selectivity, lower yield of target products and the like exist.
[ solution ]
In order to solve the problems, the invention selects the surfactant sodium dodecyl benzene sulfonate as a ligand for the first time, and coordinates the sulfonic group on the benzene ring with zirconium by a coprecipitation method, and the structure can provide an acid site necessary for reaction.
The invention provides a zirconium dodecyl benzene sulfonate catalyst, which takes sodium dodecyl benzene sulfonate and zirconium salt as raw materials, wherein the molar ratio of the sodium dodecyl benzene sulfonate to the zirconium salt is (0.25-1): 1.
the invention provides a method for preparing zirconium dodecyl benzene sulfonate catalyst, which comprises the following steps: and dropwise adding the zirconium salt solution into the sodium dodecyl benzene sulfonate solution, mixing and stirring for reaction, and washing and drying the mixture after the reaction is finished to obtain the catalyst zirconium dodecyl benzene sulfonate (Zr-DBS).
In one embodiment of the invention, the zirconium salt solution used in the method is ZrOCl2And (3) solution.
In one embodiment of the invention, in the method, sodium dodecyl benzene sulfonate and zirconium in the zirconium salt solution are mixed according to a molar ratio of (0.25-1): 1, mixing.
In one embodiment of the invention, the sodium dodecylbenzene sulfonate and the zirconium in the zirconium salt solution in the process are present in a molar ratio of 0.5: 1, mixing.
In one embodiment of the invention, after the zirconium salt solution and the sodium dodecyl benzene sulfonate solution are mixed, the mixture is continuously stirred for 3-6 hours at room temperature, and then is kept stand and aged for 3-6 hours.
In one embodiment of the invention, after the reaction is finished, the mixture is subjected to suction filtration under normal pressure, the filter residue is washed by deionized water for 3-5 times and ethanol for 3-5 times, and the washed filter residue is dried in a vacuum drying oven overnight to obtain the catalyst Zr-DBS.
The invention provides a method for catalyzing alcoholysis of furfuryl alcohol into alkyl levulinate, which takes zirconium dodecylbenzene sulfonate as a catalyst.
In one embodiment of the present invention, the method for catalyzing alcoholysis of furfuryl alcohol into alkyl levulinate comprises: the method comprises the following steps of (1) taking furfuryl alcohol as a substrate, taking zirconium dodecyl benzene sulfonate as a catalyst, and enabling the mass ratio of the catalyst to the furfuryl alcohol to be (0.5-2.0): 1, stirring and reacting for 1-4h at 120-160 ℃.
In one embodiment of the invention, any of the monohydric alcohols from C1 to C4 is used as the solvent in the catalytic alcoholysis of furfuryl alcohol into an alkyl levulinate.
In one embodiment of the present invention, ethanol is used as the solvent in the process for catalytic alcoholysis of furfuryl alcohol into alkyl levulinate.
In one embodiment of the present invention, the mass ratio of the catalyst to furfuryl alcohol in the process for catalyzing the alcoholysis of furfuryl alcohol into alkyl levulinate is 1: 2.
the invention provides the zirconium dodecyl benzene sulfonate catalyst, a method for preparing the catalyst and application of the method for catalyzing furfuryl alcohol to be converted into alkyl levulinate in the fields of synthetic spice, food and energy.
[ advantageous effects ]
(1) According to the invention, the surfactant sodium dodecyl benzene sulfonate and zirconium salt are adopted for the first time to prepare the catalyst Zr-DBS, and the catalyst is used for furfuryl alcohol alcoholysis to generate a biomass derivative alkyl levulinate, the raw materials of the prepared catalyst are easy to obtain and low in price, the preparation conditions are mild, the preparation efficiency is high, and the yield is 50-70%;
(2) the catalyst disclosed by the invention is simple in preparation process, is a heterogeneous catalyst, is easy to separate after reaction, and accords with the green sustainable development strategy;
(3) the reaction conditions for catalyzing the conversion of the carbonyl compound into the alcohol are mild, the reaction temperature is 393-433K, the reaction time is 1-4h, and the yield of catalyzing the conversion of the furfuryl alcohol into the alkyl levulinate is high and reaches more than 63%. For example, when furfuryl alcohol is catalyzed to prepare ethyl levulinate, the reaction is carried out for 2 hours at the temperature of 413K, and the yield of the ethyl levulinate can reach 95.27%; when the catalyst furfuryl alcohol is used for preparing methyl levulinate, the reaction is carried out for 2 hours at the temperature of 433K, and the yield of the methyl levulinate can reach 89.76%.
Drawings
FIG. 1 is the XRD spectrum of Zr-DBS (1:2) in example 2.
FIG. 2 is the SEM of Zr-DBS (1:2) in example 2.
FIG. 3 is a transmission electron micrograph of Zr-DBS (1:2) in example 2.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Determination of ethyl levulinate yield and furfuryl alcohol conversion by gas chromatography:
the gas chromatograph parameters were set as follows: the temperature of the column box is 280 ℃, the temperature of the detector is 300 ℃, the temperature of the auxiliary I is 300 ℃, and each sample injection is 0.3 mu L.
EXAMPLE 1 Synthesis of catalyst zirconium dodecylbenzenesulfonate (Zr-DBS)
The Zr-DBS catalyst is synthesized by the following steps:
0.652g of zirconium oxychloride and 0.396g of sodium dodecyl benzene sulfonate are taken and added with water to respectively prepare the mixture with the concentration of 0.08mol L-1And the concentration of the zirconium oxychloride solution is 0.04mol L-1The sodium dodecyl benzene sulfonate solution is prepared by mixing a sodium dodecyl benzene sulfonate solution and a zirconium oxychloride solution according to the molar ratio of 1:1, 1:2, 1:3 and 1:4 respectively, continuously stirring the mixture at room temperature for 5 hours, standing and aging for 5 hours, performing suction filtration on the mixture under normal pressure after stirring, washing the filter residue with deionized water for 5 times, washing the filter residue with ethanol for 5 times, and drying the washed filter residue in a vacuum drying oven overnight to obtain the catalyst Zr-DBS (1:1) yield of 53.67%, the Zr-DBS (1:2) yield of 68.92%, the Zr-DBS (1:3) yield of 60.34% and the Zr-DBS (1:4) yield of 62.32% respectively.
m (vacuum drying to obtain catalyst): the quality of the catalyst obtained after vacuum drying;
m (sodium dodecylbenzenesulfonate + zirconium oxychloride): the mass sum of the raw materials of sodium dodecyl benzene sulfonate and zirconium oxychloride used for preparing the catalyst.
Example 2
(1) 0.1g of furfuryl alcohol, 200mg of the catalyst Zr-DBS (1:2) prepared in example 1 was weighed into a reaction vessel containing 10mL of ethanol;
(2) respectively placing the reactors in an oil bath kettle at 140 ℃ for stirring reaction for 2h and 3h, after the reaction is finished and cooled, taking 0.3 mu L of reacted solution, and measuring the yield of ethyl levulinate and the conversion rate of furfuryl alcohol by using a gas chromatograph, wherein the conversion rate of furfuryl alcohol is 97.82% and the yield of ethyl levulinate is 92.17% after stirring reaction for 2h in the oil bath kettle at 140 ℃; the reaction was stirred in an oil bath at 140 ℃ for 3h to give a furfuryl alcohol conversion of 99.9% and an ethyl levulinate yield of 93.46%.
XRD test and scanning electron micrograph of the Zr-DBS catalyst (1:2) used in the present example were taken.
FIG. 1 is the XRD spectrum of Zr-DBS (1:2) in example 2. FIG. 2 is the SEM of Zr-DBS (1:2) in example 2. FIG. 3 is a transmission electron micrograph of Zr-DBS (1:2) in example 2. It can be seen from fig. 1 that Zr-DBS is an amorphous, non-crystalline structure, and from fig. 2 and 3 it can be seen that the catalyst is porous and has no uniform shape, many voids exist between particles, and the particles are nano-sized.
Example 3
(1) 0.1g of furfuryl alcohol, 200mg of the catalyst Zr-DBS (1:2) prepared in example 1 was weighed into a reaction vessel containing 10mL of ethanol;
(2) respectively placing the reactors in an oil bath kettle at 150 ℃ to be stirred and react for 2h and 3h, after the reaction is finished and cooled, taking 0.3 mu L of reacted solution to measure the yield of ethyl levulinate and the conversion rate of furfuryl alcohol by using a gas chromatograph, wherein the conversion rate of furfuryl alcohol is 98.83 percent and the yield of ethyl levulinate is 95.27 percent after stirring and reacting for 2h in the oil bath kettle at 150 ℃; the reaction was stirred in an oil bath at 150 ℃ for 3h to give a furfuryl alcohol conversion of 99.9% and an ethyl levulinate yield of 95.3%.
Example 4
(1) 0.1g of furfuryl alcohol, 200mg of the catalyst Zr-DBS (1:2) prepared in example 1 was weighed into a reaction vessel containing 10mL of ethanol;
(2) respectively placing the reactors in an oil bath kettle at 160 ℃ for stirring reaction for 3h and 4h, after the reaction is finished and cooled, taking 0.3 mu L of reacted solution, and measuring the yield of ethyl levulinate and the conversion rate of furfuryl alcohol by using a gas chromatograph, wherein the conversion rate of furfuryl alcohol is 99.9% and the yield of ethyl levulinate is 97.9% after stirring reaction for 3h in the oil bath kettle at 160 ℃; the reaction was stirred in an oil bath at 160 ℃ for 4h to give a furfuryl alcohol conversion of 99.9% and an ethyl levulinate yield of 99.37%.
Example 5
(1) 0.1g of furfuryl alcohol, 200mg of the catalyst Zr-DBS (1:2) prepared in example 1 was weighed into a reaction vessel containing 10mL of ethanol;
(2) placing the reactor in an oil bath kettle at 120 ℃ for stirring reaction for 2h and 3h, after the reaction is finished and cooled, taking 0.3 mu L of solution after the reaction, measuring the yield of ethyl levulinate and the conversion rate of furfuryl alcohol by using a gas chromatograph, and stirring the solution in the oil bath kettle at 120 ℃ for reaction for 2h to obtain the conversion rate of furfuryl alcohol of 67.38% and the yield of ethyl levulinate of 60.6%; the reaction was stirred in an oil bath at 120 ℃ for 3h to give a furfuryl alcohol conversion of 83.34% and an ethyl levulinate yield of 78.59%.
Example 6
(1) 0.1g of furfuryl alcohol, 200mg of the catalyst Zr-DBS (1:2) prepared in example 1 was weighed into a reaction vessel containing 10mL of ethanol;
(2) placing the reactor in an oil bath kettle at 130 ℃ for stirring and reacting for 1h, 2h and 3h, after the reaction is finished and cooled, taking 0.3 mu L of solution after the reaction, measuring the yield of ethyl levulinate and the conversion rate of furfuryl alcohol by using a gas chromatograph, and stirring and reacting for 1h in the oil bath kettle at 130 ℃ to obtain the conversion rate of the furfuryl alcohol of 82.23% and the yield of the ethyl levulinate of 74.74%; stirring and reacting for 2h in an oil bath kettle at 130 ℃ to obtain the furfuryl alcohol with the conversion rate of 91.75 percent and the yield of ethyl levulinate of 89.5 percent; the reaction was stirred in an oil bath at 130 ℃ for 3h to give a furfuryl alcohol conversion of 94.1% and an ethyl levulinate yield of 91.31%.
Example 7
(1) 0.1g of furfuryl alcohol, 200mg of the Zr-DBS catalyst prepared in example 1 (1:2) was weighed into a reaction vessel containing 10mL of methanol;
(2) and (3) placing the reactor in an oil bath kettle at 160 ℃ for stirring and reacting for 2h, after the reaction is finished and cooled, taking 0.3 mu L of solution after the reaction, and measuring the yield of the methyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph to obtain that the conversion rate of the furfuryl alcohol is 96.2 percent and the yield of the methyl levulinate is 89.8 percent.
Example 8
(1) 0.1g of furfuryl alcohol, 200mg of the Zr-DBS catalyst prepared in example 1 (1:2) was weighed into a reaction kettle containing 10mL of isopropanol;
(2) and (3) placing the reactor in an oil bath kettle at 160 ℃ for stirring and reacting for 2h, after the reaction is finished and cooled, taking 0.3 mu L of solution after the reaction, and measuring the yield of isopropyl acetoacetate and the conversion rate of furfuryl alcohol by using a gas chromatograph to obtain that the conversion rate of furfuryl alcohol is 73.4% and the yield of isopropyl acetoacetate is 63.8%.
Example 9
(1) 0.1g of furfuryl alcohol, 200mg of the catalyst Zr-DBS (1:2) prepared in example 1 was weighed into a reaction vessel containing 10mL of n-butanol;
(2) and (3) placing the reactor in an oil bath kettle at 160 ℃ for stirring and reacting for 2h, after the reaction is finished and cooled, taking 0.3 mu L of solution after the reaction, and measuring the yield of the n-butyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph to obtain that the conversion rate of the furfuryl alcohol is 81.7 percent and the yield of the n-butyl levulinate is 80.9 percent.
Example 10
(1) 0.1g of furfuryl alcohol, 200mg of the catalysts Zr-DBS (1:1), Zr-DBS (1:2), Zr-DBS (1:3) and Zr-DBS (1:4) prepared in example 1 were weighed into a reaction kettle containing 10mL of ethanol;
(2) respectively placing the reactors in an oil bath kettle at 160 ℃ for stirring reaction for 2h, after the reaction is finished and cooled, taking 0.3 mu L of solution after the reaction, and measuring the yield of ethyl levulinate and the conversion rate of furfuryl alcohol by using a gas chromatograph, wherein the conversion rate of furfuryl alcohol is 99% and the yield of ethyl levulinate is 81.85% by using Zr-DBS (1:1) as a catalyst; the conversion rate of furfuryl alcohol obtained by taking Zr-DBS (1:2) as a catalyst is 99%, and the yield of ethyl levulinate is 97.86%; the conversion rate of furfuryl alcohol obtained by taking Zr-DBS (1:3) as a catalyst is 97.62 percent, and the yield of ethyl levulinate is 88.02 percent; the conversion of furfuryl alcohol was 97.99% and the yield of ethyl levulinate was 94.62% with Zr-DBS (1:4) as catalyst.
Example 11
(1) The solution obtained in example 3 after the reaction was centrifuged to obtain used Zr-DBS (1:2), which was washed with ethanol several times and dried in a vacuum oven at 60 ℃ for 14 hours, and 200mg of the solution was added into a reaction kettle containing 0.1g of furfuryl alcohol and 10mL of ethanol.
(2) And (3) respectively placing the reactors in an oil bath kettle at 150 ℃ to stir for reaction for 2h, cooling after the reaction is finished, and measuring the yield of the ethyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph from 0.3 mu L of reacted solution. The conversion of furfuryl alcohol was 95.67% and the yield of ethyl levulinate was 91.34%.
Example 12
(1) The solution obtained in example 11 was centrifuged to obtain Zr-DBS (1:2) which was used and washed with ethanol several times, dried in a vacuum oven at 60 ℃ for 14 hours, and then 200mg of the solution was added to a reaction vessel containing 0.1g of furfuryl alcohol and 10mL of ethanol.
(2) And (3) respectively placing the reactors in an oil bath kettle at 150 ℃ to stir for reaction for 2h, cooling after the reaction is finished, and measuring the yield of the ethyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph from 0.3 mu L of reacted solution. The conversion of furfuryl alcohol was 94.11% and the yield of ethyl levulinate was 88.24%.
Example 13
(1) The solution obtained in example 12 was centrifuged to obtain Zr-DBS (1:2) which was used and washed with ethanol several times, dried in a vacuum oven at 60 ℃ for 14 hours, and then 200mg of the solution was added to a reaction vessel containing 0.1g of furfuryl alcohol and 10mL of ethanol.
(2) And (3) respectively placing the reactors in an oil bath kettle at 150 ℃ to stir for reaction for 2h, cooling after the reaction is finished, and measuring the yield of the ethyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph from 0.3 mu L of reacted solution. The conversion of furfuryl alcohol was 92.76% and the yield of ethyl levulinate was 84.32%.
Comparative example 1
The Zr-DS catalyst is synthesized by the following steps:
0.652g of zirconium oxychloride and 0.335g of sodium dodecyl sulfate are taken and added with water to respectively prepare the mixture with the concentration of 0.08mol L-1And the concentration of the zirconium oxychloride solution is 0.04mol L-1Mixing the sodium dodecyl sulfate solution with the zirconium oxychloride solution, continuously stirring the mixture at room temperature for 5 hours, standing and aging for 5 hours, stirring, and then carrying out mixingAnd (3) carrying out suction filtration at normal pressure, washing the filter residue with deionized water for 5 times, washing the filter residue with ethanol for 5 times, and drying the washed filter residue in a vacuum drying oven overnight to obtain the catalyst Zr-DS.
Catalyzing furfuryl alcohol alcoholysis:
(1) 0.1g of furfuryl alcohol and 200mg of the catalyst Zr-DS prepared in the comparative example are weighed and added into a reaction kettle containing 10mL of ethanol;
(2) and (3) placing the reactor in an oil bath kettle at 150 ℃ for stirring and reacting for 2h, after the reaction is finished and cooled, taking 0.3 mu L of solution after the reaction, measuring the yield of the ethyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph, and stirring and reacting for 2h in the oil bath kettle at 150 ℃ to obtain the conversion rate of the furfuryl alcohol of 96.75% and the yield of the ethyl levulinate of 58.92%.
Comparative example 2
(1) 0.1g of furfural and 100mg of the catalyst Zr-DBS (1:2) prepared in example 1 were weighed and added into a reaction kettle containing 5mL of ethanol;
(2) and (3) placing the reactor in an oil bath kettle at 160 ℃ to stir for reaction for 0.5h, cooling the reaction, taking a small amount of solution after the reaction, and measuring the yield of the ethyl levulinate and the conversion rate of the furfuryl alcohol by using GC (gas chromatography), wherein the conversion rate of the furfuryl alcohol is 21.31 percent, and the yield of the ethyl levulinate is 14.64 percent.
Comparative example 3
(1) Weighing 0.1g of furfuryl alcohol and 200mg of sodium dodecyl benzene sulfonate, and adding the furfuryl alcohol and the sodium dodecyl benzene sulfonate into a reaction kettle containing 10mL of ethanol;
(2) and (3) placing the reactor in an oil bath kettle at 150 ℃ to stir for reaction for 2h, cooling the reaction, and measuring the yield of the ethyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph from 0.3 mu L of the solution after the reaction to obtain that the conversion rate of the furfuryl alcohol is 6.3% and the yield of the ethyl levulinate is 0.97%.
Comparative example 4
(1) Weighing 0.1g of furfuryl alcohol and 200mg of sodium dodecyl sulfate, and adding the furfuryl alcohol and the sodium dodecyl sulfate into a reaction kettle containing 10mL of ethanol;
(2) and (3) placing the reactor in an oil bath kettle at 150 ℃ to stir for reaction for 2h, after the reaction is cooled, taking 0.3 mu L of solution after the reaction, and measuring the yield of the ethyl levulinate and the conversion rate of the furfuryl alcohol by using a gas chromatograph to obtain that the conversion rate of the furfuryl alcohol is 10.72 percent and the yield of the ethyl levulinate is 1.63 percent.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The zirconium dodecyl benzene sulfonate catalyst is characterized in that sodium dodecyl benzene sulfonate and zirconium salt are used as raw materials, and the molar ratio of the sodium dodecyl benzene sulfonate to the zirconium salt is (0.25-1): 1.
2. a method for preparing the zirconium dodecylbenzenesulfonate catalyst of claim 1, which comprises: and dropwise adding the zirconium salt solution into the sodium dodecyl benzene sulfonate solution, mixing and stirring for reaction, and washing and drying the mixture after the reaction is finished to obtain the catalyst zirconium dodecyl benzene sulfonate.
3. The method of claim 2 wherein the solution of zirconium salt is ZrOCl2And (3) solution.
4. The method according to claim 2, wherein the molar ratio of the sodium dodecyl benzene sulfonate to the zirconium salt in the zirconium salt solution is (0.25-1): 1, mixing.
5. The method of claim 2, wherein the zirconium salt solution is mixed with the sodium dodecylbenzenesulfonate solution, the mixture is continuously stirred at room temperature for 3-6 hours, and then left to stand for aging for 3-6 hours.
6. A process for catalyzing the alcoholysis of furfuryl alcohol to alkyl levulinate comprising the step of using zirconium dodecylbenzenesulfonate of claim 1 as a catalyst.
7. The method according to claim 6, wherein furfuryl alcohol is used as a substrate, zirconium dodecylbenzene sulfonate is used as a catalyst, and the mass ratio of the catalyst to the furfuryl alcohol is (0.5-2.0): 1, stirring and reacting for 1-4h at 120-160 ℃.
8. The process of claim 6 wherein the catalytic alcoholysis of furfuryl alcohol into alkyl levulinate is carried out using any one of the monohydric alcohols from C1 to C4 as solvent.
9. The process of claim 6 wherein the process for the catalytic alcoholysis of furfuryl alcohol into an alkyl levulinate comprises ethanol as solvent.
10. Use of the zirconium dodecylbenzenesulfonate catalyst as claimed in claim 1, the process for preparing the catalyst as claimed in any one of claims 2 to 5, or the process for catalyzing the conversion of furfuryl alcohol to alkyl levulinate as claimed in any one of claims 5 to 9 in the fields of synthetic flavors, foods, and energy.
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