CN103626726A - Preparation method of 5-hydroxymethyl furoic acid and 2,5-furandicarboxylic acid - Google Patents
Preparation method of 5-hydroxymethyl furoic acid and 2,5-furandicarboxylic acid Download PDFInfo
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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
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
The invention discloses a preparation method of 5-hydroxymethyl furoic acid and 2,5-furandicarboxylic acid by selective oxidation of 5-hydroxymethylfurfural. The method comprises the following steps: taking a precious metal loaded acidic carrier as the catalyst, under mild conditions (temperature is in a range of 25 to 100 DEG C, and the oxygen pressure is in a range of 0.1 to 3.0 MPa), and modulating the temperature, pressure and reaction time so as to rapidly and high-efficiently oxidize 5-hydroxymethylfurfural to generate 5-hydroxymethyl furoic acid or 2,5-furandicarboxylic acid. The conversion rate of 5-hydroxymethylfurfural can reach 100%, the selectivity of 5-hydroxymethyl furoic acid reaches 98%, and the selectivity of 2,5-furandicarboxylic acid reaches 99%. The method has the advantages of high efficiency and environment-friendliness, and the products have a big application value and a wide application prospect.
Description
Technical field
The present invention relates to chemical field, be specifically related to method and application thereof that a kind of 5 hydroxymethyl furfural catalyzed oxidation is prepared 5-HMFA and FDCA.
Background technology
Up to now, chemical hardware and software platform compound mainly obtains from petroleum resources, and along with a large amount of consumption of the Nonrenewable resources such as oil, the continuous rising of crude oil price, the chemical engineering industry cost that the oil of take is raw material will improve constantly, and to chemical engineering industry, bring white elephant.Along with being rooted in the hearts of the people of Conception of Sustainable Development, biomass are as a kind of cheap, and reserves are abundant, and the sustainable resource that can constantly regenerate, more and more receives scientist's concern.Therefore, excavating renewable biological source and prepare hardware and software platform compound, is the important channel that solves current petrochemical industry scarcity of resources and energy dilemma.
Xylogen, Mierocrystalline cellulose and hemicellulose are the chief component compositions of renewable biological source, it can be hydrolyzed into hexose (glucose and fructose) under acidic conditions, the hexose generation 5 hydroxymethyl furfural that further dewaters.5 hydroxymethyl furfural has good reactivity worth, can prepare the high added value compounds such as 5-HMFA, DFF, FDCA, levulinic acid by it.Recently, because 5 hydroxymethyl furfural technology (WO2009154566 is prepared in raw material hydrocrackings such as developing the fructose in biomass sources and glucose, US20120016141, CN201110080223.X, CN201010172717.6), 5 hydroxymethyl furfural can be obtained from non-petrochemical materials, and its expansion of originating, can be used for industrial production initial feed.
FDCA is that a kind of biomass that have application potential are carried out source compound, by USDOE, is listed in one of 12 kinds of important biomolecule based platform chemical.Its structure is similar to terephthalic acid, is considered to replace the important source material that terephthalic acid is used for manufacturing ester plastic, manufactures the bis--terephthalate's that birdss of the same feather flock together (PET) of a new generation biodegradable plastic; Its structure has five rings bifunctional feature, compares with terephthalic acid six-membered ring structure, has molecular arrangement asymmetrical type, therefore can also be for the synthesis of optics/choke specific function macromolecular material; 2,5 furandicarboxylic acids can also be as other fine chemicals, the important intermediate of medicine and agricultural chemicals.Therefore, the preparation of FDCA is considered to have the sustainable biotransformation of representational replacement oil production, has very large application prospect and potentiality.5-HMFA not only can be used as the monomer of macromolecular material, be used for synthesized degradable macromolecular material, or a kind of important medicine and pesticide intermediate, and be proved to be composition important in LIUWEI DIHUANG WAN, the effect that there is kidney tonifying, improves blood stasis and delay senility.Therefore, the novel synthesis of exploitation 5-HMFA and FDCA, is the important means of a kind of synthesising biological matter source bulk chemical and high valuable chemicals, has great application prospect and potentiality.
The main method of at present synthetic 5-HMFA and FDCA has metering oxidation style and catalytic oxidation:
1), metering oxidation style adopts potassium permanganate etc. as oxidant stoichiometry more, in the aqueous solution with 2,5-furans dicarbaldehyde is raw material, utilize metering potassium permanganate to carry out catalyzed oxidation synthetic 2,5-furandicarboxylic acid, the method stoichiometric consumption strong oxidizer, has high, the with serious pollution shortcoming of cost (US2007232815);
2), generally to adopt molecular oxygen be oxygenant to catalytic oxidation, uses the noble metal catalysts such as Au, Ag to carry out HMF catalyzed oxidation and prepare 5-HMFA and FDCA, is the most competitive and preparation method application potential.Because product 5-HMFA and FDCA have chelating properties, the active ingredient of catalyzer is produced to restraining effect, make catalyst efficiency and selectivity of product be difficult to raising.When adopting Ag
2o is catalyzer, (Na under alkaline condition
2cO
3), take 5 hydroxymethyl furfural as raw material, under 90 ° of C, react 15 hours, 5-HMFA yield reaches 75%(Bulletin de la Societe Chimique de France, and 1987,5,855-860).Adopt Au/CeO
2for catalyzer (NaOH) under alkaline condition, take 5 hydroxymethyl furfural as raw material,, under the air pressure of 10bar, 65 ~ 130 ° of C of temperature of reaction, in 8 hours reaction times, obtain FDCA yield 99%.Although the method obtains higher yields, the carrier adopting is not strong to golden nanometer particle stabilization, and catalysis inactivation occurs under reaction conditions, limits its extensive preparation and application.（ChemSusChem2009,2,1138–1144）。
The present invention, by kind and the quantity of carrier surface acid sites, coordinates active ingredient oxygenizement, has developed the catalyzed oxidation novel method of being prepared 5-HMFA and FDCA by 5 hydroxymethyl furfural selectivity.Utilization has faujusite structure molecular screen for carrier, by regulating kind and the quantity of carrier surface acid sites, strengthens the effect of catalyst component and carrier, improves catalyst efficiency and stability.Catalyzer provided by the invention has efficiently, highly selective, the advantages such as reaction conditions gentleness, and catalyst stability is good, and repeatability is high, has important using value and potentiality.
Summary of the invention
The object of the invention is, the biomass-based hardware and software platform compound 5 hydroxymethyl furfural of take is raw material, develops a kind of method that high-efficiency environment friendly is prepared 5-HMFA and FDCA.
Reaction formula is as follows:
According to content of the present invention, the active ingredient of catalysts adopts the precious metals such as Au, Pt, Pd, Ru, Ag.In order to guarantee selectivity of catalyst, the active ingredient of the present invention's design loads on carrier with single component or multi-component nanoparticle form, size of particles is even, the nanoparticle of preparing 1.0nm ~ 20.0nm size according to different preparation conditions, wherein best with the nanoparticle activity of <2.0nm.On the other hand, for the cost that improves the active of catalyzer and reduce catalyzer, the charge capacity of active ingredient is controlled between 0.5% ~ 10%, and preferably activity component load quantity is 2.0%.
According to content of the present invention, in order to improve selectivity of catalyst and controllability, reduce the generation of by product, selected and there is B acid site and L acid site simultaneously, can carry out modulation to the kind in acid site and quantity, and can form compared with the molecular sieve of the faujusite structure of strong interaction (X, Y type) as carrier with active ingredient.Described molecular sieve carrier is NaX, HX, REX, NaY, HY, REY and USY.
According to content of the present invention, in order to make the active ingredient of catalyzer bring into play efficient selective on carrier, controllably generate needed 5-HMFA and FDCA, need to carry out modulation to the acid site of carrier.When on carrier, L acid site is relatively many, reaction primary product is 5-HMFA; When on carrier, B acid site is relatively many, reaction primary product is FDCA.
According to content of the present invention, the acid site kind of described faujasite-type molecular sieve and the modulating method of quantity have:
1) modulating method of acid amount: described faujasite-type molecular sieve (NaX, HX, REX, NaY, HY, REY and USY) is stirred 1 ~ 2 hour in ammonium salt solution, whipping temp remains on 40 ° of C ~ 80 ° C, with deionized water wash, arrive solution PH=8, at high temperature calcine 4 hours, this step repeats 1 ~ 3 time, according to the number of times of exchange, acid amount is carried out to modulation;
2) calcining temperature described in step 1) is in 200 ℃, 300 ° C, 400 ℃, 500 ° C one, preferably in 200 ° of C and 300 ° of C one.Ammonium salt described in step 1) is NH
4nO
3, NH
4cl, (NH
4)
2cO
3, (NH
4)
2sO
4, (NH
4)
2hPO
4in at least one, preferred NH
4nO
3and NH
4in Cl at least one;
3) modulating method in B acid site and L acid site: the faujasite-type molecular sieve (NaX, HX, REX, NaY, HY, REY and USY) after exchanging by faujasite-type molecular sieve (NaX, HX, REX, NaY, HY, REY and USY) and in step 1) is under N2 atmosphere, adopt differing temps roasting, by the control to maturing temperature and roasting time, can sieve the relative content in upper B acid site and L acid site by Molecular regulator;
4) maturing temperature described in step 3) is at least one in 100 ° of C, 200 ℃, 300 ℃, 400 ℃, 500 ° C, preferably 400 ° of C.Roasting time described in step 3) is 1 ~ 9 hour, preferably 1 hour, 3 hours and 5 hours.
According to content of the present invention, the method for Kaolinite Preparation of Catalyst comprises the following steps:
I) according to a certain ratio the metal-salt of one or more different proportionings is made into the aqueous solution, controls 60 ° of C of bath temperature; Described metal-salt is selected from HAuCl
4, HPtCl
4, HPdCl
4in at least one or multiple;
II) molecular sieve carrier is joined to mix and blend in metal salt solution, control temperature and remain on 60 ° of C; Described molecular sieve carrier is a kind of in faujasite-type molecular sieve (NaY, HY, REY and USY), or a kind of in the faujasite-type molecular sieve (NaY, HY, REY and USY) after modulation carried out in acid site;
III) in solution, add reductive agent, make metal-salt be reduced into the nano metal particles of zero-valent state and load on carrier; Described reductive agent is one or more in trisodium citrate, xitix, sodium borohydride, POTASSIUM BOROHYDRIDE, hydrazine hydrate and sodium tartrate;
IV) catalyst precursor of preparation is repeatedly washed with deionized water, until PH=7 in washings, under atmosphere of hydrogen, 100 ° of C cure 5 hours.
Step I described in aforesaid method) and II), described molecular sieve carrier is a kind of in faujasite-type molecular sieve (NaY, HY, REY and USY), or a kind of in the faujasite-type molecular sieve (NaY, HY, REY and USY) after modulation carried out in acid site, preferably HY and REY.The mass ratio of molecular sieve carrier and active ingredient is 10 ~ 200, and charge capacity is 0.5% ~ 10%, preferably 2%.
According to content of the present invention, the method for preparing 5-HMFA and FDCA comprises the steps:
1) after being mixed with alkaline solution, 5 hydroxymethyl furfural, deionized water join in 10 milliliters of tetrafluoroethylene reactors; Described alkali is selected from LiOH, KOH, NaOH, Ca(OH)
2, CH
3oNa, CH
3at least one in OK.
2) get the catalyzer preparing and join in mixed solution, polytetrafluoro reactor is packed in autoclave, react after sealing and mix up pressure and temperature, in reaction process, need to use magnetic stirring apparatus to stir.
In the step 1) of the method for the method, described alkali is inorganic strong alkali or organic alkali, is specifically selected from LiOH, KOH, NaOH, Ca(OH)
2, CH
3oNa, CH
3at least one in OK, preferably in NaOH and KOH at least one.The consumption of alkali is 1 ~ 20 times of described 5 hydroxymethyl furfural molar mass, most preferably 4 times.The method step 2) in, described reaction gas under pressure is oxygen and air, preferably oxygen; Described reaction pressure is 0.3 ~ 3.0Mpa, most preferably 0.3Mpa.Described temperature of reaction is 20 ° of C ~ 80 ° C, most preferably 60 ° of C.1 ~ 9 hour described reaction times, most preferably 6 hours.Described reaction process remains constant temperature and pressure condition, after reaction product is centrifugal, removes supernatant liquid, uses HPLC assay products.
The invention provides and a kind ofly 5 hydroxymethyl furfural is carried out to catalyzed oxidation, the method for controlled generation 5-HMFA and FDCA.Technology and technique relatively, the catalyzer of the method exploitation can obtain two kinds of products as required, and reaction conditions is gentle, reaction efficiency and product selectivity are high, prepared by catalyzer, modification is simple to operate, stable performance, reusable, meets the aim of Green Chemistry and the requirement of product diversification.
Embodiment
The following example will contribute to understand the present invention, but content of the present invention is not limited to this.Described method if no special instructions, is ordinary method.While measuring the transformation efficiency, product 5 hydroxymethyl furfural of 5 hydroxymethyl furfural (HMF) and FDCA yield, method therefor is HPLC marker method.For clearer, subsequent embodiment is described, provide the concrete symbol abbreviation of compound used therefor in each embodiment below, specific as follows: HMF represents 5 hydroxymethyl furfural, HMFA represents 5-HMFA, and FDA represents FDCA.
Embodiment 1:
Get 1.73 grams of HAuCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of HY to stir, and adds sodium citrate solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst A u/HY.
Get 0.317 gram of HMF, 2.8 grams of KOH(20%) and 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of Au/HY(Au2wt%) be catalyzer, after temperature programming to 60 ° C, be filled with 0.3MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 98%, and reaction result is in Table one.
Embodiment 2:
Get 1.73 grams of HAuCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of HX to stir, and adds sodium borohydride solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst A u/HX.
Get 0.317 gram of HMF, 2 grams of NaOH(20%) and 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of Au/HX(Au4wt%) be catalyzer, after temperature programming to 60 ° C, be filled with 0.3MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, HMFA yield is 90%, and reaction result is in Table one.
Embodiment 3:
Get 1 gram of NaY and be dissolved in 50 grams of deionized waters, be warmed up to 60 ° of C, add 0.1 gram of NH
4cL mix and blend 2 hours, washs centrifugal solution PH=7 of arriving, and dries 4 hours the H after being exchanged under 200 ° of C
xna
1-xy.Get 1.73 grams of HAuCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of H
xna
1-xy stirs, and adds sodium citrate solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst A u/H
xna
1-xy.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, gets 0.30 gram of Au/H
xna
1-xy(Au2wt%) be catalyzer, after temperature programming to 60 ° C, be filled with 0.3MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, HMFA yield is that 39%, FDA yield is 45%, and reaction result is in Table one.
Embodiment 4:
Get 1 gram of HY under nitrogen atmosphere, 400 ° of C high-temperature roastings 5 hours, gained HY is as the carrier of catalyzer.Get 1.73 grams of HAuCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of HY to stir, and adds sodium citrate solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst A u/HY.
Get 0.317 gram of HMF, 2.8 grams of KOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of Au/HY(Au2wt%) be catalyzer, after temperature programming to 60 ° C, be filled with 0.3MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, HMFA yield is that 76%, FDA yield is 12%, and reaction result is in Table one.
Embodiment 5:
Get 1.73 grams of HPtCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds HY to stir, and adds sodium citrate solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst Pt/HY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.60 gram of Pt/HY(Pt1wt%) be catalyzer, after temperature programming to 80 ° C, be filled with 0.5MPa oxygen, react 8 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 90%, and reaction result is in Table one.
Embodiment 6:
Get 1.73 grams of HPtCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of REY to stir, and adds sodium citrate solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst Pt/REY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.60 gram of Pt/REY(Pt1wt%) be catalyzer, after temperature programming to 80 ° C, be filled with 0.5MPa oxygen, react 8 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 85%, and reaction result is in Table one.
Embodiment 7:
Get 1.73 grams of HPtCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of NaY to stir, and adds sodium citrate solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst Pt/NaY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of Pt/NaY(Pt1wt%) be catalyzer, after temperature programming to 80 ° C, be filled with 0.5MPa oxygen, react 12 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, HMFA yield is 92%, and reaction result is in Table one.
Embodiment 8:
Get 2.36 grams of HPdCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of HY to stir, and adds sodium borohydride solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst P d/HY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of Pd/HY(Pt1wt%) be catalyzer, after temperature programming to 80 ° C, be filled with 0.3MPa oxygen, react 9 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 89%, and reaction result is in Table one.
Embodiment 9:
Get 2.36 grams of HPdCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of USY to stir, and adds sodium borohydride solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst P d/USY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of Pd/USY(Pd1wt%) be catalyzer, after temperature programming to 80 ° C, be filled with 0.3MPa oxygen, react 9 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 95%, and reaction result is in Table one.
Embodiment 10:
Get 1 gram of NaY and be dissolved in 50 grams of deionized waters, be warmed up to 60 ° of C, add 0.1 gram of NH
4cL mix and blend 2 hours, washs centrifugal solution PH=7 of arriving, and dries 4 hours the H after being exchanged under 200 ° of C
xna
1-xy.Get 2.36 grams of HPdCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of H
xna
1-xy stirs, and adds sodium borohydride solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst P d/H
xna
1-xy.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, gets 0.30 gram of Pd/H
xna
1-xy(Au2wt%) be catalyzer, after temperature programming to 80 ° C, be filled with 0.3MPa oxygen, react 9 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, HMFA yield is that 52%, FDA yield is 34%, and reaction result is in Table one.
Embodiment 11:
Get 1.18 grams of grams of HPdCl
4solution (1wt%), 0.85 gram of HAuCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of HY to stir, and adds sodium borohydride solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst A uPd/HY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of AuPd/HY(Pt0.5wt%, Au0.5wt%) be catalyzer, after temperature programming to 70 ° C, be filled with 0.3MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 98%, and reaction result is in Table one.
Embodiment 12:
Get 1.18 grams of HPdCl
4solution (1wt%), 0.85 gram of HPtCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of HY to stir, and adds sodium tartrate solution reduction to stir 2 hours, and washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst Pt Pd/HY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of AuPd/HY(Pt0.5wt%, Pt0.5wt%) be catalyzer, after temperature programming to 70 ° C, be filled with 0.5MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 89%, and reaction result is in Table one
Embodiment 13:
Get 0.85 gram of HAuCl
4solution (1wt%), 0.85 gram of HPtCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of NaX to stir, add sodium tartrate solution reduction to stir 2 hours, washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst Pt Au/NaX.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of PtAu/NaX(Pt0.5wt%, Pt0.5wt%) be catalyzer, after temperature programming to 70 ° C, be filled with 0.3MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 93%, and reaction result is in Table one
Embodiment 14:
Get 0.58 gram of HAuCl
4solution (1wt%), 0.58 gram of HPtCl
4solution (1wt%), 0.79 gram of HPdCl
4solution (1wt%) joins in 50 grams of deionized waters, is heated to 60 ° of C, adds 0.3 gram of HY to stir, add sodium tartrate solution reduction to stir 2 hours, washing catalyst, to PH=7, is dried 5 hours under 100 ° of C atmosphere of hydrogen, finally makes catalyst A uPtPd/HY.
Get 0.317 gram of HMF, 2 grams of NaOH(20%), 3 ml waters add in reactor, reaction vessel is included 10 milliliters of teflon-lined autoclaves, get 0.30 gram of AuPtPd/HY(Au0.33wt%, Pt 0.33wt%, Pd0.33wt%) be catalyzer, after temperature programming to 70 ° C, be filled with 0.3MPa oxygen, react 6 hours, continuous supplemental oxygen in reaction process, guarantees to react and carries out under constant temperature and pressure.After reaction product is centrifugal, remove supernatant liquid, use HPLC to analyze.After testing, raw material HMF transformation efficiency is that 100%, FDA yield is 96%, and reaction result is in Table one.
Table one HMF catalyzed oxidation is prepared HMFA and FDA reaction result
Claims (7)
1. prepare 5-HMFA and 2 for one kind, the method of 5-furandicarboxylic acid, it is characterized in that: under gentle condition, by the regulation and control to temperature, pressure and reaction times, adopt noble metal carrier catalyst optionally by the synthetic 5-HMFA of 5 hydroxymethyl furfural efficiently catalyzing and oxidizing or FDCA;
Catalyzed reaction pressure is 0.1 ~ 3.0MPa, and temperature is 25 ~ 100 ° of C, needs to add a certain amount of alkali to promote the carrying out of reaction in reaction process, and the amount of the alkali adding and reaction substrate mol ratio are 1 ~ 20.
2. in accordance with the method for claim 1, it is characterized in that: catalyzer is loaded catalyst, its active ingredient is to take Au, Pd, Pt, Ru, Ag as main monometallic or more than two kinds blending ingredients or the more than two kinds alloy compositions of metal of metal, the gross weight charge capacity of active ingredient is 0.5 ~ 10%, and metal active constituent is the nanoparticle of 1.0nm ~ 20.0nm size.
3. according to the method described in claim 1 or 2, it is characterized in that: the carrier of catalyzer is the molecular sieve with faujusite structure, comprise X-type, Y zeolite, it consists of Na
x(SiO
2)
y(AlO
2)
zmH
2o, SiO
2: Al
2o
3mol ratio is 2-50, Na
2o content is 0.01wt%-20wt%, y/z=1 ~ 5.
4. according to catalyzer claimed in claim 3, it is characterized in that:
The preparation of catalyzer comprises the following steps:
I) by required proportioning, the metal-salt of one or more different proportionings is made into the aqueous solution, controls 30 ° of C ~ 80 ° C of bath temperature;
Described metal-salt is selected from HAuCl
4, HPtCl
4, HPdCl
4, H Ru Cl
4, H Ag Cl
4in at least one or multiple;
II) molecular sieve carrier is joined to mix and blend in metal salt solution, control temperature and remain on 30 ° of C ~ 80 ° C; Described molecular sieve carrier is that faujasite-type molecular sieve is a kind of in NaX, HX, REX, NaY, HY, REY or USY, or a kind of in faujasite-type molecular sieve NaX, HX, REX, NaY, HY, REY or the USY after modulation carried out in acid site;
III) in solution, add reductive agent, make metal-salt be reduced into the nano metal particles of zero-valent state and load on carrier;
Described reductive agent is one or more in trisodium citrate, xitix, sodium borohydride, POTASSIUM BOROHYDRIDE, hydrazine hydrate, sodium tartrate and hydrogen;
IV) catalyst precursor of preparation is washed with deionized water, until PH=7 in washings, under atmosphere of hydrogen, 80 ° of C～150 ° C cure 3 ~ 8 hours.
5. according to method described in claim 1, it is characterized in that: catalyzed reaction oxygen source is oxygen, air or hydrogen peroxide; The kind of alkali has LiOH, KOH, NaOH, Ca(OH)
2, CH
3oNa or CH
3oK, the mol ratio of added alkali and substrate is 1 ~ 10.
6. according to method described in claim 1,2 or 3, it is characterized in that:
In order to make the active ingredient of catalyzer bring into play efficient selective on carrier, controllably generate needed 5-HMFA and FDCA, need to carry out modulation to the acid site of carrier; When on carrier, L acid site is relatively many, reaction primary product is 5-HMFA; When on carrier, B acid site is relatively many, reaction primary product is FDCA;
Described faujasite-type molecular sieve comprises X-type, Y zeolite, is NaX, HX, REX, NaY, HY, REY or USY;
The acid site kind of described faujasite-type molecular sieve and the modulating method of quantity have:
1) modulating method of acid amount: described faujasite-type molecular sieve is stirred 1 ~ 2 hour in ammonium salt solution, whipping temp remains on 40 ° of C ~ 80 ° C, with deionized water wash, arrive solution PH=8, at high temperature calcine 4 hours, this step repeats 1 ~ 3 time, according to the number of times of exchange, acid amount is carried out to modulation; Calcining temperature is 200 ° of C-500 ° of C;
Described ammonium salt is NH
4nO
3, NH
4cl, (NH
4)
2cO
3, (NH
4)
2sO
4, (NH
4)
2hPO
4in at least one, preferred NH
4nO
3and NH
4in Cl at least one; The mol ratio of the ammonium salt adding and faujasite-type molecular sieve Surface acidity is 1 ~ 10;
2) modulating method in B acid site and L acid site: the faujasite-type molecular sieve after exchanging by faujasite-type molecular sieve or in step 1) is under N2 atmosphere, adopt differing temps roasting, by the control to maturing temperature and roasting time, can sieve the relative content in upper B acid site and L acid site by Molecular regulator; Described maturing temperature is 100 ° of C-500 ° of C, and roasting time is 1 ~ 9 hour.
7. according to method described in claim 1, it is characterized in that: this reaction is for catalytic oxidation, in reaction, the consumption of alkali is 1 ~ 10 times of described 5 hydroxymethyl furfural molar mass; Described reaction pressure is 0.3Mpa; Temperature of reaction is 60 ° of C; Reaction times 1-9 hour.
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