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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- CN103626726A CN103626726A CN201210302990.5A CN201210302990A CN103626726A CN 103626726 A CN103626726 A CN 103626726A CN 201210302990 A CN201210302990 A CN 201210302990A CN 103626726 A CN103626726 A CN 103626726A
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 52
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000243 solution Substances 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 28
- 239000002808 molecular sieve Substances 0.000 claims description 25
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 16
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 5
- 239000001433 sodium tartrate Substances 0.000 claims description 5
- 229960002167 sodium tartrate Drugs 0.000 claims description 5
- 235000011004 sodium tartrates Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 2
- 229910021536 Zeolite Inorganic materials 0.000 claims 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 2
- 239000010457 zeolite Substances 0.000 claims 2
- 229910017090 AlO 2 Inorganic materials 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000003570 air Substances 0.000 claims 1
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000003643 water by type Substances 0.000 description 30
- 238000003756 stirring Methods 0.000 description 29
- 239000002994 raw material Substances 0.000 description 20
- 239000007795 chemical reaction product Substances 0.000 description 15
- 238000004128 high performance liquid chromatography Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000006228 supernatant Substances 0.000 description 15
- 230000009466 transformation Effects 0.000 description 15
- 230000009467 reduction Effects 0.000 description 14
- 230000000153 supplemental effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000002402 hexoses Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- -1 5-HMFA Chemical class 0.000 description 1
- 241000271566 Aves Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000010268 HPLC based assay Methods 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000406668 Loxodonta cyclotis Species 0.000 description 1
- 229910018949 PtAu Inorganic materials 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000036983 biotransformation Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07D307/56—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- 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
- B01J29/12—Noble metals
- B01J29/123—X-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- 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
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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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