CN113117706B - Metal modified ruthenium-based catalyst and method for preparing 2, 5-furan dicarboxylic acid by catalysis of metal modified ruthenium-based catalyst - Google Patents
Metal modified ruthenium-based catalyst and method for preparing 2, 5-furan dicarboxylic acid by catalysis of metal modified ruthenium-based catalyst Download PDFInfo
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- CN113117706B CN113117706B CN201911415408.4A CN201911415408A CN113117706B CN 113117706 B CN113117706 B CN 113117706B CN 201911415408 A CN201911415408 A CN 201911415408A CN 113117706 B CN113117706 B CN 113117706B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 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 40
- 238000000034 method Methods 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 150000003303 ruthenium Chemical class 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title description 3
- ASHVULSQMDWKFO-UHFFFAOYSA-N MMF Natural products COCC1=CC=C(C=O)O1 ASHVULSQMDWKFO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 15
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical group 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 5
- -1 zinc metal oxides Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 7
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 3
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004913 activation Effects 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004451 qualitative analysis Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a metal modified ruthenium-based catalyst and a method for preparing FDCA by catalyzing MMF by using the same, wherein the preparation of the catalyst comprises the following steps: loading at least one selected from zirconium, iron and zinc as modified metal onto hydroxyapatite, calcining, and mixing with Ru-containing material 3+ And (3) carrying out solid-liquid separation after adsorption is completed, washing and drying the separated solid, and obtaining the catalyst. The catalyst can be used for catalyzing 5-methoxymethyl furfural to prepare 2, 5-furan dicarboxylic acid. The catalyst is Ru 3+ The active component is a metal oxide of zirconium, iron and/or zinc, which is used as a modified component, and the preparation method is simple; and the introduction of zirconium, iron and/or zinc metal oxides well regulates the electron cloud around ruthenium atoms, and has synergistic effect with the hydroxyl groups of the carrier hydroxyapatite, at lower temperature and lower pressureUnder the reaction condition, the activation of aldehyde group C-H of furan ring side chain is promoted, and Ru is improved 3+ Is used as a catalyst.
Description
Technical Field
The invention relates to a preparation technology of 2, 5-furan dicarboxylic acid, in particular to a method for preparing 2, 5-furan dicarboxylic acid by oxidizing 5-methoxymethyl furfural with a metal-modified ruthenium-based-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 2, 5-furandicarboxylic acid is easy to polymerize with alcohols, so that a polymeric material with market prospect is formed. The material can be effectively degraded by microorganisms in nature, and is a biological-based material which has the highest potential to replace petroleum-based terephthalic acid.
Currently, synthetic FDCA is mostly obtained by oxidation of 5-Hydroxymethylfurfural (HMF). CN201480051571.6 discloses a process for producing 2, 5-furandicarboxylic acid, which comprises oxidizing HMF in an acidic aqueous solution with an activated carbon-supported noble metal as a catalyst to produce FDCA, wherein the process is carried out in two stages, i.e., a low-temperature process and a high-temperature process, to thereby increase the yield of FDCA, but the decrease in FDCA liquid yield due to the large amount of by-products produced by HMF in an acidic aqueous solution system is unavoidable. 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 the 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 technology for synthesizing FDCA has the defects of harsh reaction conditions, low FDCA liquid yield and the like.
Disclosure of Invention
In order to solve the problems of harsh reaction conditions and low yield of FDCA liquid in the preparation of 2, 5-furandicarboxylic acid by taking 5-hydroxymethylfurfural as a raw material 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 metal modified ruthenium-based catalyst, and the method for synthesizing 2, 5-furandicarboxylic acid by taking 5-methoxymethylfurfural as the raw material under the catalysis of the modified catalyst has the advantages of mild reaction conditions and high yield of product liquid.
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 for impregnation, performing solid-liquid separation after impregnation, and washing, drying and roasting the solid;
(2) The solid obtained in the step (1) and Ru-containing 3+ And (3) mixing and impregnating, carrying out solid-liquid separation after the impregnation is finished, washing and drying the separated solid, and obtaining the metal modified ruthenium-based catalyst.
Further, the loading of zirconium, iron and/or zinc in the catalyst is 5% -10% by weight of the mass of each metal oxide, ru 3+ The loading of (2) 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, preferably zirconyl nitrate; the soluble salt of iron is selected from at least one of ferric nitrate, ferric chloride and ferric sulfate, preferably ferric nitrate; the soluble salt of zinc is selected from at least one of zinc nitrate, zinc chloride and zinc sulfate, preferably zinc nitrate.
Further, the soaking time in the step (1) is 0.5-24 hours; the roasting temperature is 300-600 ℃, preferably 450-550 ℃.
Further, the Ru-containing material 3+ Is selected from ruthenium chloride (RuCl) 3 ) Ruthenium nitrate (RuNO (NO) 3 ) 3 ) Or ruthenium acetate (C) 6 H 9 O 6 Ru) solution.
Further, the Ru-containing material 3+ The solvent of the solution of (2) is at least one selected from methanol, ethanol or water.
Further, the time of the soaking 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.
Further, the hydroxyapatite is nano hydroxyapatite, and more specifically, the particle size of the nano hydroxyapatite is 1-100 nm.
The technical object of the second aspect of the present invention is 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 state 3+ As active component, zirconium, iron and/or zinc metal oxides are used as modifying components. The loading of zirconium, iron and/or zinc in the catalyst is 5-10% by weight of the mass of each metal oxide, ru 3+ The loading of (2) is 0.1% -10%, preferably 3% -7%.
The technical object of the third aspect of the present invention is to provide a method for preparing 2, 5-furandicarboxylic acid (2, 5-FDCA), wherein 5-methoxymethyl furfural (MMF) reacts with oxygen in an aqueous solution in the presence of the metal-modified ruthenium-based catalyst to prepare 2,5-FDCA.
Further, MMF is reacted with a catalyst (or Ru in catalyst 3+ Mass ratio of 1:0.1-5).
Furthermore, the oxygen gas is introduced into the reaction system to enable the initial pressure of the reaction system to reach 0.1-2 MPa.
Further, the reaction temperature is 70-130 ℃, preferably 70-110 ℃; the reaction time is 12-24 hours.
Compared with the prior art, the invention has the following advantages:
(1) The metal modified ruthenium-based catalyst of the invention uses Ru 3+ The active component is a metal oxide of zirconium, iron and/or zinc, which is used as a modified component, and the preparation method is simple; the introduction of the metal oxide of zirconium, iron and/or zinc well regulates electron cloud around ruthenium atoms, and has synergistic effect with the hydroxyl of carrier hydroxyapatite, so as to promote the activation of furan ring side chain aldehyde group C-H and improve Ru under the mild reaction condition of lower temperature and lower pressure 3+ Is used as a catalyst.
(2) In the preparation method of the 2, 5-furan dicarboxylic acid, the raw material 5-methoxymethyl furfural is stably present in an aqueous solution system, the activity of the catalyst is good in stability under the reaction system, the activity is high, and the liquid yield of the 2, 5-furan dicarboxylic 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 will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The metal loadings of the catalysts in the following examples and comparative examples were detected by Inductively Coupled Plasma (ICP). Qualitative and quantitative analysis of the oxidized products of MMF in the examples were all detected by Agilent liquid chromatography (Agilent-1260).
Example 1
Preparing a metal modified catalyst Z1:
(1) Will be 0.069g ZrONO 3 ·6H 2 O is added into 50mL of water, vigorously stirred for 20min, 0.5g of HAP with the diameter of 1-100 nm is added, stirred for 24h, filtered, and the solid is washed, dried and roasted in a muffle furnace at 500 ℃ for 3h to obtain a white solid.
(2) 0.0388g RuCl 3 .3H 2 O is added into 50mL of water, vigorously stirred for 10min, 0.5g of the white solid obtained in the step (1) is added, dipping is carried out for 10min, filtering is carried out, the solid is washed and dried for 12h at 55 ℃, and light gray solid powder is obtained, namely the catalyst Z1. The solid was ground for use in the oxidation of MMF.
Example 2
Preparing a metal modified catalyst Z2:
(1) Will be 0.14g ZrONO 3 ·6H 2 O is added into 50mL of water, vigorously stirred for 20min, 0.5g of HAP with the diameter of 1-100 nm is added, stirred for 12h, filtered, and the solid is washed, dried and roasted in a muffle furnace at 500 ℃ for 3h to obtain a white solid.
(2) Adding 0.0050g of ruthenium nitrate into 50mL of water, vigorously stirring for 10min, adding 0.5g of the white solid obtained in the 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
Preparing a metal modified catalyst Z3:
(1) 0.15g of Fe (NO) 3 ) 3 ·6H 2 O is added into 50mL of water, vigorously stirred for 20min, 0.5g of HAP with the diameter of 1-100 nm is added, stirred for 24h, filtered, and the solid is washed, dried and roasted in a muffle furnace at 500 ℃ for 3h to obtain a white solid.
(2) 0.0426g of ruthenium acetate is added into 50mL of water, stirred vigorously for 10min, 0.5g of the white solid obtained in the step (1) is added, immersed for 30min, filtered, and the solid is washed and dried for 12h at 55 ℃ to obtain dark gray solid powder, namely the catalyst Z3. The solid was ground for use in the oxidation of MMF.
Example 4
Preparing a metal modified catalyst Z4:
(1) 0.1g Zn (NO) 3 ) 2 ·6H 2 O is added into 50mL of water, vigorously stirred for 20min, 0.5g of HAP with the diameter of 1-100 nm is added, stirred for 24h, filtered, and the solid is washed, dried and roasted in a muffle furnace at 500 ℃ for 3h to obtain a white solid.
(2) 0.1471g RuCl 3 ·3H 2 O is added into 50mL of water, vigorously stirred for 10min, 0.5g of the white solid obtained in the step (1) is added, the mixture is immersed for 2h and filtered, the solid is washed and dried for 12h at 55 ℃ to obtain gray solid powder, namely the catalyst Z4. The solid was ground for use in the oxidation of MMF.
Example 5
Preparing a metal modified catalyst Z5:
(1) Will be 0.111g ZrONO 3 ·6H 2 O is added into 50mL of water, vigorously stirred for 20min, 0.5g of HAP with the diameter of 1-100 nm is added, stirred for 24h, filtered, and the solid is washed, dried and roasted in a muffle furnace at 500 ℃ for 3h to obtain a white solid.
(2) 0.1029g RuCl 3 ·3H 2 Adding O into 50mL of water, vigorously stirring for 10min, adding 0.5g of the white solid obtained in the step (1), soaking for 5h, filtering, and concentratingWashing the solid, and drying at 55 ℃ for 12 hours 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 RuCl 3 .3H 2 O was added to 50mL of water, vigorously stirred for 10min, 0.5g of HAP was added, immersed for 10min, filtered, and the solid was washed and dried at 55℃for 12h to give catalyst Z6. The solid was ground for use in the oxidation of MMF.
The mass percentages of ruthenium (based on the mass of ruthenium element) and metal oxide (based on the mass of metal oxide of Zr, fe or Zn) in the catalysts Z1 to Z6 were measured using Inductively Coupled Plasma (ICP), and the results are shown in table 1.
Table 1.
Performance evaluation of catalysts Z1-Z6 for MMF reaction to prepare 2, 5-FDCA:
the evaluation test was carried out in a six-bar reactor with a volume of 8 mL. The specific catalyst evaluation process is as follows: adding 20mg of 5-methoxymethyl furfural, 3mL of water and 2-100 mg of catalyst into a reaction kettle, screwing, adding oxygen until the initial pressure is 0.1-2 MPa, sealing, and putting the reaction kettle into a six-link heating sleeve to react at 70-130 ℃ respectively. And after reacting for 8-24 hours, immediately taking out the reaction kettle, putting the reaction kettle into cold water for cooling, opening the reaction kettle after cooling is finished, washing the reaction kettle by using a methanol aqueous solution, transferring the reaction kettle into a 50mL volumetric flask by using a dropper for constant volume, centrifuging, and filtering the reaction kettle into a sample injection bottle. Qualitative and quantitative analysis of the product was performed using Agilent-1260. Specific reaction conditions and MMF conversion, 2,5-FDCA selectivity and yield results are shown in table 2.
Table 2.
Claims (16)
1. 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 for impregnation, performing solid-liquid separation after impregnation, and washing, drying and roasting the solid;
(2) The solid obtained in the step (1) and Ru-containing 3+ After the impregnation is completed, carrying out solid-liquid separation, washing and drying the separated solid to obtain the metal modified ruthenium-based catalyst;
the catalyst takes hydroxyapatite as a carrier and Ru exists in an ionic state 3+ As active component, zirconium, iron and/or zinc metal oxides are used as modifying components.
2. The method according to claim 1, wherein Ru in the catalyst 3+ The load of the catalyst is 0.1 to 10 percent by mass.
3. The method according to claim 1, wherein Ru in the catalyst 3+ The load of the catalyst is 3 to 7 percent by mass.
4. The preparation method according to claim 1, wherein the loading of zirconium, iron and/or zinc in the catalyst is 5-10% based on the mass of each metal oxide.
5. The method according to claim 1, wherein the Ru-containing material 3+ Is selected from at least one of ruthenium chloride, ruthenium nitrate or ruthenium acetate containing solutions.
6. 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 selected from at least one of zinc nitrate, zinc chloride and zinc sulfate.
7. The method according to claim 1, wherein the dipping time in the step (1) is 0.5 to 24 hours, and the baking temperature is 300 to 600 ℃.
8. The method according to claim 1, wherein the time of the impregnation in the step (2) is 10min to 24h.
9. The method according to claim 1, wherein the drying in step (2) is carried out at a temperature of 55 to 120 ℃ for a time of 6 to 12 hours.
10. The method according to claim 1, wherein the Ru-containing material of step (2) 3+ The solvent of the solution of (2) is at least one selected from methanol, ethanol or water.
11. The method according to claim 1, wherein the particle size of the hydroxyapatite is 1 to 100nm.
12. A metal-modified ruthenium-based catalyst prepared according to the method of any one of claims 1 to 11.
13. A process for producing 2, 5-furandicarboxylic acid, characterized in that 2, 5-furandicarboxylic acid is produced by reacting 5-methoxymethyl furfural with oxygen in an aqueous solution in the presence of the catalyst according to claim 12.
14. The preparation method of claim 13, wherein the mass ratio of the 5-methoxymethyl furfural to the catalyst is 1:0.1-5.
15. The process according to claim 13, wherein the oxygen is introduced into the reaction system in such an amount that the initial pressure of the reaction system is 0.1 to 2MPa.
16. The method according to claim 13, wherein the reaction temperature is 70 to 130 ℃ and the reaction time is 12 to 24 hours.
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