CN104628682A - Method for preparing alkoxymethyl furfural by catalyzing 5-hydroxymethylfurfural - Google Patents
Method for preparing alkoxymethyl furfural by catalyzing 5-hydroxymethylfurfural Download PDFInfo
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- CN104628682A CN104628682A CN201510084722.4A CN201510084722A CN104628682A CN 104628682 A CN104628682 A CN 104628682A CN 201510084722 A CN201510084722 A CN 201510084722A CN 104628682 A CN104628682 A CN 104628682A
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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
- 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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- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
Abstract
The invention relates to a method for preparing alkoxymethyl furfural by catalyzing 5-hydroxymethylfurfural. Etherification reaction is performed on 5-hydroxymethylfurfural (5-HMF) and tert butyl alcohol in the presence of a protic acid catalyst, and the technical key points are as follows: the protic acid catalyst is a functional graphene catalyst; and the functional graphene catalyst takes graphene as a carrier, and an acidic organic functional group with catalytic activity is connected on graphene. A benzene sulfonic acid functional group is chemically grafted to the surface of graphene to prepare the functional graphene catalyst, not only the advantage of the sulfonic acid functional group can be realized, but also the adverse factors of homogeneous catalytic reaction of p-methyl benzene sulfonic acid can be avoided, thereby providing a new chance for catalyzing the etherification reaction of 5-HMF and tert butyl alcohol. The reaction has the advantages of high reaction activity and high product yield, and toluene and other organic solvents do not need to be used for reaction.
Description
Technical field
The present invention relates to chemical field, particularly relating to a kind of is the fuel of main raw material composition or the preparation method of fuel dope based on biomass platform chemicals, specifically a kind of method being prepared alkoxymethylfurfuralethers ethers by catalysis 5 hydroxymethyl furfural (hereinafter referred to as 5-HMF) and the etherification reaction of fatty alcohol.The invention still further relates to a kind of preparation method of the functionalization graphene catalyzer for etherification reaction.
Background technology
The non-renewable people of impelling of fossil resource pay close attention to biomass energy.5-HMF is a kind of renewable industrial raw material, can produce in a large number from glucose or fructose dehydration reaction.Glucose is the main component of plant, and be also cellulosic structural unit, can obtain glucose by hydrocellulose, namely further dehydration obtains 5-HMF; Also glucose isomerization can be become fructose, then obtain 5-HMF by fructose dehydration.The etherification product of 5-HMF and fatty alcohol has the physico-chemical property being suitable as fuel oil additive, etherification product (5-ethyl oxygen ylmethyl furfural) as 5-HMF and ethanol can be used in diesel oil and biofuel, to improve the low-temperature fluidity (cloud point and toughness) of fuel oil and to improve cetane value.But, in prior art, still lack a kind of catalyzer for efficient etherification reaction.
In prior art, the preparation method of alkoxymethylfurfural compounds, if application publication number is the application for a patent for invention of CN102260229A, disclose " a kind of method preparing 5 hydroxymethyl furfural and 5-alkoxymethylfurfural ", the method with the biomass containing lignocellulose for raw material, at ZnBr
2or/and in inorganic acid solution, ZSM-5 zeolite molecular sieve, Beta zeolite molecular sieve or Zeo-karb is adopted to be catalyzer, make derived products 5-HMF and methyl alcohol, ethanol or the isopropanol reaction of biomass, generate alkoxymethylfurfural compounds, as 5-alkoxymethylfurfuralethers ethers.
If application publication number is the application for a patent for invention of CN103842349A, disclose " one in presence of organic solvent, spent ion exchange resin is made to produce the method for 5-hydroxymethyl-furfural or its alkyl ether derivative ", glucose is changed into fructose by the method under anion exchange resin catalyzed, fructose changes into 5-hydroxymethyl-furfural (i.e. 5 hydroxymethyl furfural under the catalysis of Zeo-karb afterwards, 5-HMF), 5-HMF further with ethanol, Virahol or propyl carbinol generation etherification reaction, generate alkyl etherified product, as 5-alkoxy methyl-2 furan carboxyaldehyde (AMF).Above-mentioned two kinds of methods only disclose straight chain and the etherification reaction with simple branched-chain alcoho and 5-HMF, and prove through test, above-mentioned reaction all cannot be used for the efficient etherification reaction of the trimethyl carbinol and 5-HMF.
Eric R.Sacia, Deng, in <conversion to diesel via the etherification of furanyl alcohols catalyzed by Amberlyst-15> (Journal ofCatalysis 313 (2014) 70 – 79), adopt Amberlyst-15 resin catalyst to make 5-HMF and ethanol, propyl alcohol, the reaction of Virahol or propyl carbinol, find that the active order from high to low of the etherification reaction of this several alcohol is ethanol > propyl alcohol > propyl carbinol > Virahol, namely the reactive behavior that the ratio that alkyl carbon number is many is low is low, side chain is lower than direct-connected reactive behavior, the etherification reaction of the trimethyl carbinol is almost difficult to carry out.
Eero Salminen etc., in <Etherification of5-Hydroxymethylfurfural to a Biodiesel Component Over Ionic Liquid Modified Zeolites> (Top Catal (2013) 56:765-769), disclose the H-Beta zeolite adopting acidic ionic liquid modifies is catalyzer, have studied the etherification reaction of HMF and the trimethyl carbinol.Running off from Beta carrier to slow down the ionic liquid supported, reacting and carrying out in a large amount of toluene solvants, obtain t-butoxymethyl furfural (tBMF) with optimal conditions, but its yield is only 35%, and employs not green toluene solvant.In sum, adopt the method for prior art to prepare alkoxymethylfurfural and there is suitable difficulty.
Summary of the invention
The object of this invention is to provide a kind of adopt heterogeneous catalytic reaction have that reactive behavior is high, the preparation method of the alkoxymethylfurfural of the gentle good stability of reaction conditions.This catalysis 5 hydroxymethyl furfural prepares the method for alkoxymethylfurfural, and it carries out etherification reaction by 5 hydroxymethyl furfural and the trimethyl carbinol under bronsted acid catalyst exists, and its technical essential is: described bronsted acid catalyst is functionalization graphene catalyzer; Functionalization graphene catalyzer is carrier with Graphene, and Graphene connects the acid organo-functional group with catalytic activity.
This acid organo-functional group is preferably Phenylsulfonic acid base.
Method of the present invention can be carried out under any pressure, and in view of the multiple factors of cost and reaction efficiency is considered, the reaction pressure of preferred etherification reaction is 0.1MPa ~ 2MPa; Can determine that its temperature of reaction is 60 ~ 130 DEG C by test; The amount of the alcohol used in the process of preparation HMF ether is preferably at least equal with the mole number of furfural, but consumption is far more than this lower value usually.The mol ratio of 5 hydroxymethyl furfural and the trimethyl carbinol is 1:1 ~ 1:1000.
For ensureing reaction effect, as the Graphene of carrier, after its preparation method can adopt oxidation graft process, in conjunction with ultrasonic separation or dilatometry, crystalline flake graphite is prepared into graphene oxide, then graphene oxide is obtained through reduction reaction.
Present invention also offers a kind of preparation method of functionalization graphene catalyzer, the diazonium compound of Graphene and the acid organo-functional group containing catalytic activity is disperseed in ethanol, the mass ratio of Graphene and diazonium compound is 1:10 ~ 90, the amount ratio of diazonium compound and ethanol is 1g:10 ~ 15ml, Keep agitation in the ice-water bath of 0 ~ 5 DEG C, add 50wt% Hypophosporous Acid, 50 solution to react, the amount ratio of diazonium compound and Hypophosporous Acid, 50 solution is 1g:20 ~ 30ml, reaction product is filtered successively, after dilute hydrochloric acid solution is washed and is washed to neutrality, lyophilize and get final product.
The introducing of the acid activity position of functionalization graphene catalyzer adopts chemical grafting, and preparation principle is as follows: on Graphene, key connects the C atom of-H functional group and the-Ar-SO of diazonium compound
3the grafting of H functional group, the diazonium compound be about to containing sulfonic group active sites is dissolved in the mixing solutions of deionized water and ethanol, and by a certain amount of graphene dispersion in this deionized water, low temperature temperature controlled water baths is within the scope of 0 ~ 5 DEG C, add Hypophosporous Acid, 50, react.Reacted product after salt pickling and washing, then through lyophilize, just obtains functionalization graphene catalyzer.Reaction equation can be expressed as: SO
3h-Ar-N=N
+cl
-+ H
+-C
-(Graphene) → SO
3h-Ar-C (Graphene)+N
2+ HCl 1.
Reaction equation 1. in, the relative usage of each component is respectively:
The consumption of diazonium compound: every gram of Graphene needs 10g ~ 90g diazonium compound;
The consumption of ethanol: every grammes per square metre nitrogen compound needs 10ml ~ 15ml ethanol;
The consumption of Hypophosporous Acid, 50: every grammes per square metre nitrogen compound needs the Hypophosporous Acid, 50 of 20ml ~ 30ml 50wt%.
As preferably, described diazonium compound is selected from diazobenzene sulfonic acid.
In prior art, the modifies Beta molecular sieve of acidic ionic liquid reacts 5-HMF and the trimethyl carbinol and has certain catalytic activity, but must carry out in a large amount of toluene solutions.And Graphene presents two dimensional surface sheet structure, sterically hindered little, open space can be provided for macromolecular reaction.With regard to the prior art of catalyzer aspect, as c-based nanomaterial of new generation, Graphene has attracted the interest of large quantities of researcher once coming out.Pure Graphene (Pristine Graphene) is sp
2two dimension (2D) crystal that hydbridized carbon atoms forms with six-ring.And adopting the Graphene that natural flake graphite chemical separation is made, its surface, containing a large amount of oxygen-containing functional group, is called as graphene oxide or graphene oxide (Graphene Oxide).Graphene oxide generates redox graphene (Reduced Graphene Oxide) after reduction.The C-C bond of Graphene is very firm, has 2630m
2the bigger serface of/g, physical strength is high, stable chemical performance.Basal plane and the edge section of the Graphene produced after graphene oxide reduction are sp
3hydbridized carbon atoms stores hydrogen bond, therefore has the ability of carrying out chemical reaction with other organic molecules, can be synthesized the graphen catalyst of functionalization by surface chemical modification.Sulfonic acid functional group shows good catalyst activity in acid catalyzed reaction.By Phenylsulfonic acid functional group chemical grafting to graphenic surface, prepare functionalization graphene catalyzer, both the advantage of sulfonic acid functional group can have been played, the unfavorable factor to first (base) Phenylsulfonic acid homogeneous catalytic reaction can be avoided again, for the etherification reaction of catalysis 5-HMF and the trimethyl carbinol provides new opportunity.This reaction has the advantage that reactive behavior is high, product yield is high, and without the need to adopting the organic solvents such as toluene directly to react.
Embodiment
Content of the present invention is described in detail below by way of specific embodiment.
One, the preparation of catalyzer
1. Graphene
The carrier of functionalization graphene catalyzer adopts Graphene, and chemical method can be adopted to prepare, and as crystalline flake graphite is prepared into graphene oxide in conjunction with ultrasonic separation or dilatometry by oxidation graft process, then graphene oxide is prepared into Graphene through certain method of reducing.Detailed synthetic method is see N.I.Kovtyukhova etc., at <Layer-by-layer assembly of ultrathin composite films from μm of-sized graphite oxide sheets and polycations> (Chem.Mater., 1999,11,771 – 778) in the method that adopts.Certainly, also commercially available Graphene can directly be adopted.
2. sulfonated graphene
Hydrogen bond containing many suspensions on the basal plane of Graphene and edge, can in-H active sites other organo-functional groups of grafting.The preparation method of the graphen catalyst of proton acid type is described as exemplary embodiments below by way of the preparation process of " sulfonated graphene catalyzer ", and the preparation of this catalyzer can adopt chemical grafting to prepare, and concrete steps are as follows:
(1) dispersion of Graphene: get in the ethanol/water solution of 0.3g Graphene and 150ml 50wt%, adds in the beaker of 200ml, at room temperature 50Hz ultrasonic disperse 0.5h.
(2) grafting reaction: the 1000ml beaker that 150ml 50wt% Hypophosporous Acid, 50 is housed is placed in ice bath, in control beaker, solution temperature is at 2 ~ 5 DEG C, then by 4g (2.17*10
-2mol) to diazo Phenylsulfonic acid (M=184) (, diazonium product is made by Sulphanilic Acid, detailed preparation process is asked for an interview " Experiment of Organic Chemistry " (second edition), Lanzhou University, Fudan University, Wang Qinglian writes, P203) beaker of capacity 1000ml is put into, then the graphene suspension that step (1) is obtained is added in beaker, under 300r/min after stirring reaction 40min, add the Hypophosporous Acid, 50 of 150ml 50wt% again, stirring reaction 2h under continuation ice bath.
(3) aftertreatment: by the product filtering separation of step (2), obtain the Graphene filter cake that grafting is modified, use the hydrochloric acid soln washing leaching cake of the 1M of 200ml afterwards, extremely neutral with deionized water wash again, the dry 24h of vacuum freeze drier is put into after filter cake is freezing, obtain fluffy functionalization graphene catalyzer, i.e. " sulfonated graphene catalyzer ".
Two, etherification reaction experimental implementation explanation
Preparation " tertiary butyl oxygen ylmethyl furfural ether " process below by way of the interval etherification reaction of sulfonated graphene catalyst 5-HMF and the trimethyl carbinol illustrates the preparation method of alkoxymethylfurfural as exemplary embodiments, and concrete steps are as follows:
(1) 100mg (8*10 is got
-4mol) 5-HMF (M=126) joins in reactor, adds 308mg (4*10 wherein
-3mol) the trimethyl carbinol (M=74), then 5mg sulfonated graphene is added in reactor, tighten reactor and inspection units resistance to air loss, reacting by heating still, make its temperature-stable start timing 100 DEG C time, carry out etherification reaction, reaction times 2h.
(2), after reaction terminates, liquid product is collected, with its composition of gas chromatographic analysis.Chromatographiccondition: hydrogen flame detector (FID), take hydrogen as carrier gas, marker method, diethylene glycol dimethyl ether is as internal standard substance.
Molar weight/the reaction of the 5-HMF that 5-HMF transformation efficiency (%)=conversion is fallen drops into molar weight × 100% of 5-HMF
TBMF yield (%)=(generating the 5-HMF of the 5-HMF/ reaction input that tBMF consumes) × 100%
TBMF selectivity (%)=generation tBMF consume 5-HMF molar weight × 100% of 5-HMF that falls of molar weight/conversion
The conditions such as other reaction meeting transformationreation time, temperature of reaction, catalyst levelss, specific experiment parameter asks for an interview table 1.
Three, result gathers
It is 100mg that table 1 is 5-HMF charging capacity, the experimental result when charging capacity of the trimethyl carbinol is 308mg.
The corresponding experimental result of table 1 transformationreation condition
Note: embodiment 1 ~ 5 is the reaction result under differential responses temperature condition, embodiment 5 ~ 8 is the reaction result under different catalysts input amount condition, and embodiment 3,9,10 is the reaction result under differential responses time conditions.
It should be noted that, embodiment 1 ~ 10 fills still all at ambient pressure, and reacts under the pressure of self-generating after the heating, and those of ordinary skill in the art can know, and suitably pours rare gas element raising reaction pressure and contributes to improving speed of response.But for this reaction, actual effect is also not obvious, but cost significantly improves, and is unfavorable for increasing economic efficiency.
The result in <Etherification of5-Hydroxymethylfurfural to a Biodiesel Component Over Ionic Liquid Modified Zeolites> (Top Catal (2013) 56:765 – 769) such as the test-results of embodiment in table 11 ~ 8 and Eero Salminen is compared known: sulfonated graphene catalyzer is when the reaction of catalysis 5-HMF and the trimethyl carbinol, there is reactive behavior high, the features such as selectivity height and catalyst levels lack, and reaction does not need toluene solvant, there is obvious advantage.
Claims (6)
1. catalysis 5 hydroxymethyl furfural prepares a method for alkoxymethylfurfural, and it carries out etherification reaction by 5 hydroxymethyl furfural and the trimethyl carbinol under bronsted acid catalyst exists, and it is characterized in that: described bronsted acid catalyst is functionalization graphene catalyzer; Functionalization graphene catalyzer is carrier with Graphene, and Graphene connects the acid organo-functional group with catalytic activity.
2. catalysis 5 hydroxymethyl furfural prepares the method for alkoxymethylfurfural according to claim 1, it is characterized in that: described acid organo-functional group is sulfonic group.
3. catalysis 5 hydroxymethyl furfural prepares the method for alkoxymethylfurfural according to claim 1, it is characterized in that: the temperature of reaction of described etherification reaction is 60 ~ 130 DEG C, and the mol ratio of 5 hydroxymethyl furfural and the trimethyl carbinol is 1:1 ~ 1:1000.
4. catalysis 5 hydroxymethyl furfural prepares the method for alkoxymethylfurfural according to claim 1, it is characterized in that: after the described Graphene being used as carrier adopts oxidation graft process, in conjunction with ultrasonic separation or dilatometry, crystalline flake graphite is prepared into graphene oxide, then graphene oxide is obtained through reduction reaction.
5. the preparation method of a functionalization graphene catalyzer, the diazonium compound of Graphene and the acid organo-functional group containing catalytic activity is disperseed in ethanol, the mass ratio of Graphene and diazonium compound is 1:10 ~ 90, the amount ratio of diazonium compound and ethanol is 1g:10 ~ 15ml, Keep agitation in the ice-water bath of 0 ~ 5 DEG C, add 50wt% Hypophosporous Acid, 50 solution to react, the amount ratio of diazonium compound and Hypophosporous Acid, 50 solution is 1g:20 ~ 30ml, reaction product carries out filtering successively, dilute hydrochloric acid solution is washed and after being washed to neutrality, lyophilize and get final product.
6. the preparation method of functionalization graphene catalyzer according to claim 5, is characterized in that: described diazonium compound is selected from diazobenzene sulfonic acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105618133A (en) * | 2015-12-23 | 2016-06-01 | 北京林业大学 | Magnetic glucose-based solid acid catalyst as well as preparation method and application thereof |
| CN111495419A (en) * | 2019-01-31 | 2020-08-07 | 中国科学院宁波材料技术与工程研究所 | Metal-loaded hierarchical-pore ZSM-5 molecular sieve, and preparation method and application thereof |
| CN111589468A (en) * | 2019-02-21 | 2020-08-28 | 中国科学院宁波材料技术与工程研究所 | Bifunctional catalyst, preparation method and application of bifunctional catalyst in one-step method for synthesizing 2, 5-furan dialkyl ether by 5-hydroxymethylfurfural |
| CN113023922A (en) * | 2021-03-11 | 2021-06-25 | 金为环保科技(常州)有限公司 | Treatment method and application of cleaning waste liquid of positive pole homogenizing equipment |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618133A (en) * | 2015-12-23 | 2016-06-01 | 北京林业大学 | Magnetic glucose-based solid acid catalyst as well as preparation method and application thereof |
| CN105618133B (en) * | 2015-12-23 | 2018-01-09 | 北京林业大学 | Magnetic glucosyl group solid acid catalyst and its preparation method and application |
| CN111495419A (en) * | 2019-01-31 | 2020-08-07 | 中国科学院宁波材料技术与工程研究所 | Metal-loaded hierarchical-pore ZSM-5 molecular sieve, and preparation method and application thereof |
| CN111495419B (en) * | 2019-01-31 | 2023-12-01 | 中国科学院宁波材料技术与工程研究所 | Metal-supported hierarchical pore ZSM-5 molecular sieve and preparation method and application thereof |
| CN111589468A (en) * | 2019-02-21 | 2020-08-28 | 中国科学院宁波材料技术与工程研究所 | Bifunctional catalyst, preparation method and application of bifunctional catalyst in one-step method for synthesizing 2, 5-furan dialkyl ether by 5-hydroxymethylfurfural |
| CN111589468B (en) * | 2019-02-21 | 2023-10-20 | 中国科学院宁波材料技术与工程研究所 | Difunctional catalyst, preparation and one-step method for synthesizing 2, 5-furan dialkyl ether by using 5-hydroxymethylfurfural |
| CN113023922A (en) * | 2021-03-11 | 2021-06-25 | 金为环保科技(常州)有限公司 | Treatment method and application of cleaning waste liquid of positive pole homogenizing equipment |
| CN113023922B (en) * | 2021-03-11 | 2022-11-15 | 金为环保科技(常州)有限公司 | Treatment method and application of cleaning waste liquid of positive pole homogenizing equipment |
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