CN103724303A - Method for preparing 2,5-furandicarboxylic acid through catalytic oxidation - Google Patents
Method for preparing 2,5-furandicarboxylic acid through catalytic oxidation Download PDFInfo
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Abstract
The invention discloses a method for synthesizing 2,5-furandicarboxylic acid through catalytic oxidation by using 5-hydroxymethylfurfural as a raw material. 5-hydroxymethylfurfural can be oxidized by using oxygen or air as an oxidant in the presence of a catalyst prepared by loading an alkaline carrier with noble metal with high efficiency and high selectivity to synthesize 2,5-furandicarboxylic acid. A catalytic reaction is easy to operate and mild in conditions; when 5-hydroxymethylfurfural is fully converted, the selectivity of the product-2,5-furandicarboxylic acid can reach more than 99%; the catalyst is good in reusability.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of method of synthetic FDCA.
Background technology
FDCA, also referred to as furans-2,5-dicarboxylic acid, is a kind of important organic compound, can be used as starting raw material, produces biodegradable polyesters plastics, anticorrosive and fire-retardant material, energy chemical, pharmaceutical intermediate etc.According to its important value and application prospect, within 2004, USDOE proposes to be listed in 12 kinds of bio-based platform chemicals (T.Werpy, G.Petersen, Top value added chemicals from biomass volume i:results of screening for potential candidates from sugars and synthesis gas.US Department of Energy Report, 2004, Oak Ridge).FDCA has furans ring texture and two carboxyl functional groups, and this constitutional features is similar to terephthalic acid.Because terephthalic acid (PTA) is the great bulk chemical of the market requirement (PTA consumption reached 2,370 ten thousand tons in 2011) always, mainly for the preparation of polyester materials such as polyethylene terephthalates (PET).In recent years, along with the research of the synthetic FDCA of biomass route is carried out, researcher starts to pay close attention to and utilizes FDCA as monomer, synthetic biodegradable polyesters class plastics of new generation.Therefore, the novel synthesis of exploitation FDCA has significant application value and biomass sustainable use meaning.
By 5 hydroxymethyl furfural catalyzed oxidation, preparing FDCA, is a kind of biomass material route efficient, environmental protection that has.Recently, the raw material Dehydration such as Mierocrystalline cellulose, glucose that lot of documents has been reported biomass source is for 5 hydroxymethyl furfural technology (Xu Jie, Ren Qiuhe, Huang Yizheng, height enters, Ma Hong, Miao Hong, Che Penghua, a kind of saccharide compound transforms the method for preparing 5 hydroxymethyl furfural, CN201010122864.2, China, 2010), 5 hydroxymethyl furfural can be obtained from non-petrochemical materials, can become raw material and carry out derived product production.Therefore the synthetic FDCA of 5 hydroxymethyl furfural catalyzed oxidation that develops Non oil-based route has feasibility.
The synthetic FDCA of existing 5 hydroxymethyl furfural oxidation is mainly divided into metering oxidation style, homogeneous catalysis method, heterogeneous catalyst method.Metering oxidation style adopts KMnO
4, N
2o
4, HNO
3deng as oxygenant, 5 hydroxymethyl furfural is oxidized to synthetic FDCA.These oxygenants are serious to equipment corrosion, cause environmental pollution during discharge, do not have considerable application advantage (
a.m.Toshinari, K.Hirokazu, K.Takenobu and M.Hirohide, US Pat., 232815,2007;
b.l.Cottier, G.Descotes, J.Lewkowski and R.Skowronski, Pol.J.Chem., 1994,68,693-698).Homogeneous oxidizing method adopts Co (OAc)
2/ Mn (OAc)
2/ Br
-catalyst system, take acetic acid as solvent, carries out atmospheric oxidation 5 hydroxymethyl furfural, can obtain the FDCA (W.Partenheimer and V.V.Grushin, Adv.Synth.Catal., 2001,343,102-111) of 61% yield.Use Co (OAc)
2/ Zn (OAc)
2/ Br
-catalyzer, reaction easily rests on the intermediate steps such as DFF, adds trifluoroacetic acid can promote 2, the formation of 5-furandicarboxylic acid, but also only obtain 60% yield (B.Saha, S.Dutta, M.M.Abu-Omar, Catalysis Science Technology, 2012,2 (1), 79-81).Meanwhile, these homogeneous catalysis systems also exist metal-salt to separate difficult, the bromine environmental pollution shortcoming such as heavily.By contrast, heterogeneous catalyst method has environmental protection, product is easy to separation, the more high advantage of catalytic efficiency.Use the heterogeneous catalysts such as Au, Pt, Pd, first the aldehyde radical of 5 hydroxymethyl furfural is converted into carboxyl, forms 5-methylol-2-furancarboxylic acid; Hydroxyl continues to be oxidized to carboxyl subsequently, obtains FDCA.Obtain high yield FDCA and have difficulty, reaction easily rests on 5-methylol-2-furancarboxylic acid stage.Find that at present adding certain proportion NaOH can improve FDCA yield, and can fast reaction speed, avoid carboxylic acid product to poison in catalyst surface absorption.Davis is used Au/TiO
2for catalyzer, when NaOH and 5 hydroxymethyl furfural ratio are 2, at 690kPaO
2with 295K reaction 6 hours, when transforming completely, 5 hydroxymethyl furfural mainly obtains 5-methylol-2-furancarboxylic acid (selectivity 97%); When improving NaOH and 5 hydroxymethyl furfural ratio to 20 time, at 2000kPa O
2with 295K reaction 22 hours, 5 hydroxymethyl furfural transforms completely, 5-methylol-2-furancarboxylic acid, 2,5-furandicarboxylic acid selectivity is respectively 35% and 65%(S.E.Davis, B.N.Zope and R.J.Davis, Green Chem., 2012,14 (1), 143-147) this result shows to use high alkalinity can promote Au/TiO
2upper 5 hydroxymethyl furfural is oxidized to FDCA, but that shortcoming is alkali consumption is large.Pt/C and Pd/C are also applied to 5 hydroxymethyl furfural oxidation, and during transformation efficiency 100%, the selectivity of FDCA is respectively 79% and 71%.（S.E.Davis,L.R.Houk,E.C.Tamargo,A.K.Datye,R.J.Davis,Catal.Today，2011,160(1),55-60）。Changing carrier is one of important catalyst performance adjustment means, can strongly change the effect, surface properties of metal component character, metal and carrier etc., thereby improves catalytic efficiency, change products distribution.Use nano Ce O
2the Au catalyzer of load, NaOH/5-hydroxymethylfurfural mol ratio is 4,130 ° of C, under 10bar air pressure, reacts, and obtains the FDCA of 99% yield.But this catalyzer reusability is poor, at 130 ° of C, to use for the second time, activity obviously reduces.（O.Casanova,S.Iborra,A.Corma,ChemSusChem,2009,2,1138-1144）。
Compared with having been reported, this catalyzer has the following advantages: (1) this catalyzer can be realized 5 hydroxymethyl furfural efficient catalytic under mild conditions and transform, can high selectivity FDCA.(2) the invention provides and be applicable to the base catalysis agent carrier that FDCA is prepared in 5 hydroxymethyl furfural oxidation, active ingredient noble metal nano particles can be stablized by basic supports, and the unique basic sites of carrier transforms and has promoter action for hydroxyl oxidize.(3) the prepared catalyzer of the present invention has good repeat performance.Catalyzer provided by the invention and FDCA synthetic method have novelty and stronger application value.
Summary of the invention
In order to realize the direct efficient oxidation of 5 hydroxymethyl furfural, transform system 2,5-furandicarboxylic acid, need a kind of 5 hydroxymethyl furfural catalyzed oxidation that is used for of invention to prepare 2, new catalyst of 5-furandicarboxylic acid and preparation method thereof, under the effect of basic supports load heterogeneous catalyst, using oxygen or air is oxygenant, under mild conditions, 5 hydroxymethyl furfural efficiently catalyzing and oxidizing is synthesized to FDCA.
According to the present invention, the active ingredient of catalyzer is prepared as to homodisperse nanostructure, to improve activity or the catalytic performance of catalyzer.For avoiding nanostructured metal particle accumulation and growing up; by adding protective material; such as polyvinylpyrrolidone, polyoxyethylene-poly-oxypropylene polyoxyethylene block polymer, citric acid and Trisodium Citrate, polyvinyl alcohol etc.; protective material and metallics can produce interaction, thereby nanoparticle is stabilized in to certain size.
According to the present invention, the performance of catalyzed reaction is relevant with kind and the content of active ingredient in catalyzer.By adding other metal components in the active ingredient of catalyzer, for example, by two kinds in Au, Ag, Pd, Pt, Ru and above component formation nano structured alloy or nucleocapsid structure, change the electronic property of metal and utilize the synergy between metal component, to improve the catalytic capability that 5 hydroxymethyl furfural is oxidized to FDCA.The too high speed of response that improves of consumption of active ingredient, but can increase the cost of catalyzer; The too low selectivity that can reduce speed of response and affect catalyzed reaction of consumption, therefore in the present invention, the consumption range of choice of metal component is: the total loading amount of the metals such as Au, Ag, Pd, Pt, Ru is 0.1-20%, and preferably total loading amount is 0.5%-2.0%.
According to the present invention, the catalytic performance of the basic supports strong effect loaded catalyst of use.The invention provides a kind of basic supports system of with low cost, excellent performance, with MgO, Mg (OH)
2mgO-Al
2o
3or Mg
6al
2(CO
3) (OH)
164H
2the inorganic materials that O etc. have basic center is carrier, and this class carrier has basic center, and can take hydrogen step by force for hydroxyl in 5 hydroxymethyl furfural provides basic sites, thereby promotes reaction to carry out.When carrier is used with nanostructure form, can further improve the catalytic performance of active ingredient.
According to the present invention, the preparation of catalyzer adopts chemical reduction technology, metal component is reduced to and has nanostructure, finely dispersed metal or metal alloy, and typical synthetic method is as follows:
Typical case's synthetic method A: by HAuCl
4in solution, add protective material polyvinylpyrrolidone (polyvinylpyrrolidone: Au mass ratio is 2:1), with 10% sodium hydroxide solution, regulating pH value is 8 ~ 9, stirs 10 minutes.Add nano-sized magnesium hydroxide carrier, stir 2 hours.Control 80 ℃ of bath temperatures, use nitrogen protection, stir the lower reductive agent sodium citrate solution that drips.Continue to stir 2 hours, centrifugation, after abundant water washing, 40 ℃ of vacuum-dryings, obtain catalyst A u/Mg (OH)
2.
Typical case's synthetic method B: control 65 ℃ of bath temperatures, use nitrogen protection, under vigorous stirring, 5wt% sodium citrate solution is added drop-wise to HAuCl
4, RuCl
3, H
2ptCl
4mixing solutions in, stir after 1 hour, add nano-MgO-Al
2o
3carrier, then stir centrifugation after 12 hours, after abundant water washing, 100 ℃ are dried 12 hours, obtain catalyst A uRuPt/MgO-Al
2o
3.
Typical case's synthetic method C: at HAuCl
4in solution, add protective material polyvinyl alcohol (polyvinyl alcohol: Au mass ratio is 1:1), under ice bath and nitrogen protection condition, add NaBH
4solution also stirs 1 hour, adds afterwards carrier Mg
6al
2(CO
3) (OH)
164H
2o, stirs 4 hours, adds subsequently AgNO
3solution, stirs and adds NaBH after 4 hours
4solution, then continue to stir 1 hour.120 ℃ are dried 12 hours, obtain catalyst A uAg/Mg
6al
2(CO
3) (OH)
164H
2o.
Above catalyzer synthesis condition gentleness, step are simple, easy to operate.
According to the present invention, along with the carrying out of 5 hydroxymethyl furfural oxidation, FDCA constantly forms, and meeting strong adsorption, at catalyst surface, causes catalyst deactivation.Therefore, the present invention adds a certain proportion of alkali in 5 hydroxymethyl furfural raw material, comprises NaOH, KOH, Na
2cO
3deng, wherein OH
-with CO
3 2-be respectively 1 ~ 20 and 1 ~ 10 with the mol ratio of reaction raw materials 5 hydroxymethyl furfural, thereby product FDCA is existed with the form of salt.Add fast response on the one hand, improve on the other hand catalyzer work-ing life and repeat performance.
According to the present invention, for fear of using the oxidant stoichiometries such as potassium permanganate, this process choosing molecular oxygen (oxygen or air) cheap and easy to get is oxygen source, in temperature of reaction, be 30-130 ° of C, reaction pressure is to react 1 ~ 24 hour under the mild conditionss such as 0.1 ~ 3MPa, by efficient 5 hydroxymethyl furfural, highly selective catalyzed oxidation, it is FDCA product.The method provides the green method of a kind of biomass source compou nd synthesis FDCA, and catalyzer is efficient, highly selective, reusable.
Embodiment
The following example will contribute to understand the present invention, but content of the present invention is not limited to this.
Embodiment 1:
By Au/MgO(Au 0.5wt%) catalyzer, 1mmol 5 hydroxymethyl furfural, NaOH, 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.015:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 30 ° of C of temperature of reaction, add 0.3MPa oxygen, react 5 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 2:
By Ru/MgO(Ru 5%) catalyzer, 1mmol 5 hydroxymethyl furfural, NaOH and 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.015:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 5 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 3:
By Pt/MgO(Pt 2wt%) catalyzer, 2mmol 5 hydroxymethyl furfural, Na
2cO
3add stainless steel autoclave with 10 ml waters, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: Na
2cO
3=0.015:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 80 ° of C of temperature of reaction, add 0.3MPa oxygen, react 12 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 4:
By Au/Mg (OH)
2(Au1.4wt%) catalyzer, 2mmol 5 hydroxymethyl furfural, NaOH and 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 30 ° of C of temperature of reaction, add 1MPa oxygen, react 4 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 5:
By AuPdRu/Mg (OH)
2(Au1.4wt%, Pt1.4wt%) catalyzer, 5mmol 5 hydroxymethyl furfural, NaOH and 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 1MPa oxygen, react 4 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 6:
By AuPt/Mg (OH)
2(Au1.2wt%, Pt 0.2wt%) catalyzer, 2mmol 5 hydroxymethyl furfural, NaOH and 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 1MPa oxygen, react 10 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 7:
By AuPt/MgO-Al
2o
3(Au 1.5wt%, Ru 0.12wt%, Pt 0.1wt%) catalyzer, 2mmol 5 hydroxymethyl furfural, NaOH and 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:2(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 50 ° of C of temperature of reaction, add 0.4MPa oxygen, react 1 hour, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 8:
By AuRu/MgO-Al
2o
3(Au1.2wt%, Ru0.2wt%) catalyzer, 1mmol 5 hydroxymethyl furfural, NaOH and 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:2(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 50 ° of C of temperature of reaction, add 0.4MPa oxygen, react 3 hours, in reaction process, keep pressure constant.Reaction product use HPLC analyze, reaction result in Table
Embodiment 9:
By AuRu/Mg
6al
2(CO
3) (OH)
164H
2o(Au 1.2wt%, Ru 0.5wt%) catalyzer, 1mmol 5 hydroxymethyl furfural, NaOH and 10 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:2(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 50 ° of C of temperature of reaction, add 2MPa oxygen, react 24 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table one.
Embodiment 10:
By AuPt/MgO(Au 2wt%, Pt 0.5wt%) catalyzer, 0.5mmol 5 hydroxymethyl furfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:2(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
Embodiment 11:
By AuPt/MgO(Au 2wt%, Pt 0.5wt%) catalyzer, 0.5mmol 5 hydroxymethyl furfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
Embodiment 12
By AuPt/MgO(Au 2wt%, Pt 0.5wt%) catalyzer, 0.5mmol 5 hydroxymethyl furfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:10(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
Embodiment 13
By AuPd/Mg (OH)
2(Au 0.5wt%, Pd 0.5wt%) catalyzer, 0.5mmol 5 hydroxymethyl furfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.02:1:2(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
Embodiment 14
By AuPd/Mg (OH)
2(Au 0.5wt%, Pd 0.5wt%) catalyzer, 0.5mmol 5 hydroxymethyl furfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:4(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
Embodiment 15:
By AuPd/Mg (OH)
2(Au 0.5wt%, Pd 0.5wt%) catalyzer, 0.5mmol 5 hydroxymethyl furfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.01:1:10(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product use HPLC analyze, reaction result in Table
Embodiment 16:
By AuRuPt/MgO-Al
2o
3(Au0.2wt%, Ru 1wt%, Pt 1wt%) catalyzer, 1mmol5-hydroxymethylfurfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.015:1:2(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
Embodiment 17
By AuRuPt/MgO-Al
2o
3(Au0.2wt%, Ru 1wt%, Pt 1wt%) catalyzer, 1mmol5-hydroxymethylfurfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.05:1:10(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
Embodiment 18
By AuAg/Mg
6al
2(CO
3) (OH)
164H
2o(Au1.0wt%, Ag0.1wt%) catalyzer, 1mmol 5 hydroxymethyl furfural, NaOH and 5 ml waters add stainless steel autoclave, included polytetrafluoroethyllining lining, wherein metal: 5 hydroxymethyl furfural: NaOH=0.025:1:10(mol:mol:mol).Adopt automatic temperature control instrument temperature programming to 60 ° of C of temperature of reaction, add 0.3MPa oxygen, react 8 hours, in reaction process, keep pressure constant.Reaction product is used HPLC to analyze, and reaction result is in Table two.
5 hydroxymethyl furfural catalyzed oxidation result in table one different catalysts
HMF:5-hydroxymethylfurfural, HFCA:5-methylol-2-furancarboxylic acid, FDA:2,5-furandicarboxylic acid
In different catalysts, 5 hydroxymethyl furfural catalyzed oxidation result shows, different basic supports have promoter action for reaction, can make substrate Efficient Conversion.Temperature of reaction has material impact for selectivity of product: under 30 ° of C of lesser temps, react, be conducive to obtain compared with 5-methylol-2-furancarboxylic acid of highly selective; Improve temperature of reaction to 60 ° C, the selectivity of FDCA obviously improves.Therefore, choosing suitable temperature of reaction and control the reaction times, is the key of obtaining target product FDCA.
5 hydroxymethyl furfural catalyzed oxidation result under table two, different N aOH consumption
Reaction conditions: 60 ° of C, 0.3MPa O
2, 8 hours
HMF:5-hydroxymethylfurfural, HMFCA:5-methylol-2-furancarboxylic acid, FDA:2,5-furandicarboxylic acid
Above result shows, NaOH consumption is larger on the impact of 5 hydroxymethyl furfural catalyzed oxidation, and when the molar ratio of NaOH:5-hydroxymethylfurfural is 2, reaction product is the mixture of 5-methylol-2-furancarboxylic acid and FDCA; When this ratio brings up to 4 or 10, the selectivity of FDCA obviously improves.Therefore, improving NaOH consumption can promote 5 hydroxymethyl furfural catalyzed oxidation to FDCA.
Claims (9)
1. catalyzed oxidation is prepared a method for FDCA, it is characterized in that: under the effect of basic supports supported precious metal catalyst, using oxygen or air is oxygenant, by synthetic 5 hydroxymethyl furfural efficiently catalyzing and oxidizing FDCA.
2. in accordance with the method for claim 1, it is characterized in that: in this basic supports supported precious metal catalyst, catalytic active component is the plural components of one or two or more kinds composition in Au, Ag, Pd, Pt, Ru metal;
The carrier of catalyzer is MgO, Mg (OH)
2, MgO-Al
2o
3or Mg
6al
2(CO
3) (OH)
164H
2o basic material, or there is MgO, the Mg (OH) of nanostructure
2, MgO-Al
2o
3or Mg
6al
2(CO
3) (OH)
164H
2o basic material.
3. according to catalyzer claimed in claim 2, it is characterized in that: the metal total loading amount of basic supports supported precious metal catalyst is 0.1%-20.0%.
4. according to catalyzer claimed in claim 2, it is characterized in that: catalyzer adopts colloidal deposition method, immersion reduction method or the preparation of the deposition-precipitator method, and the reductive agent using in preparation process is: the chemical reagent KBH with reducing power
4, NaBH
4, formaldehyde, acetaldehyde, xitix, Trisodium Citrate, propylene glycol or ethylene glycol.
5. according to catalyzer claimed in claim 2; it is characterized in that: in catalyst preparation process; can add noble metal protective material; protective material comprises polyvinyl alcohol, polyoxyethylene glycol, polyvinylpyrrolidone, polyoxyethylene-poly-oxypropylene polyoxyethylene block polymer, and the mass ratio of protective material and metal is 0.1 ~ 200:1.
6. according to method described in claim 1, it is characterized in that: in reaction process, add and have NaOH in system, the mol ratio of NaOH and reaction raw materials 5 hydroxymethyl furfural is 1 ~ 20.
7. according to method described in claim 1, it is characterized in that: catalytic conversion process is that reaction pressure is 0.1MPa ~ 3MPa take air or molecular oxygen as oxygen source.
8. according to method described in claim 1, it is characterized in that: mild condition, temperature of reaction is 30 ~ 130 ° of C, the reaction times is 1 ~ 24 hour.
9. according to method described in claim 1, it is characterized in that: reaction process is carried out in water, in system, the concentration of reaction raw materials 5 hydroxymethyl furfural is 1% ~ 25%.
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