CN113117706A - Metal modified ruthenium-based catalyst and method for preparing 2, 5-furandicarboxylic acid by using same - Google Patents

Metal modified ruthenium-based catalyst and method for preparing 2, 5-furandicarboxylic acid by using same Download PDF

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CN113117706A
CN113117706A CN201911415408.4A CN201911415408A CN113117706A CN 113117706 A CN113117706 A CN 113117706A CN 201911415408 A CN201911415408 A CN 201911415408A CN 113117706 A CN113117706 A CN 113117706A
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catalyst
zirconium
zinc
preparation
ruthenium
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CN113117706B (en
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马会霞
周峰
傅杰
乔凯
张淑梅
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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

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Abstract

The invention provides a metal modified ruthenium-based catalyst and a method for preparing FDCA by using the same to catalyze MMF, wherein the preparation of the catalyst comprises the following steps: loading at least one of zirconium, iron and zinc as modified metal onto hydroxyapatite, calcining, and mixing with Ru3+The solution (2) is mixed, solid-liquid separation is carried out after adsorption is finished, and the separated solid is washed and dried to obtain the catalyst. The catalyst can be used for catalyzing 5-methoxymethyl furfural to prepare 2, 5-furandicarboxylic acid. Catalyst with Ru3+As an active component, metal oxides of zirconium, iron and/or zinc are used as modified components, and the preparation method is simple; and metals of zirconium, iron and/or zincThe introduction of the oxide well regulates the electron cloud around the ruthenium atom, generates synergistic effect with the hydroxyl of the hydroxyapatite as a carrier, promotes the activation of the side chain aldehyde group C-H of the furan ring under the mild reaction condition of lower temperature and lower pressure, and improves the Ru content3+The oxidizing ability of (a).

Description

Metal modified ruthenium-based catalyst and method for preparing 2, 5-furandicarboxylic acid by using same
Technical Field
The invention relates to a preparation technology of 2, 5-furandicarboxylic acid, in particular to a method for preparing 2, 5-furandicarboxylic acid by oxidizing 5-methoxymethylfurfural with a metal modified ruthenium-hydroxyapatite catalyst, belonging to the field of biomass resource utilization.
Background
The two ends of the 2, 5-furandicarboxylic acid (FDCA) have symmetrical carboxylic acid structures, and the FDCA can be easily polymerized with alcohols to form a polymeric material with market prospect. The material can be effectively degraded by microorganisms in nature, and is a bio-based material with the highest potential to replace petroleum-based terephthalic acid.
Currently, synthetic FDCA is obtained mostly through oxidation of 5-Hydroxymethylfurfural (HMF). CN201480051571.6 discloses a method for producing 2, 5-furandicarboxylic acid by oxidizing HMF with a noble metal supported on activated carbon as a catalyst in an acidic aqueous solution to produce FDCA, which is an effort to improve the yield of FDCA by a two-stage method of a low-temperature step and a high-temperature step, but cannot avoid the decrease in the yield of FDCA due to the production of a large amount of by-products from HMF in an acidic aqueous solution system. CN201811610011.6 discloses a method for preparing 2, 5-furandicarboxylic acid, which aims to solve the problems of low concentration and low efficiency of reaction substrates, but the reaction process involves adjusting pH with concentrated hydrochloric acid, the reaction pressure is 4.0-5.0 MPa, the reaction temperature is 90-150 ℃, and the conditions are not mild.
The existing FDCA synthesis technology has the defects of harsh reaction conditions, low FDCA liquid yield and the like.
Disclosure of Invention
In order to solve the problems that the reaction conditions for preparing 2, 5-furandicarboxylic acid by taking 5-hydroxymethylfurfural as a raw material are harsh and the yield of a product FDCA solution is low in the prior art, the invention aims to provide a metal modified ruthenium-based catalyst and a method for preparing 2, 5-furandicarboxylic acid by utilizing the same, wherein 5-methoxymethylfurfural is taken as a raw material, and the 2, 5-furandicarboxylic acid is synthesized under the catalysis of the modified catalyst, so that the method has the advantages of mild reaction conditions and high yield of the product solution.
The technical object of the first aspect of the present invention is to provide a method for preparing a metal-modified ruthenium-based catalyst, comprising the steps of:
(1) adding hydroxyapatite into soluble salt solution containing at least one of zirconium, iron and zinc, soaking, performing solid-liquid separation after soaking, washing the solid, drying and roasting;
(2) mixing the solid obtained in the step (1) with Ru3+The solution is mixed and impregnated, solid-liquid separation is carried out after the impregnation is finished, and the separated solid is washed and dried to obtain the metal modified ruthenium-based catalyst.
Further, in percentage by weight, the loading amount of zirconium, iron and/or zinc in the catalyst is 5-10% of the mass of each metal oxide, and Ru is3+The loading amount is 0.1-10%, preferably 3-7%.
Further, the soluble salt of zirconium is selected from at least one of zirconyl nitrate, zirconium acetate, zirconium chloride, zirconium n-butoxide and zirconium n-propoxide, and is preferably zirconyl nitrate; the soluble salt of iron is selected from at least one of ferric nitrate, ferric chloride and ferric sulfate, and is preferably ferric nitrate; the soluble salt of zinc is at least one selected from zinc nitrate, zinc chloride and zinc sulfate, and is preferably zinc nitrate.
Further, the dipping time in the step (1) is 0.5-24 h; the roasting temperature is 300-600 ℃, and preferably 450-550 ℃.
Further, the compound contains Ru3+The solution of (A) is selected from the group consisting of ruthenium chloride (RuCl)3) Ruthenium nitrate (RuNO (NO))3)3) Or ruthenium acetate (C)6H9O6Ru) solution.
Further, the compound contains Ru3+The solvent of the solution of (1) is selected from at least one of methanol, ethanol or water.
Further, the dipping time in the step (2) is 10 min-24 h, preferably 10 min-5 h.
Further, the drying temperature is 55-120 ℃, and the drying time is 6-12 hours.
Furthermore, the hydroxyapatite is nano hydroxyapatite, and more specifically, the particle size of the hydroxyapatite is 1-100 nm.
It is a technical object of the second aspect of the present invention to provide a metal-modified ruthenium-based catalyst prepared by the above method. The catalyst takes hydroxyapatite as a carrier and Ru exists in an ionic state3+As an active component, metal oxides of zirconium, iron and/or zinc are used as a modification component. The weight percentage of the loading amount of zirconium, iron and/or zinc in the catalyst is 5-10% of the mass of each metal oxide, and Ru is3+The loading amount is 0.1-10%, preferably 3-7%.
The technical purpose of the third aspect of the invention is to provide a preparation method of 2, 5-furandicarboxylic acid (2, 5-FDCA), wherein 5-methoxymethylfurfural (MMF) is reacted with oxygen in an aqueous solution in the presence of the metal-modified ruthenium-based catalyst to prepare the 2, 5-FDCA.
Further, MMF is reacted with a catalyst (or Ru in a catalyst)3+In mass) is mixed and reacted according to the mass ratio of 1: 0.1-5.
Furthermore, the introduction amount of oxygen in the reaction enables the initial pressure of the reaction system to reach 0.1-2 MPa.
Further, the temperature of the reaction is 70-130 ℃, and preferably 70-110 ℃; the reaction time is 12-24 h.
Compared with the prior art, the invention has the following advantages:
(1) the metal modified ruthenium-based catalyst of the invention is prepared from Ru3+As an active component, metal oxides of zirconium, iron and/or zinc are used as modified components, and the preparation method is simple; and the introduction of metal oxides of zirconium, iron and/or zinc well regulates electron cloud around ruthenium atoms, generates synergistic effect with hydroxyl of carrier hydroxyapatite, promotes the activation of furan ring side chain aldehyde group C-H under mild reaction conditions of lower temperature and lower pressure, and improves the activity of Ru3+The oxidizing ability of (a).
(2) In the preparation method of the 2, 5-furandicarboxylic acid, the raw material 5-methoxymethylfurfural exists stably in an aqueous solution system, the activity of the catalyst is good in stability and high in activity in the reaction system, and the yield of the 2, 5-furandicarboxylic acid is high;
additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The metal loading of the catalysts in the following examples and comparative examples was measured by Inductively Coupled Plasma (ICP). Qualitative and quantitative analysis of the oxidation products of MMF in the examples were uniformly detected by Agilent liquid chromatography (Agilent-1260).
Example 1
Preparation of metal modified catalyst Z1:
(1) 0.069g ZrONO3·6H2Adding O into 50mL of water, stirring vigorously for 20min, adding 0.5g of HAP with the diameter of 1-100 nm, stirring for 24h, filtering, washing and drying the solid, and roasting at 500 ℃ for 3h in a muffle furnace to obtain a white solid.
(2) 0.0388g of RuCl3.3H2And (2) adding O into 50mL of water, stirring vigorously for 10min, adding 0.5g of the white solid obtained in the step (1), soaking for 10min, filtering, washing the solid, and drying at 55 ℃ for 12h to obtain light gray solid powder, namely the catalyst Z1. The solid was ground for use in the oxidation of MMF.
Example 2
Preparation of metal modified catalyst Z2:
(1) 0.14g ZrONO3·6H2Adding O into 50mL of water, stirring vigorously for 20min, adding 0.5g of HAP with the diameter of 1-100 nm, stirring for 12h, filtering, washing and drying the solid, and roasting at 500 ℃ for 3h in a muffle furnace to obtain a white solid.
(2) Adding 0.0050g of ruthenium nitrate into 50mL of water, stirring vigorously for 10min, adding 0.5g of the white solid obtained in step (1), soaking for 1h, filtering, washing the solid, and drying at 110 ℃ for 6h to obtain gray solid powder, namely the catalyst Z2. The solid was ground for use in the oxidation of MMF.
Example 3
Preparation of metal modified catalyst Z3:
(1) 0.15g of Fe (NO)3)3·6H2Adding O into 50mL of water, stirring vigorously for 20min, adding 0.5g of HAP with the diameter of 1-100 nm, stirring for 24h, filtering, washing and drying the solid, and roasting at 500 ℃ for 3h in a muffle furnace to obtain a white solid.
(2) 0.0426g of ruthenium acetate is added into 50mL of water, the mixture is stirred vigorously for 10min, 0.5g of the white solid obtained in the step (1) is added, the white solid is soaked for 30min, the solid is filtered, the solid is washed and dried for 12h at the temperature of 55 ℃, and dark gray solid powder is obtained, namely the catalyst Z3. The solid was ground for use in the oxidation of MMF.
Example 4
Preparation of metal modified catalyst Z4:
(1) 0.1g of Zn (NO)3)2·6H2Adding O into 50mL of water, stirring vigorously for 20min, adding 0.5g of HAP with the diameter of 1-100 nm, stirring for 24h, filtering, washing and drying the solid, and roasting at 500 ℃ for 3h in a muffle furnace to obtain a white solid.
(2) 0.1471g RuCl3·3H2And (2) adding O into 50mL of water, stirring vigorously for 10min, adding 0.5g of the white solid obtained in the step (1), soaking for 2h, filtering, washing the solid, and drying at 55 ℃ for 12h to obtain gray solid powder, namely the catalyst Z4. The solid was ground for use in the oxidation of MMF.
Example 5
Preparation of metal modified catalyst Z5:
(1) 0.111g ZrONO3·6H2Adding O into 50mL of water, stirring vigorously for 20min, adding 0.5g of HAP with the diameter of 1-100 nm, stirring for 24h, filtering, washing and drying the solid, and roasting at 500 ℃ for 3h in a muffle furnace to obtain a white solid.
(2) 0.1029g RuCl3·3H2And (2) adding O into 50mL of water, stirring vigorously for 10min, adding 0.5g of the white solid obtained in the step (1), soaking for 5h, filtering, washing the solid, and drying at 55 ℃ for 12h to obtain gray solid powder, namely the catalyst Z5. The solid was ground for use in the oxidation of MMF.
Comparative example 1
0.0388g of RuCl3.3H2O into 50mL of water, vigorously stirred for 10min, added with 0.5g of HAP, soaked for 10min, filtered, the solid washed, dried at 55 ℃ for 12h to give catalyst Z6. The solid was ground for use in the oxidation of MMF.
The catalysts Z1-Z6 were tested for the mass percent of ruthenium (based on the mass of the ruthenium element) and metal oxide (based on the mass of the Zr, Fe or Zn metal oxide) using Inductively Coupled Plasma (ICP), and the results are shown in Table 1.
Table 1.
Figure DEST_PATH_IMAGE001
Evaluation of the performances of catalysts Z1-Z6 in the preparation of 2,5-FDCA by MMF reaction:
the evaluation test was carried out in a six-stage reaction vessel having a volume of 8 mL. The specific catalyst evaluation procedure was as follows: adding 20mg of 5-methoxymethylfurfural, 3mL of water and 2-100 mg of catalyst into a reaction kettle, screwing up, adding oxygen until the initial pressure is 0.1-2 MPa, sealing, putting the reaction kettle into a six-connection heating jacket, and reacting at 70-130 ℃ respectively. And (3) after 8-24 hours of reaction, immediately taking out the reaction kettle, putting the reaction kettle into cold water for cooling, after cooling is completed, opening the reaction kettle, washing the reaction kettle with a methanol aqueous solution, transferring the reaction kettle into a 50mL volumetric flask by using a dropper for constant volume, centrifuging, and filtering to a sample injection bottle. The product was analyzed qualitatively and quantitatively using Agilent-1260. The specific reaction conditions, MMF conversion, 2,5-FDCA selectivity and yield results are shown in Table 2.
Table 2.
Figure DEST_PATH_IMAGE003

Claims (15)

1. A preparation method of a metal modified ruthenium-based catalyst comprises the following steps:
(1) adding hydroxyapatite into soluble salt solution containing at least one of zirconium, iron and zinc, soaking, performing solid-liquid separation after soaking, washing the solid, drying and roasting;
(2) mixing the solid obtained in the step (1) with Ru3+The solution is mixed and impregnated, solid-liquid separation is carried out after the impregnation is finished, and the separated solid is washed and dried to obtain the metal modified ruthenium-based catalyst.
2. The method according to claim 1, wherein the Ru in the catalyst is3+The loading amount is 0.1-10% by mass, and preferably 3-7%.
3. The preparation method according to claim 1, wherein the loading amount of zirconium, iron and/or zinc in the catalyst is 5-10% by mass of each metal oxide.
4. The method according to claim 1, wherein the Ru-containing compound is a compound containing Ru3+The solution of (a) is selected from at least one of ruthenium chloride-containing, ruthenium nitrate or ruthenium acetate-containing solutions.
5. The method according to claim 1, wherein the soluble salt of zirconium is at least one selected from the group consisting of zirconyl nitrate, zirconium acetate, zirconium chloride, zirconium n-butoxide and zirconium n-propoxide; the soluble salt of iron is selected from at least one of ferric nitrate, ferric chloride and ferric sulfate; the soluble salt of zinc is at least one selected from zinc nitrate, zinc chloride and zinc sulfate.
6. The preparation method according to claim 1, wherein the dipping time in the step (1) is 0.5-24 hours, and the roasting temperature is 300-600 ℃.
7. The preparation method according to claim 1, wherein the time for the impregnation in the step (2) is 10min to 24 h.
8. The preparation method according to claim 1, wherein the drying temperature in the step (2) is 55-120 ℃ and the drying time is 6-12 h.
9. The method according to claim 1, wherein the Ru-containing material of step (2)3+The solvent of the solution of (1) is selected from at least one of methanol, ethanol or water.
10. The method according to claim 1, wherein the hydroxyapatite has a particle size of 1 to 100 nm.
11. A metal-modified ruthenium-based catalyst prepared by the process of any one of claims 1 to 10.
12. A process for producing 2, 5-furandicarboxylic acid, which comprises reacting 5-methoxymethylfurfural with oxygen in an aqueous solution in the presence of the catalyst according to claim 11 to produce 2, 5-furandicarboxylic acid.
13. The preparation method according to claim 11, wherein the 5-methoxymethyl furfural and the catalyst are mixed and reacted at a mass ratio of 1: 0.1-5.
14. The method according to claim 11, wherein the oxygen is introduced in an amount such that the initial pressure of the reaction system is 0.1 to 2 MPa.
15. The method according to claim 11, wherein the reaction temperature is 70 to 130 ℃ and the reaction time is 12 to 24 hours.
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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001519A (en) * 2007-06-21 2009-01-08 Canon Inc Method for producing 2,5-furandicarboxylic acid
CN101745411A (en) * 2008-12-17 2010-06-23 中国科学院大连化学物理研究所 Catalyst using ruthenium based halogen to substitute hydroxyapatite and preparation and application thereof
CN102441393A (en) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst with modified alumina as carrier and application thereof
CN102476052A (en) * 2010-11-29 2012-05-30 中国石油化工股份有限公司 Supported ruthenium catalyst and preparation method thereof
CN104059037A (en) * 2014-03-25 2014-09-24 浙江理工大学 Preparation method of 2,5-furandicarboxylic acid
CN105032427A (en) * 2015-04-22 2015-11-11 华东理工大学 Preparation method of 2,5-dimethylfuran
CN106279075A (en) * 2016-08-15 2017-01-04 中国石油大学(北京) The method that a kind of catalysis 5 Hydroxymethylfurfural prepare 2,5 dimethyl furans
CN106565647A (en) * 2016-10-29 2017-04-19 华东理工大学 Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural
CN106795130A (en) * 2014-08-19 2017-05-31 阿彻丹尼尔斯米德兰德公司 Catalyst And Method for producing 2,5 furandicarboxylic acids in water by hydroxymethylfurfural
CN107365287A (en) * 2016-05-11 2017-11-21 中国石油化工股份有限公司 A kind of method of synthesis 2,5- furandicarboxylic acids
CN107961778A (en) * 2016-10-20 2018-04-27 中国石油化工股份有限公司 A kind of silicon zinc modification catalyst carrier and its preparation method and application
CN108314667A (en) * 2017-01-18 2018-07-24 中国科学院过程工程研究所 A kind of preparation method of non-alkali systems biology base 2,5- furandicarboxylic acids
CN108712931A (en) * 2016-03-07 2018-10-26 韩国生产技术研究院 It is used to prepare the catalyst of 2,5- furandicarboxylic acids and the method using catalyst preparation 2,5- furandicarboxylic acids

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001519A (en) * 2007-06-21 2009-01-08 Canon Inc Method for producing 2,5-furandicarboxylic acid
CN101745411A (en) * 2008-12-17 2010-06-23 中国科学院大连化学物理研究所 Catalyst using ruthenium based halogen to substitute hydroxyapatite and preparation and application thereof
CN102441393A (en) * 2010-10-12 2012-05-09 中国石油化工股份有限公司 Fischer-Tropsch synthesis catalyst with modified alumina as carrier and application thereof
CN102476052A (en) * 2010-11-29 2012-05-30 中国石油化工股份有限公司 Supported ruthenium catalyst and preparation method thereof
CN104059037A (en) * 2014-03-25 2014-09-24 浙江理工大学 Preparation method of 2,5-furandicarboxylic acid
CN106795130A (en) * 2014-08-19 2017-05-31 阿彻丹尼尔斯米德兰德公司 Catalyst And Method for producing 2,5 furandicarboxylic acids in water by hydroxymethylfurfural
CN105032427A (en) * 2015-04-22 2015-11-11 华东理工大学 Preparation method of 2,5-dimethylfuran
CN108712931A (en) * 2016-03-07 2018-10-26 韩国生产技术研究院 It is used to prepare the catalyst of 2,5- furandicarboxylic acids and the method using catalyst preparation 2,5- furandicarboxylic acids
CN107365287A (en) * 2016-05-11 2017-11-21 中国石油化工股份有限公司 A kind of method of synthesis 2,5- furandicarboxylic acids
CN106279075A (en) * 2016-08-15 2017-01-04 中国石油大学(北京) The method that a kind of catalysis 5 Hydroxymethylfurfural prepare 2,5 dimethyl furans
CN107961778A (en) * 2016-10-20 2018-04-27 中国石油化工股份有限公司 A kind of silicon zinc modification catalyst carrier and its preparation method and application
CN106565647A (en) * 2016-10-29 2017-04-19 华东理工大学 Method for preparing 2, 5-furandicarboxylic acid by conducting catalytic oxidation on 5-hydroxymethylfurfural
CN108314667A (en) * 2017-01-18 2018-07-24 中国科学院过程工程研究所 A kind of preparation method of non-alkali systems biology base 2,5- furandicarboxylic acids

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHRISTIAN M. PICHLER等: "Ruthenium Supported on High-Surface-Area Zirconia as an Efficient Catalyst for the Base-Free Oxidation of 5-Hydroxymethylfurfural to 2, 5-Furandicarboxylic Acid", 《CHEMSUSCHEM》, vol. 11, no. 13, pages 2083 - 2090 *
TIANYU GAO 等: "Highly dispersed ruthenium nanoparticles on hydroxyapatite as selective and reusable catalyst for aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid under base-free conditions", 《MOLECULAR CATALYSIS》, vol. 450, pages 55 - 64, XP055697725, DOI: 10.1016/j.mcat.2018.03.006 *
ZHENZHEN YANG 等: "Selective synthesis of 2, 5-diformylfuran and 2, 5-furandicarboxylic acid from 5-hydroxymethylfurfural and fructose catalyzed by magnetically separable catalysts", 《ENERGY & FUELS》, vol. 31, no. 1, pages 533 - 541 *

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