CN114621167B - Preparation method of 2, 5-furandicarboxylic acid - Google Patents
Preparation method of 2, 5-furandicarboxylic acid Download PDFInfo
- Publication number
- CN114621167B CN114621167B CN202011455844.7A CN202011455844A CN114621167B CN 114621167 B CN114621167 B CN 114621167B CN 202011455844 A CN202011455844 A CN 202011455844A CN 114621167 B CN114621167 B CN 114621167B
- Authority
- CN
- China
- Prior art keywords
- reaction
- hmf
- methyl nitrite
- catalyst
- fdca
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 108
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 96
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 43
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 25
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 238000011068 loading method Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000010412 oxide-supported catalyst Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 6
- -1 zrO 2 Inorganic materials 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 3
- 229960001545 hydrotalcite Drugs 0.000 claims description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 30
- 230000001590 oxidative effect Effects 0.000 abstract description 20
- 239000007800 oxidant agent Substances 0.000 abstract description 13
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000003245 coal Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- RSGPROFUAZQXLV-UHFFFAOYSA-N hydrogen peroxide;2-hydroperoxy-2-methylpropane Chemical compound OO.CC(C)(C)OO RSGPROFUAZQXLV-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000000463 material 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application discloses a preparation method of 2, 5-furandicarboxylic acid (FDCA), which at least comprises the following steps: and (3) reacting the reaction solution containing methyl nitrite and 5-hydroxymethylfurfural under the action of an oxidation reaction catalyst to obtain 2, 5-furandicarboxylic acid. The method can realize the full utilization of the important intermediate methyl nitrite in the process of preparing the ethylene glycol from the coal. The method takes methyl nitrite as an oxidant to realize the efficient oxidation of HMF to prepare FDCA under the condition of no alkali and non-noble metal catalyst.
Description
Technical Field
The application relates to a preparation method for oxidizing 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid by taking methyl nitrite as an oxidant, belonging to the field of organic chemical preparation.
Background
In recent years, high value-added chemicals produced from renewable biomass resources have been of great interest. HMF is one of the most potential chemicals, an important platform compound for achieving comprehensive utilization of biomass resources. FDCA is an important derivative of HMF and is also one of twelve biomass-based platform compounds of great value recommended by the U.S. department of energy. FDCA is very similar in chemical nature and structure to conventional petroleum-based monomer terephthalic acid, and therefore FDCA is used as a substitute for terephthalic acid to make polymers such as polyesters, polyamides, and the like. For example, as a biobased substitute for polyethylene terephthalate (PET) with annual output exceeding 7000 ten thousand tons, polyethylene furandicarboxylate (PEF) not only has better sustainability, but also has significant advantages in performance, including higher heat resistance, mechanical strength, and gas barrier properties of about one order of magnitude higher. Therefore, the development of a process route for preparing FDCA by HMF oxidation has wide application prospect.
At present, the industrial mass production of the FDCA is not realized, the research progress of the FDCA is only stopped at a laboratory stage, and the research focus is mainly focused on the high-efficiency conversion from HMF to FDCA by taking noble metal as an oxidation catalyst and performing metered oxidation by oxygen or a strong oxidant under an alkaline condition. The problems of high cost, serious three wastes and the like restrict the industrialized application of the FDCA. Therefore, a new process route is developed to realize the non-noble metal alkali-free catalytic oxidation of the HMF to the FDCA, and the method has very important significance for realizing the industrial application of the HMF to the FDCA.
The reported oxidants for HMF to FDCA and the main synthesis method are as follows:
(1) Air oxidation: in the process of preparing FDCA by using air as an oxidant, most of the catalyst is noble metal (Au, pt, pd and the like), and the noble metal catalytic system often needs excessive alkali to promote the formation of 2, 5-furandicarboxylic acid salt, so that the strong adsorption of carboxylic acid on the surface of the catalyst is avoided. (2) oxygen oxidation: the oxygen atom utilization rate of oxygen oxidation is high, only water is a byproduct, and the method is environment-friendly and is an ideal reaction system.
(3) Other oxidants oxidize: compared with the oxidation of HMF in alkaline environment, the oxidation of HMF in non-alkaline environment can also select weak acid organic hydrogen peroxide tert-butyl hydroperoxide (TBMP) as an oxidant.
The prior FDCA method can increase the production cost of FDCA and can generate a large amount of pollutants, and the post-treatment steps are complicated.
Ethylene glycol is a large number of petrochemical products, and is mainly used for antifreeze and preparation of PET polyester. Ethylene glycol is currently produced mainly by petrochemical technology route: ethylene is taken as a raw material, ethylene oxide is prepared through epoxidation, and then ethylene glycol is prepared through hydration; the technology needs to consume a large amount of petroleum resources, and the dehydration separation energy consumption is large. The development and application of the coal chemical technology provide a new technical route for producing glycol by a non-petroleum route. In the process of preparing ethylene glycol from coal, methyl nitrite is an important intermediate, and a large amount of methyl nitrite exists in the process flow of preparing ethylene glycol and the process flow of treating byproduct dilute nitric acid. Has the characteristics of wide sources, low cost and easy availability, but is not widely applied.
The existing method for preparing FDCA by oxidizing HMF mainly focuses on taking noble metal as an oxidation catalyst, and realizing high-efficiency conversion from HMF to FDCA by metering and oxidizing with oxygen or a strong oxidant under alkaline conditions. The problems of high cost, serious three wastes and the like restrict the industrialized application of the FDCA. Therefore, a new process route is developed to realize the non-noble metal alkali-free catalytic oxidation of the HMF to the FDCA, and the method has very important significance for realizing the industrial application of the HMF to the FDCA.
Disclosure of Invention
According to one aspect of the application, the preparation method of the FDCA can fully utilize the important intermediate methyl nitrite in the process of preparing the ethylene glycol from the coal, and can realize the efficient conversion of the HMF into the FDCA under the alkali-free condition by using the methyl nitrite as an oxidant.
A preparation method of 2, 5-furandicarboxylic acid comprises the step of reacting a reaction solution containing methyl nitrite and 5-hydroxymethylfurfural under the action of an oxidation reaction catalyst to obtain 2, 5-furandicarboxylic acid.
Methyl nitrite, which is a nitrogen oxide, also has more efficient oxidation properties than molecular oxygen and can be used as a metering oxidant for HMF to FDCA. Therefore, the realization of the metered oxidation of HMF to FDCA by the oxidative properties of methyl nitrite is a new approach to the preparation of FDCA. Has very important practical significance for reducing the preparation cost of FDCA and improving the comprehensive utilization of the intermediate product of the coal-to-ethylene glycol.
Optionally, the oxidation reaction catalyst is a transition metal oxide supported catalyst.
Optionally, the transition metal oxide supported catalyst comprises a transition metal oxide and a catalyst support;
alternatively, the transition metal oxide is selected from MnO 2 、Co 3 O 4 、Fe 3 O 4 、CuO、CeO 2 At least one of them.
Preferably, the transition metal oxide is Co 3 O 4 . Optionally, the catalyst carrier is selected from activated carbon, alpha-Al 2 O 3 、γ-Al 2 O 3 MgO, hydrotalcite, zrO 2 、SiO 2 At least one of them.
Optionally, the transition metal oxide supported catalyst has a loading of 0.1 to 5wt% of the transition metal oxide.
Preferably, the transition metal oxide loading is 1 to 3wt%;
wherein the loading is calculated based on the catalyst carrier.
When the loading of the transition metal oxide is selected within 0.1-5 wt%, the HMF conversion rate and the FDCA yield are both higher than 75%.
Alternatively, the loading of the transition metal oxide is independently selected from any value or range of values between any two of 0.1wt%, 0.2wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 4wt%, 5wt%.
Optionally, the particle size of the oxidation catalyst is less than or equal to 5 mesh.
Optionally, the particle size of the oxidation catalyst is less than or equal to 20 mesh.
Preferably, the particle size of the oxidation catalyst is 20 to 5 mesh. The oxidation reaction catalyst is prepared by tabletting, crushing and sieving, and then selecting particles with the particle size of less than 5 meshes. Preferably, the reduction catalyst has a particle size of less than 20 mesh. As particle size increases, HMF conversion gradually decreases. The reason is probably that the larger the particle diameter, the smaller the specific surface, and the larger the stacking pores, resulting in a smaller contact area of HMF and methyl nitrite with the catalyst active site, and thus a reduction in conversion. When the particle size of the oxidation catalyst is selected within the preferred range, both the HMF conversion and the FDCA yield are higher than 80%.
Optionally, in the reaction solution containing methyl nitrite and 5-hydroxymethylfurfural, the molar ratio of the methyl nitrite to the 5-hydroxymethylfurfural is 1-10: 1, a step of;
preferably, the molar ratio of methyl nitrite to HMF is 3 to 10:1.
more preferably, the molar ratio of methyl nitrite to HMF is from 5 to 10:1.
when the molar ratio of methyl nitrite to HMF is selected from 5-10, both the HMF conversion rate and the FDCA yield are higher than 80%.
More preferably, the molar ratio of methyl nitrite to HMF is 8:1.
alternatively, the molar ratio of methyl nitrite to HMF is independently selected from any value or range of values between any two of 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.
Optionally, the reaction solution is formed by mixing a reaction solution I and a reaction solution II;
the reaction solution I is a 5-hydroxymethylfurfural solution, the solvent is dimethyl sulfoxide, and the concentration range of the 5-hydroxymethylfurfural is 30-60 wt%;
the reaction solution II is methyl nitrite solution, the solvent is methanol, and the concentration range of the methyl nitrite is 5-75wt%.
Preferably, the concentration of HMF solution in DMSO is 50wt%. Preferably, the concentration of the methyl nitrite solution is 50wt% by taking methanol as a solvent.
Optionally, the space velocity of the reaction solution is 0.1 to 1h -1 ；
Preferably, the space velocity of the reaction liquid is 0.1 to 0.5h -1 . The space velocity of the reaction solution is 0.1 to 0.5h -1 When the range is selected, the HMF conversion rate and the FDCA yield are both higher than 75 percent.
More preferably, the optimal reaction space velocity is 0.2h -1 。
Alternatively, the space velocity of the reaction solution is independently selected from 0.1h -1 、0.2h -1 、0.3h -1 、0.4h -1 、0.5h -1 、0.6h -1 、0.7h -1 、0.8h -1 、0.9h -1 、1h -1 Any value therein or any range therebetween.
Optionally, the temperature of the reaction is 80-150 ℃;
preferably, the temperature of the reaction is 90-130 ℃;
more preferably, the temperature of the reaction is 100 to 120 ℃.
When the reaction temperature is selected within the range of 100-120 ℃, the HMF conversion rate and the FDCA yield are both higher than 80 percent.
More preferably, the temperature of the reaction is 120 ℃.
Alternatively, the temperature of the reaction solution is independently selected from any value or range of values between any two of 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃.
Alternatively, the pressure of the reaction is 0.05-0.2 MPa.
Preferably, the reaction pressure is normal pressure. The reaction conditions are very mild.
The pressure of the reaction is normal pressure. The normal pressure can be determined according to the actual production site, and can be usually 0.1MPa.
Alternatively, the reactor of the reaction is a fixed bed reactor. The method has mild reaction conditions, can carry out continuous reaction by adopting a fixed bed, and is beneficial to improving the production efficiency.
Specifically, the catalyst can be packed by adding it to a glass tube reactor, and filling silica pellets (preheated raw material) in the upper part of the catalyst and stainless steel wires (supporting catalyst layer) in the lower part. The reaction was carried out at normal pressure.
In the present application, "FDCA" means 2, 5-furandicarboxylic acid.
In the present application, "HMF" refers to 5-hydroxymethylfurfural.
The beneficial effects that this application can produce include:
1) According to the preparation method of the FDCA, methyl nitrite is used as an oxidant, under the alkali-free condition, the raw material containing the HMF is oxidized into the FDCA through catalytic oxidation, the method is environment-friendly and easy to operate, the conversion efficiency of the HMF is high, and the FDCA is easy to separate from the reaction raw material. The oxidant used in the method can be intermediate product methyl nitrite in the process of preparing ethylene glycol from coal, so that the method is convenient for realizing large-scale industrial production by being used with the existing coal-based ethylene glycol.
2) The FDCA preparation method provided by the application adopts continuous reaction and uses a fixed bed reaction device, thereby being beneficial to improving the production efficiency and being easy to realize industrial production. The whole reaction process is carried out under normal pressure, so that the requirement of the reaction on equipment is greatly reduced, and the method has wide industrial application prospect.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials and catalysts used in the examples of this application were commercially available and the reagents used were all analytically pure. If not specified, the test methods are all conventional methods, and the instrument settings are all recommended by manufacturers.
In the examples, activated carbon was purchased from Shanghai Ara Ding Shiji company;
ɑ-Al 2 O 3 purchased from the company Tianjin Miou reagent;
γ-Al 2 O 3 purchased from the company Tianjin Miou reagent;
MgO is purchased from Shanghai Ara Ding Shiji company;
HT is hydrotalcite, purchased from shanghai alaa Ding Shiji company;
ZrO 2 purchased from Shanghai Ara Ding Shiji company;
SiO 2 purchased from the company Miou reagent, tianjin.
Preparing 5-hydroxymethylfurfural solution with concentration of 45wt% by taking dimethyl sulfoxide as a solvent; methanol is used as a solvent to prepare methyl nitrite solution with the concentration of 50wt%; then mixing the two materials to prepare raw material liquid.
The analytical method in the examples of the present application is as follows:
the contents of HMF and FDCA were analyzed by gas chromatography equipped with a thermal conductivity detector, and the conversion of HMF and the yield of FDCA were calculated by an internal standard method.
Conversion and yield in the examples of the present application were calculated as follows:
conversion of hmf= (moles of HMF ester before reaction-moles of HMF after reaction)/moles of HMF before reaction ×100%
Yield of FDCA = moles of FDCA/moles of HMF converted 100%
The space velocity of the reaction liquid means the volume space velocity.
As a specific embodiment, the oxidation catalyst is prepared by immersing the support in an equal volume of a transition metal salt solution by an equal volume immersion method, standing at room temperature for 12 hours, and drying at 100 ℃. Before use, the mixture is roasted for 2 to 12 hours at the temperature of 350 to 450 ℃ by air.
As a specific embodiment, the reaction for preparing FDCA by catalyzing the oxidation of methyl nitrite to HMF is carried out on a fixed bed reaction device, an oxidation catalyst with the particle size of 5-20 meshes is added into a glass tube reactor, the upper part of the catalyst is filled with silicon oxide pellets (preheated raw materials), and the lower part is filled with stainless steel wires (supporting catalyst layers). The reaction device is heated to a certain temperature. Wherein the reaction temperature is 90-130 ℃ and the pressure is normal pressure.
The transition metal oxide supported catalysts used in the examples can be obtained by the prior art. The preparation method can also be adopted:
in the examples, the oxidation catalyst was prepared by immersing the support in an equal volume of a transition metal salt solution by an equal volume immersion method, standing at room temperature for 12 hours, and drying at 100 ℃. Before use, the mixture is roasted for 5 hours at 400 ℃ by air.
Example 1 alpha-Al 2 O 3 Reaction for preparing FDCA by oxidizing HMF by using methyl nitrite catalyzed by different transition metal oxide supported catalysts
alpha-Al 2 O 3 Loading different transition metal oxide catalysts, respectively tabletting, crushing, sieving with a 10-mesh sieve, loading 10mL of catalyst (loading 2 wt%) with particle size smaller than 10 meshes into a glass tube reactor with diameter of 15mm, and reacting at normal pressure and 120 ℃ under conditions that molar ratio of methyl nitrite to HMF in the raw material liquid is 8 and airspeed of the raw material liquid is 0.2h -1 。
The results obtained on the different transition metal oxide catalysts are shown in Table 1.
TABLE 1 different transition metal oxide loadings alpha-Al 2 O 3 Catalyst for preparing FDCA by oxidizing HMF by methyl nitrite
As can be seen from Table 1, different transition metal oxides are loaded with alpha-Al 2 O 3 Co in the catalyst 3 O 4 Exhibiting higher HMF oxidative conversion and FDCA yield.
EXAMPLE 2 Co with different Carriers 3 O 4 Catalyst for catalyzing reaction of preparing FDCA by oxidizing HMF by methyl nitrite
Co with different supports 3 O 4 The catalyst is respectively pressed into tablets, crushed and sieved by a 10-mesh sieve, and the particle size is smaller than 10 mu of 10mLCo 3 O 4 The catalyst (load 2 wt%) is placed into a glass tube reactor with a diameter of 15mm, the reaction temperature is 120 deg.C, the mole ratio of methyl nitrite and HMF in the raw material solution is 8, and the space velocity of the raw material solution is 0.2h -1 。
The results obtained on the different supported catalysts are shown in Table 2.
TABLE 2 Co for different Carriers 3 O 4 Catalyst for preparing FDCA by oxidizing HMF by methyl nitrite
| Examples | Carrier body | HMF conversion (mol%) | FDCA yield (mol%) |
| 2-1 | Activated carbon | 81 | 82 |
| 2-2 | ɑ-Al 2 O 3 | 87 | 85 |
| 2-3 | γ-Al 2 O 3 | 80 | 82 |
| 2-4 | MgO | 89 | 83 |
| 2-5 | HT | 86 | 86 |
| 2-6 | ZrO 2 | 85 | 83 |
| 2-7 | SiO 2 | 86 | 83 |
As can be seen from the results of Table 2, co for different supports 3 O 4 The catalyst can catalyze the reaction of preparing FDCA by oxidizing HMF by methyl nitrite, the conversion rate of HMF is more than 80%, and the yield of FDCA is more than 80%.
Example 3 influence of catalyst particle size
2wt% Co 3 O 4 /ɑ-Al 2 O 3 The catalyst is pressed into tablets, crushed and respectively sieved by sieves with different meshes, and 10mL 2wt% Co with the particle size smaller than the corresponding 10 meshes is taken 3 O 4 /ɑ-Al 2 O 3 Placing into a glass tube reactor with a diameter of 15mm, performing oxidation reaction under normal pressure at 120deg.C, wherein the molar ratio of methyl nitrite to HMF in the raw material liquid is 8, and the space velocity of the raw material liquid is 0.2h -1 。
The results of the reactions with catalysts of different particle sizes are shown in Table 3.
TABLE 3 different particle size 2wt% Co 3 O 4 /ɑ-Al 2 O 3 Preparation of FDCA by catalyzing oxidation of HMF by methyl nitrite
As can be seen from the results in table 3, the catalyst particle size has a significant effect on HMF conversion, which gradually decreases as the particle size increases. The reason is probably that the larger the particle diameter, the smaller the specific surface, and the larger the stacking pores, resulting in a smaller contact area between methyl nitrite and HMF at the active site of the catalyst, and thus the conversion rate is lowered.
Example 4 load impact
Co with different loading amounts and particle size of less than 20 meshes and 10mL 3 O 4 /ɑ-Al 2 O 3 The catalyst is put into a glass tube reactor with the diameter of 15mm, and is subjected to oxidation reaction under normal pressure, the reaction temperature is 120 ℃, the mole ratio of methyl nitrite to HMF in the raw material liquid is 8, and the space velocity of the raw material liquid is 0.2h -1 。
The results of the reactions over the different catalysts are shown in Table 4.
TABLE 4 Co loading at different levels 3 O 4 /ɑ-Al 2 O 3 Preparation of FDCA by catalyzing oxidation of HMF by methyl nitrite
As can be seen from the results in Table 4, co 3 O 4 The loading has a significant effect on the conversion of HMF, with Co 3 O 4 The loading increases and the HMF conversion gradually increases and then levels out. The yield of FDCA is substantially stable.
Example 5 reaction temperature Effect
10mL of 2wt% Co with particle size less than 20 mesh 3 O 4 /ɑ-Al 2 O 3 Placing the mixture into a glass tube reactor with the diameter of 15mm, carrying out oxidation reaction under normal pressure, wherein the reaction temperature is 90-130 ℃, the molar ratio of methyl nitrite to HMF in the raw material liquid is 8, and the space velocity of the raw material liquid is 0.2h -1 。
The reaction results at different temperatures are shown in Table 5.
TABLE 5 2wt% Co at different reaction temperatures 3 O 4 /ɑ-Al 2 O 3 Preparation of FDCA by catalyzing oxidation of HMF by methyl nitrite
| Examples | Reaction temperature (. Degree. C.) | HMF conversion (mol%) | FDCA yield (mol%) |
| 5-1 | 90 | 72 | 89 |
| 5-2 | 100 | 85 | 88 |
| 5-3 | 110 | 90 | 86 |
| 5-4 | 120 | 93 | 86 |
| 5-5 | 130 | 94 | 80 |
As can be seen from the results of Table 5, the reaction temperature has a significant effect on the HMF conversion, and as the reaction temperature increases, the HMF conversion gradually increases and then levels off, the FDCA yield decreases with increasing temperature, and the optimum reaction temperature is 120 ℃.
Example 6 reaction space velocity Effect
10mL of 2wt% Co with particle size less than 20 mesh 3 O 4 /ɑ-Al 2 O 3 Placing the mixture into a glass tube reactor with the diameter of 15mm, carrying out oxidation reaction under normal pressure, wherein the reaction temperature is 120 ℃, the molar ratio of methyl nitrite to HMF in the raw material liquid is 8, and the space velocity of the raw material liquid is 0.1-1 h -1 。
The results of the reaction at different space velocities are shown in Table 6.
TABLE 6 2wt% Co at different reaction space velocities 3 O 4 /ɑ-Al 2 O 3 Preparation of FDCA by catalyzing oxidation of HMF by methyl nitrite
| Examples | Airspeed (h) -1 ) | HMF conversion (mol%) | FDCA yield (mol%) |
| 6-1 | 0.1 | 95 | 87 |
| 6-2 | 0.2 | 93 | 86 |
| 6-3 | 0.3 | 91 | 87 |
| 6-4 | 0.4 | 82 | 81 |
| 6-5 | 0.5 | 75 | 78 |
| 6-6 | 0.6 | 63 | 73 |
| 6-7 | 0.8 | 52 | 60 |
| 6-8 | 1 | 32 | 52 |
As can be seen from the results in Table 6, the reaction space velocity was in the range of 0.1 to 0.3h -1 When the reaction time is over, the conversion rate of HMF is not obviously influenced, but the reaction space velocity exceeds 0.4h -1 When the reaction space velocity is increased, the conversion rate of HMF is obviously reduced, and the optimal reaction space velocity is 0.2h -1 . The reaction space velocity has the same trend in the yield of FDCA as the conversion of HMF.
Example 7 influence of methyl nitrite and HMF content in feed solution
10mL of 2wt% Co with particle size less than 20 mesh 3 O 4 /ɑ-Al 2 O 3 Placing the mixture into a glass tube reactor with the diameter of 15mm, carrying out oxidation reaction under normal pressure, wherein the reaction temperature is 120 ℃, the molar ratio of methyl nitrite to HMF in the raw material liquid is 3-10, and the space velocity of the raw material liquid is 0.2h -1 。
The results of the reactions of the various methyl nitrite with HMF content are shown in Table 7.
TABLE 7 2wt% Co at different methyl nitrite and HMF contents 3 O 4 /ɑ-Al 2 O 3 Preparation of FDCA by catalyzing oxidation of HMF by methyl nitrite
As can be seen from the results in table 6, when the molar ratio of methyl nitrite to HMF is less than 5, the HMF oxidation conversion is lower, and as the content of methyl nitrite increases, the HMF conversion increases significantly, and the HMF conversion tends to stabilize with continued increase in the content of methyl nitrite. The reason may be that the increased content of methyl nitrite as the oxidizing agent is more advantageous for the oxidation of HMF. The molar ratio of methyl nitrite to HMF has the same trend in the yield of FDCA as the conversion of HMF.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (9)
1. The preparation method of the 2, 5-furandicarboxylic acid is characterized in that a reaction solution containing methyl nitrite and 5-hydroxymethylfurfural reacts under the action of an oxidation reaction catalyst to obtain the 2, 5-furandicarboxylic acid;
the oxidation reaction catalyst is a transition metal oxide supported catalyst;
the transition metal oxide supported catalyst comprises a transition metal oxide and a catalyst carrier;
the transition metal oxide is selected from MnO 2 、Co 3 O 4 、Fe 3 O 4 、CuO、CeO 2 At least one of (a) and (b);
the catalyst carrier is selected from activated carbon, alpha-Al 2 O 3 、γ-Al 2 O 3 MgO, hydrotalcite, zrO 2 、SiO 2 At least one of (a) and (b);
in the reaction solution containing methyl nitrite and 5-hydroxymethylfurfural, the molar ratio of the methyl nitrite to the 5-hydroxymethylfurfural is 1-10: 1, a step of;
the reaction solution is formed by mixing a reaction solution I and a reaction solution II;
the reaction solution I is a 5-hydroxymethylfurfural solution, the solvent is dimethyl sulfoxide, and the concentration range of the 5-hydroxymethylfurfural is 30-60 wt%;
the reaction solution II is methyl nitrite solution, the solvent is methanol, and the concentration range of the methyl nitrite is 5-75wt%;
the airspeed of the reaction liquid is 0.1 to 1h -1 ；
The temperature of the reaction is 80-150 ℃;
the pressure of the reaction is 0.05-0.2 MPa.
2. The preparation method according to claim 1, wherein the transition metal oxide supported catalyst has a loading of transition metal oxide of 0.1 to 5wt%.
3. The preparation method according to claim 1, wherein the transition metal oxide supported catalyst has a transition metal oxide loading of 1 to 3wt%;
wherein the loading is calculated based on the catalyst carrier.
4. The method according to claim 1, wherein the particle size of the oxidation catalyst is 5 mesh or less.
5. The method according to claim 1, wherein the particle size of the oxidation catalyst is 20 to 5 mesh.
6. The preparation method according to claim 1, wherein the molar ratio of methyl nitrite to HMF in the reaction liquid containing methyl nitrite and 5-hydroxymethylfurfural is 3-10: 1.
7. the process according to claim 1, wherein the space velocity of the reaction solution is 0.1 to 0.5h -1 。
8. The process according to claim 1, wherein the temperature of the reaction is 90 to 130 ℃.
9. The process according to claim 1, wherein the temperature of the reaction is 100 to 120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011455844.7A CN114621167B (en) | 2020-12-10 | 2020-12-10 | Preparation method of 2, 5-furandicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011455844.7A CN114621167B (en) | 2020-12-10 | 2020-12-10 | Preparation method of 2, 5-furandicarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114621167A CN114621167A (en) | 2022-06-14 |
| CN114621167B true CN114621167B (en) | 2024-02-23 |
Family
ID=81896332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011455844.7A Active CN114621167B (en) | 2020-12-10 | 2020-12-10 | Preparation method of 2, 5-furandicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114621167B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7572925B2 (en) * | 2006-06-06 | 2009-08-11 | Wisconsin Alumni Research Foundation | Catalytic process for producing furan derivatives in a biphasic reactor |
-
2020
- 2020-12-10 CN CN202011455844.7A patent/CN114621167B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114621167A (en) | 2022-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111377890B (en) | Method for producing 2,5-furandicarboxylic acid from 5-hydroxymethylfurfural | |
| CN111298806B (en) | Propylene epoxidation catalyst Au/TiO 2 @SiO 2 @Fe 3 O 4 Preparation method and application of | |
| CN110102350A (en) | Catalyst and its preparation method and application for oxidative synthesis 2,5- furandicarboxylic acid | |
| CN111013598B (en) | Catalyst for preparing H2 by methanol steam conversion and application thereof | |
| AU2010286451B2 (en) | Vapor-phase decarbonylation process | |
| TW482759B (en) | Vapor phase oxidation of acrolein to acrylic acid | |
| CN102284304A (en) | Method for preparing high-efficiency catalyst for vinyl acetate synthesis by acetylene method | |
| CN107739297A (en) | It is a kind of to directly select the method that oxidation prepares methanol, formaldehyde, CO for methane | |
| Zheng et al. | Boosting 2, 5-Furandicarboxylic acid production via coating carbon over CeO2 in a Pt catalyst | |
| CN114621167B (en) | Preparation method of 2, 5-furandicarboxylic acid | |
| CN111187238B (en) | Synthetic method of 2, 5-furandicarboxylic acid | |
| CN110172049B (en) | Method for preparing furan-2, 5-dimethyl diformate by oxidizing and esterifying 5-hydroxymethylfurfural | |
| US8574522B2 (en) | Process for selective oxidative dehydrogenation of a hydrogen-containing CO mixed gas | |
| CN102219213B (en) | Method for hydrogen removal of CO mixed gas by selective oxidation | |
| CN101993353A (en) | Method for preparing 3-methyl-3-butene-1-alcohol | |
| CN105032421A (en) | Preparation method of attapulgite-supported Cu-ZrO2 catalyst and application of attapulgite-supported Cu-ZrO2 catalyst to methanol steam reforming for hydrogen production | |
| CN109847777A (en) | A kind of solid-carrying type Cu base catalyst and its preparation method and application | |
| CN101653731B (en) | Catalyst for synthesizing diethyl oxalate with carbon monoxide, preparation method and application thereof | |
| CN101176850B (en) | Catalyzer for preparing ethylene by ethanol dehydration as well as preparation method and usage | |
| CN103772198B (en) | The barkite production method of catalyst combination loading | |
| CN109574844A (en) | The manufacturing method of glyoxylic ester | |
| CN112246240A (en) | Preparation and application of dimethyl carbonate catalyst | |
| CN101462081A (en) | Method for preparing catalyst for synthesizing dimethyl oxalate | |
| CN112142600A (en) | Preparation method and application of methyl nitrite | |
| CN112206812A (en) | Preparation and application of metal modified isolated iron site catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |