CN115057834A - Method for preparing 2, 5-tetrahydrofuran dimethanol through two-step hydrogenation - Google Patents
Method for preparing 2, 5-tetrahydrofuran dimethanol through two-step hydrogenation Download PDFInfo
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- CN115057834A CN115057834A CN202210825328.1A CN202210825328A CN115057834A CN 115057834 A CN115057834 A CN 115057834A CN 202210825328 A CN202210825328 A CN 202210825328A CN 115057834 A CN115057834 A CN 115057834A
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- YCZZQSFWHFBKMU-UHFFFAOYSA-N [5-(hydroxymethyl)oxolan-2-yl]methanol Chemical compound OCC1CCC(CO)O1 YCZZQSFWHFBKMU-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 362
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 76
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 13
- -1 copper-zinc-aluminum Chemical group 0.000 claims description 58
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 49
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 28
- 230000035484 reaction time Effects 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical group C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000012467 final product Substances 0.000 abstract description 14
- 238000009776 industrial production Methods 0.000 abstract description 8
- 239000007795 chemical reaction product Substances 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 88
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 44
- 239000004810 polytetrafluoroethylene Substances 0.000 description 44
- 238000004458 analytical method Methods 0.000 description 40
- 239000012295 chemical reaction liquid Substances 0.000 description 28
- 239000011261 inert gas Substances 0.000 description 23
- 238000004817 gas chromatography Methods 0.000 description 22
- 238000004321 preservation Methods 0.000 description 22
- 230000008859 change Effects 0.000 description 18
- 238000005070 sampling Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 239000013067 intermediate product Substances 0.000 description 14
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000013341 scale-up Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical group [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XCWZSWBOSVVZGV-UHFFFAOYSA-N oxolane-2,5-diol Chemical compound OC1CCC(O)O1 XCWZSWBOSVVZGV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- 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
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- Chemical & Material Sciences (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and particularly discloses a method for preparing 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation. The method takes 5-hydroxymethylfurfural as a raw material, respectively carries out a first-stage reaction and a second-stage reaction in a hydrogen atmosphere, and prepares the 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation, and compared with the prior method, the method has the following advantages: 1) the required reaction pressure is reduced, the consumption of the noble metal catalyst is reduced, and the industrial production cost is greatly reduced; 2) the final product 2, 5-tetrahydrofuran dimethanol has high yield and good purity, few by-products are generated in the reaction process, and the product has stable properties; 3) the synthesis process is simple, the reaction product is easy to separate, the separated noble metal catalyst and the solvent can be recycled, the reaction process is energy-saving and environment-friendly, and the method has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation.
Background
2, 5-tetrahydrofuran dimethanol is used as a bio-based platform derivative, has an oxygen-containing rigid ring structure and a symmetrical diol functional group, can be widely applied to the fields of solvents, surfactants, polyesters and the like, and is expected to show unique advantages in the aspects of barrier property, dyeing property, degradability and the like.
The traditional method for preparing 2, 5-tetrahydrofuran dimethanol is mainly a microbiological method, and the method has the problems of difficulty in controlling reaction, low production efficiency and yield, generation of a large amount of waste materials and waste liquids and the like, and is difficult to realize industrial large-scale production. The method for preparing 2, 5-tetrahydrofuran dimethanol by a one-step method reported in recent years also has the problems of high hydrogen pressure, large amount of noble metal catalyst and the like, so that the real industrial production is difficult to realize. For example, the method for preparing 2, 5-tetrahydrofuran dimethanol by one-step hydrogenation reduction disclosed in chinese patent application CN113666891A, uses 5-hydroxymethylfurfural as a raw material, and performs a first-stage reaction and a second-stage reaction in the presence of a supported noble metal catalyst (such as Pd/C, Pt/C) in a hydrogen-containing atmosphere, wherein the first-stage reaction temperature is 90-130 ℃, the pressure is 2-5MPa, the time is 1-3h, the second-stage reaction temperature is 150-170 ℃, the pressure is 6.5-10MPa, and the time is 4-10h, and the obtained 2, 5-tetrahydrofuran dimethanol has high yield and good purity. However, the method requires a higher hydrogen pressure and a larger amount of noble metal catalyst in the production process, has higher requirement on the pressure resistance of equipment, and is not beneficial to controlling the production cost.
Therefore, there is a need for a low-cost process for producing 2, 5-tetrahydrofuran dimethanol which is suitable for industrial production.
Disclosure of Invention
First, technical problem to be solved
The invention mainly solves the technical problem of providing the preparation method of the 2, 5-tetrahydrofuran dimethanol, which has low cost and is suitable for industrial production. The method takes 5-hydroxymethylfurfural as a raw material, adopts two-step hydrogenation to prepare the 2, 5-tetrahydrofuran dimethanol, can ensure the purity and yield of a final product, can reduce the requirement on high pressure resistance of equipment, improves the safety of reaction, enables the equipment to be more suitable for industrial production, and greatly reduces the production cost.
Second, technical scheme
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation takes 5-hydroxymethylfurfural as a raw material, and respectively carries out a first-stage reaction and a second-stage reaction in a hydrogen atmosphere to prepare 2, 5-tetrahydrofuran dimethanol;
the first reaction catalyst of the first stage reaction is a non-noble metal oxide catalyst, the first reaction temperature is 140-;
the second reaction catalyst of the second stage reaction is a supported noble metal catalyst, the second reaction temperature is 140-.
As a preferred embodiment, the purity of the 5-hydroxymethylfurfural is 50% to 99%.
As a preferred embodiment, the reaction is carried out in the presence of a solvent. The solvent is one or more of methanol, ethanol, 1, 4-dioxane, water, isopropanol and n-hexane.
Preferably, the solvent is analytically pure (concentration > 99.8%) absolute ethanol.
Preferably, the dosage ratio of the solvent to the 5-hydroxymethylfurfural is 20-50 mL: 2-10 g.
As a preferred embodiment, the non-noble metal element in the non-noble metal oxide catalyst is one or more of copper, manganese, nickel, zinc, aluminum and zirconium, and more preferably one or more of copper, zinc and aluminum.
Preferably, the non-noble metal oxide catalyst is a copper zinc aluminium catalyst.
As a preferred embodiment, the non-noble metal oxide catalyst is used in an amount of 2% to 15%, more preferably 4% to 12% of 5-hydroxymethylfurfural.
As a preferred embodiment, the supported noble metal catalyst includes a carrier and an active component, and the active component is supported on the carrier. The support comprises a carbon material. The active component comprises a noble metal element, and the active component exists in the form of one or more of a simple substance of the noble metal element and an oxide of the noble metal element. The mass percentage of the active component in the supported noble metal catalyst is 1-10%, and the mass of the active component is calculated by the mass of the noble metal element. The noble metal element is one or more of platinum, gold, palladium and ruthenium, and more preferably one or more of platinum, gold and palladium.
Preferably, the supported noble metal catalyst is a palladium-carbon (Pd/C) catalyst, and the palladium content is 1% to 10%.
As a preferred embodiment, the supported noble metal catalyst is used in an amount of 1% to 10%, more preferably 2% to 6% of 5-hydroxymethylfurfural.
As a preferred embodiment, the method comprises: dissolving 5-hydroxymethylfurfural in a solvent, adding a first reaction catalyst, transferring into a high-pressure reaction kettle, replacing gas for multiple times, introducing hydrogen to a first reaction pressure (for example, replacing the gas for more than 3 times by using inert gas), heating to a first reaction temperature, and carrying out a first-stage reaction; and (3) removing (such as decompressing and filtering the solution after the reaction) the first reaction catalyst after the reaction is finished, adding a second reaction catalyst, replacing the gas for multiple times, introducing hydrogen to a second reaction pressure, heating to a second reaction temperature, and then carrying out a second-stage reaction to obtain the 2, 5-tetrahydrofuran dimethanol.
As a preferred embodiment, the reaction conditions of the first stage reaction further comprise a rotation speed, and the rotation speed is controlled to be 400-800rpm, more preferably 600 rpm.
As a preferred embodiment, the first reaction temperature of the first stage reaction is 150-170 ℃, the first reaction pressure is 1.5-2.5MPa, and the first reaction time is 3-6 h. More preferably, the first reaction temperature is 160 ℃, the first reaction pressure is 2MPa, and the first reaction time is 4 h.
As a preferred embodiment, the reaction conditions of the second stage reaction further include a rotation speed, and the rotation speed is controlled to be 400-800rpm, more preferably 600 rpm.
As a preferred embodiment, the second reaction temperature of the second stage reaction is 150-170 ℃, the second reaction pressure is 2.5-3.5MPa, and the second reaction time is 4-10 h. More preferably, the second reaction temperature is 160 ℃, the second reaction pressure is 3MPa, and the second reaction time is 7 h.
The first reaction time and the second reaction time are reaction times which are started to be timed after the reaction temperature and the reaction pressure are reached.
The final product 2, 5-tetrahydrofuran dimethanol is colorless transparent viscous liquid at room temperature, has special fragrance, melting point of less than-70 deg.C, and relative density of 1.130/cm 3 (25℃)。
Third, beneficial effect
The method for preparing the 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation takes 5-hydroxymethylfurfural as a raw material, and respectively carries out a first-stage reaction and a second-stage reaction under a hydrogen atmosphere, wherein the pressure of the first-stage reaction is set to be 1-4MPa, and the pressure of the second-stage reaction is set to be 2-5 MPa. In addition, the first reaction catalyst of the method is a cheap and easily-obtained non-noble metal oxide catalyst, the second reaction catalyst is a reduced supported noble metal catalyst, and the catalyst still has high catalytic activity after being recycled, so that the cost of the catalyst required by the whole reaction is obviously reduced, and the control of the production cost of the 2, 5-tetrahydrofuran dimethanol is facilitated. Meanwhile, the final product 2, 5-tetrahydrofuran dimethanol obtained by the method has the advantages of high yield, good stability, simple reaction system, low requirement on equipment, suitability for industrial production and the like. In addition, the method can directly prepare another high value-added product, namely 2, 5-furandimethanol as an intermediate product.
Specifically, the method of the invention can produce the following beneficial effects:
(1) the used raw material 5-hydroxymethylfurfural has wide source and can be prepared from abundant renewable energy sources such as fructose, glucose and the like;
(2) compared with the existing one-step method, the reaction pressure is reduced, the consumption of the noble metal catalyst is reduced, and the industrial production cost can be greatly reduced;
(3) the final product 2, 5-tetrahydrofuran dimethanol has high yield and good purity, and byproducts generated in the reaction process are less, and the product property is stable;
(4) the separation operation of the reaction product is simple, the separated noble metal catalyst and the solvent can be recycled, the reaction process is energy-saving and environment-friendly, and the method has good industrial application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the embodiments of the present invention will be briefly described below. It is obvious that the drawings described below are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a chemical reaction scheme of a two-step hydrogenation process for preparing 2, 5-tetrahydrofuran dimethanol according to example 1 of the present invention;
FIG. 2 is an analytical spectrum of 2, 5-tetrahydrofuran dimethanol prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the following examples. However, the detailed description of the embodiments is only for exemplary purposes to illustrate the technical solutions of the present invention, and does not limit the scope of the present invention. Moreover, the implementation of the technical solution of the present invention is not limited to the embodiments described in the examples. The following examples are only a part of the examples of the present invention, and not all of them.
It should be noted that, in the case of no conflict, the technical features in the embodiment of the present invention and the test example may be combined with each other.
The test methods used in the following examples and test examples are conventional unless otherwise specified. The materials, reagents and equipment used are commercially available unless otherwise specified. The copper-zinc-aluminum catalyst can be prepared by adopting a codeposition method, and the dosage ratio of copper to aluminum is 4: 1, the dosage ratio of zinc to aluminum is 4: 1; the palladium-carbon catalyst can be prepared by adopting an impregnation method, and the palladium content is 5 percent; the above catalysts are also commercially available.
The detection of 5-Hydroxymethylfurfural (HMF), 2, 5-Furandimethanol (FDM), and 2, 5-Tetrahydrofurandinol (THFDM) in the following examples and experimental examples was carried out using a GC5190 high performance gas chromatograph, model number a, of the chromatography instruments, inc: the chromatographic column is DB-WAX; the injector temperature was 250 ℃; setting the initial temperature of the column furnace to 40 ℃, and raising the temperature to 260 ℃ at 10 ℃/min (keeping the temperature for 10 min); the carrier gas is nitrogen and is 3 mL/min; the split ratio is 20: 1.
the calculation formulas of the 5-Hydroxymethylfurfural (HMF) conversion rate, the 2, 5-Furandimethanol (FDM) yield, the 2, 5-Tetrahydrofurandinol (THFDM) yield, the first reaction catalyst selectivity, and the second reaction catalyst selectivity are as follows:
formula 1: the conversion of 5-Hydroxymethylfurfural (HMF) × 100% (mass of HMF actually participating in the reaction in the first stage/mass of HMF as raw material);
formula 2: 2, 5-Furandimethanol (FDM) conversion (mass of the second stage reaction FDM actually participating in the reaction/mass of FDM in the first stage reaction product) x 100%;
formula 3: 2, 5-Furandimethanol (FDM) yield (mass of FDM in the first stage reaction product/theoretical generated mass of FDM in the first stage reaction) × 100%;
formula 4: 2, 5-Tetrahydrofurandiol (THFDM) yield (mass of THFDM in the second stage reaction product/theoretical generated mass of THFDM in the second stage reaction) × 100%;
formula 5: first reaction catalyst selectivity ═ 100% of (FDM yield/HMF conversion);
formula 6: the second reaction catalyst selectivity (THFDM yield/FDM conversion) × 100%.
Test examples 1 to 10 were designed, and the reaction conditions of the first-stage reaction were investigated.
Test example 1
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.25g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 10%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 4MPa (the pressure is maintained at 3.7-4MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed at 600rpm, setting the heat preservation time at 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in Table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
TABLE 1 analytical results of test examples 1 to 10
| Test examples | Reaction time | FDM yield | HMF conversion | First |
| 1 | 4h | 98.59％ | 100.00％ | 98.59％ |
| 2 | 4h | 98.49％ | 100.00％ | 98.49％ |
| 3 | 4h | 98.15％ | 100.00％ | 98.15％ |
| 4 | 6h | 68.99％ | 70.78％ | 97.47％ |
| 5 | 6h | 65.90％ | 68.47％ | 96.24％ |
| 6 | 4h | 98.04％ | 100.00％ | 98.04％ |
| 7 | 4h | 98.21％ | 100.00％ | 98.21％ |
| 8 | 4h | 98.19％ | 100.00％ | 98.19％ |
| 9 | 6h | 83.18％ | 85.32％ | 97.49％ |
| 10 | 5.5h | 96.58％ | 100.00％ | 96.58％ |
Test example 2
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.25g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 10%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, replacing air with inert gas for three times, introducing hydrogen until the reaction pressure is 3MPa (the pressure is maintained at 2.7-3MPa in the reaction period), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to operate, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
As is clear from the analysis results of comparative test examples 1 and 2, when the first reaction pressure was reduced to about 3MPa, the yield of the intermediate 2, 5-furandimethanol and the conversion of the raw material 5-hydroxymethylfurfural were almost unchanged.
Test example 3
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.25g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 10%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, replacing air with inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
As is clear from the results of the analyses of comparative test examples 2 and 3, when the reaction pressure is further lowered to about 2MPa, the yield of the intermediate product, 2, 5-furandimethanol, is reduced by only 0.34%, and it is more preferable to use 2MPa for the reaction pressure from the viewpoint of economy and safety.
Test example 4
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.25g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 10%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 1MPa (the pressure is maintained at 0.7-1MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
The analysis results of comparative test examples 3 and 4 show that when the reaction pressure is further reduced to about 1MPa, the yield of the intermediate product 2, 5-furandimethanol and the conversion rate of the raw material 5-hydroxymethylfurfural are both greatly reduced, which indicates that too low reaction pressure is not favorable for the catalytic hydrogenation reaction.
Test example 5
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.25g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 10%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 150 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
The analysis results of comparative test examples 3 and 5 show that the reaction temperature is reduced to 150 ℃, the yield of the intermediate product 2, 5-furandimethanol and the conversion rate of the raw material 5-hydroxymethylfurfural are greatly reduced, and the reduction of the reaction temperature is not favorable for the catalytic hydrogenation reaction.
Test example 6
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.25g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 10%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 170 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
As is apparent from the results of comparative test examples 3 and 6, when the reaction temperature was raised to 170 ℃, the yield of 2, 5-furandimethanol as an intermediate product was slightly lowered, and it was more preferable to use 160 ℃ for the reaction temperature from the viewpoint of economy and safety.
Test example 7
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.15g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 6%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
As can be seen from the results of comparative test examples 3 and 7, the yield of intermediate 2, 5-furandimethanol and the conversion of 5-hydroxymethylfurfural as a starting material were substantially unchanged by reducing the amount of catalyst to wt 6% HMF (i.e., by reducing the ratio of the first reaction catalyst to the substrate).
Test example 8
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.1g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight of 4%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
As is clear from the analysis results of comparative test examples 3, 7 and 8, the amount of catalyst was further reduced to wt 4% HMF, and the yield of intermediate 2, 5-furandimethanol and the conversion of the starting material, 5-hydroxymethylfurfural, were almost unchanged.
Test example 9
2.5g of 5-hydroxymethyl furfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.075g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight percentage of 3%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, replacing air with inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, and then the first reaction catalyst is filtered out, so that reaction liquid containing the 2, 5-furandimethanol is obtained.
The analysis results of comparative test examples 3 and 7-9 show that further reduction of the catalyst dosage to 3 wt% of HMF significantly reduces the yield of intermediate 2, 5-furandimethanol and the conversion of 5-hydroxymethylfurfural as the raw material, indicating that too low a catalyst dosage is not favorable for the catalytic hydrogenation reaction.
Test example 10
5g of 5-hydroxymethylfurfural raw material and 30mL of ethanol are added into the polytetrafluoroethylene lining, and then 0.2g of copper-zinc-aluminum catalyst is added, wherein the catalyst is HMF with the weight percentage of 4%. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 6h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 1. After the reaction is finished, when the temperature of the reaction kettle is cooled to room temperature, releasing gas in the reaction kettle, and then filtering out the first reaction catalyst to obtain reaction liquid containing the 2, 5-furandimethanol.
As is apparent from the analysis results of comparative test examples 8 and 10, the yield of 2, 5-furandimethanol as an intermediate product was decreased by 1.61% when the substrate concentration was increased, and the substrate concentration was increased as appropriate from the viewpoint of economy.
Experimental examples 11 to 18 were designed, and the reaction conditions of the second stage reaction were investigated.
Test example 11
After the optimal reaction conditions for preparing the intermediate product FDM from the HMF with lower concentration in the experimental example 8 in the 50mL reaction kettle are obtained, the reaction is amplified to the 5L reaction kettle for the first-stage reaction, and the obtained analysis result is almost not different from the analysis result of the 50mL reaction kettle, so that the amplification production can be carried out.
The scale-up procedure was carried out according to the reaction conditions of test example 8, in which 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to a polytetrafluoroethylene liner, followed by the addition of 0.15g of palladium on carbon catalyst, which was wt 6% HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 150 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 10h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in Table 2. After the reaction is finished, when the temperature of the reaction kettle is cooled to room temperature, releasing gas in the reaction kettle, and then filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
TABLE 2 analytical results of test examples 11 to 18
Test example 12
In the same manner as in test example 11, 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to a polytetrafluoroethylene liner, followed by 0.15g of palladium on carbon catalyst, which was wt 6% HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle. After air is replaced by inert gas for three times, hydrogen is introduced until the reaction pressure is 3MPa (the pressure is maintained at 2.7-3MPa during the reaction), the reaction temperature is set to be 150 ℃, the rotation speed is adjusted to be 600rpm, the heat preservation time is set to be 10 hours, the reaction kettle is started to run, samples are taken according to the change condition of the reaction pressure in the middle for GC analysis, and the analysis result is shown in the table 2. After the reaction is finished, when the temperature of the reaction kettle is cooled to room temperature, releasing gas in the reaction kettle, and then filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
The analysis results of the comparative test examples 11 and 12 show that when the reaction pressure is increased to about 3MPa, the yield of the final product 2, 5-tetrahydrofuran dimethanol and the conversion rate of the intermediate product 2, 5-furan dimethanol are both greatly improved, which indicates that the catalytic hydrogenation reaction is facilitated by increasing the reaction pressure.
Test example 13
In the same manner as in test example 11, 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to a polytetrafluoroethylene liner, followed by 0.15g of palladium on carbon catalyst, which was wt 6% HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 2MPa (the pressure is maintained at 1.7-2MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed to 600rpm, setting the heat preservation time to 10h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 2. After the reaction is finished, when the temperature of the reaction kettle is cooled to room temperature, releasing gas in the reaction kettle, and then filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
The analysis results of comparative test examples 11 and 13 show that when the reaction temperature is increased to 160 ℃, the yield of the final product 2, 5-tetrahydrofuran dimethanol and the conversion rate of the intermediate product 2, 5-furan dimethanol are greatly improved, but a small amount of 2, 5-furan dimethanol is not completely converted, which indicates that the catalytic hydrogenation reaction is facilitated by increasing the reaction temperature.
Test example 14
In the same manner as in test example 11, 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to a polytetrafluoroethylene liner, followed by 0.15g of palladium on carbon catalyst, which was wt 6% HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 3MPa (the pressure is maintained at 2.7-3MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed at 600rpm, setting the heat preservation time at 10h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 2. And after the reaction is finished, cooling the temperature of the reaction kettle to room temperature, releasing gas in the reaction kettle, and filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
The analysis results of comparative test examples 11 to 14 show that increasing the reaction pressure and increasing the reaction temperature greatly increase the yield of the final product 2, 5-tetrahydrofuran dimethanol and the conversion rate of the intermediate product 2, 5-furan dimethanol, and shorten the reaction time, which indicates that the reaction pressure is 3MPa and the reaction temperature is 160 ℃.
Test example 15
In the same manner as in test example 11, 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to a polytetrafluoroethylene liner, followed by 0.075g of palladium on carbon catalyst, which is now wt 3% HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 3MPa (the pressure is maintained at 2.7-3MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed at 600rpm, setting the heat preservation time at 10h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 2. And after the reaction is finished, cooling the temperature of the reaction kettle to room temperature, releasing gas in the reaction kettle, and filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
As can be seen from the results of comparing test examples 14 and 15, the yield of the final product 2, 5-tetrahydrofuran dimethanol and the conversion of the intermediate product 2, 5-furan dimethanol were almost unchanged by reducing the amount of catalyst to wt 3% HMF (i.e., by reducing the ratio of the second reaction catalyst to the substrate).
Test example 16
In the same manner as in test example 11, 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to a polytetrafluoroethylene liner, followed by 0.0375g of palladium on carbon catalyst, which was now 1.5% by weight HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 3MPa (the pressure is maintained at 2.7-3MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed at 600rpm, setting the heat preservation time at 10h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 2. And after the reaction is finished, cooling the temperature of the reaction kettle to room temperature, releasing gas in the reaction kettle, and filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
As can be seen from the results of comparative test examples 14 to 16, the time required for further reducing the amount of catalyst to complete conversion of 1.5 wt% of HMF, 2, 5-furandimethanol was prolonged by 1 hour, but the yield of the final product 2, 5-tetrahydrofurandinol and the conversion of the intermediate product 2, 5-furandimethanol were almost unchanged.
Test example 17
In the same manner as in test example 11, 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to a polytetrafluoroethylene liner, followed by 0.025g of palladium on carbon catalyst, which was wt 1% HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 3MPa (the pressure is maintained at 2.7-3MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed at 600rpm, setting the heat preservation time at 10h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 2. And after the reaction is finished, cooling the temperature of the reaction kettle to room temperature, releasing gas in the reaction kettle, and filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
As can be seen from the results of the analyses of comparative test examples 16 and 17, when the amount of catalyst used was further reduced to wt 1% HMF, the reaction time was extended by 3 hours, and the yield of the final product, 2, 5-tetrahydrofuran dimethanol, and the conversion of the intermediate product, 2, 5-furan dimethanol, were slightly reduced. In view of further conducting the higher concentration test, the reaction conditions of test example 16 were adopted as the optimum reaction conditions for the second stage reaction.
Test example 18
After obtaining the optimal reaction conditions for preparing the intermediate product FDM from the HMF with higher concentration in the experimental example 10 in the 50mL reaction kettle, amplifying the optimal reaction conditions to a 5L reaction kettle for carrying out the first-stage reaction, wherein the obtained analysis result is almost not different from the analysis result of the 50mL reaction kettle, so that the amplification production can be carried out.
The scale-up procedure was carried out according to the reaction conditions of test example 10, except that 32mL of the first reaction catalyst filtered solution containing 2, 5-furandimethanol obtained after the end of the first stage reaction was added to the polytetrafluoroethylene liner, followed by 0.075g of palladium on carbon catalyst, which is now 1.5% by weight of HMF. Transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, after air is replaced by inert gas for three times, introducing hydrogen until the reaction pressure is 3MPa (the pressure is maintained at 2.7-3MPa during the reaction), setting the reaction temperature at 160 ℃, adjusting the rotating speed at 600rpm, setting the heat preservation time at 10h, starting the reaction kettle to run, sampling according to the change condition of the reaction pressure in the middle, and carrying out GC analysis, wherein the analysis result is shown in the table 2. And after the reaction is finished, cooling the temperature of the reaction kettle to room temperature, releasing gas in the reaction kettle, and filtering out a second reaction catalyst to obtain reaction liquid containing the 2, 5-tetrahydrofuran dimethanol.
As is clear from the results of the analyses of comparative examples 16 and 18, it was found that the reaction time required to be prolonged by 1.5 hours and the yield of the final product, 2, 5-tetrahydrofuran dimethanol, was slightly decreased, but the production efficiency was approximately doubled, and the increase in the substrate concentration was economically advantageous for industrial scale production.
Example 1
In this example, a chemical reaction scheme of the method for preparing 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation is shown in fig. 1, and specifically includes the following steps:
(1) first stage reaction
Adding 2.5g of 5-hydroxymethylfurfural raw material and 30mL of ethanol into a polytetrafluoroethylene lining of a 50mL reaction kettle, and then adding 0.1g of copper-zinc-aluminum catalyst, wherein the catalyst is HMF with the weight of 4%; transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, replacing air with inert gas for three times, introducing hydrogen until the first reaction pressure is 2MPa (maintaining the pressure at 1.7-2MPa during the reaction), setting the first reaction temperature at 160 ℃, adjusting the rotation speed at 600rpm, setting the heat preservation time at 4h, and starting the reaction kettle to run; after the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, then the first reaction catalyst is filtered, reaction liquid containing the 2, 5-furandimethanol is obtained, and GC analysis is carried out on the reaction liquid. The analysis results were substantially the same as those of test example 8.
(2) Second stage reaction
Adding 32mL of 2, 5-furandimethanol reaction solution obtained by the first-stage reaction into a polytetrafluoroethylene lining of a 50mL reaction kettle, and then adding 0.0375g of palladium-carbon catalyst, wherein the catalyst is HMF (1.5 wt%); transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, replacing air with inert gas for three times, introducing hydrogen until the second reaction pressure is 3MPa (maintaining the pressure at 2.7-3MPa during the reaction), setting the second reaction temperature at 160 ℃, adjusting the rotation speed at 600rpm, setting the heat preservation time at 7h, and starting the reaction kettle to run; after the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, then a second reaction catalyst is filtered, reaction liquid containing 2, 5-tetrahydrofuran dimethanol is obtained, the reaction liquid is subjected to reduced pressure distillation at 38 ℃ to remove ethanol, then the reaction liquid is subjected to reduced pressure distillation at 160 ℃ to remove other impurities, finally the final product is subjected to GC analysis, the analysis spectrogram is shown in figure 2, and the analysis data is shown in the following table 3. The analysis results were substantially the same as those of test example 16.
Table 3 analytical results of example 1
As is clear from Table 3, the end product, 2, 5-tetrahydrofuran dimethanol, was designated by number 2, and the purity was > 99%.
Example 2
The method for preparing 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation in the embodiment comprises the following steps:
(1) first stage reaction
Adding 5g of 5-hydroxymethylfurfural raw material and 30mL of ethanol into a polytetrafluoroethylene lining of a 50mL reaction kettle, and then adding 0.2g of copper-zinc-aluminum catalyst, wherein the catalyst is HMF (high molecular weight polyethylene) with the weight of 4%; transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, replacing air with inert gas for three times, introducing hydrogen until the first reaction pressure is 2MPa (maintaining the pressure at 1.7-2MPa during the reaction), setting the first reaction temperature at 160 ℃, adjusting the rotating speed at 600rpm, setting the heat preservation time at 5.5h, and starting the reaction kettle to run; after the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, then the first reaction catalyst is filtered, reaction liquid containing the 2, 5-furandimethanol is obtained, and GC analysis is carried out on the reaction liquid. The analysis results were substantially the same as those of test example 10.
(2) Second stage reaction
Adding 32mL of reaction liquid of the 2, 5-furandimethanol obtained by the first-stage reaction into a polytetrafluoroethylene lining of a 50mL reaction kettle, and then adding 0.075g of palladium-carbon catalyst, wherein the catalyst is HMF with the weight of 1.5%; transferring the polytetrafluoroethylene lining into a high-pressure reaction kettle, replacing air with inert gas for three times, introducing hydrogen until the second reaction pressure is 3MPa (maintaining the pressure at 2.7-3MPa during the reaction), setting the second reaction temperature at 160 ℃, adjusting the rotation speed at 600rpm, setting the heat preservation time at 8.5h, and starting the reaction kettle to run; after the reaction is finished, the temperature of the reaction kettle is cooled to room temperature, gas in the reaction kettle is released, then a second reaction catalyst is filtered out, reaction liquid containing 2, 5-tetrahydrofuran dimethanol is obtained, and GC analysis is carried out on the reaction liquid. The analysis results were substantially the same as those of test example 18.
In summary, the method for preparing 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation provided by the invention takes 5-hydroxymethylfurfural as a raw material, and performs the first-stage reaction and the second-stage reaction respectively in a hydrogen atmosphere, and has the following beneficial effects: 1) the source of the raw material 5-hydroxymethylfurfural is wide and renewable; 2) compared with the prior one-step method, the reaction pressure is reduced, the consumption of the noble metal catalyst is reduced, and the industrial production cost is greatly reduced; 3) the final product 2, 5-tetrahydrofuran dimethanol has high yield and good purity, generates fewer by-products in the reaction process, has high product activity and stable property, and has good application in various fields; 4) the synthesis process is simple, the separation operation of the reaction product is simple, the separated noble metal catalyst and the solvent can be recycled, the reaction process is energy-saving and environment-friendly, and the method has good industrial application prospect.
The above are merely examples of the present invention, and do not limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications and variations can be made in the embodiments of the present invention without departing from the technical spirit of the invention. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing 2, 5-tetrahydrofuran dimethanol by two-step hydrogenation is characterized in that: the method comprises the steps of taking 5-hydroxymethylfurfural as a raw material, and respectively carrying out a first-stage reaction and a second-stage reaction in a hydrogen atmosphere to obtain 2, 5-tetrahydrofuran dimethanol;
the first reaction catalyst of the first stage reaction is a non-noble metal oxide catalyst, the first reaction temperature is 140-;
the second reaction catalyst of the second stage reaction is a supported noble metal catalyst, the second reaction temperature is 140-.
2. The two-step hydrogenation process for producing 2, 5-tetrahydrofuran dimethanol according to claim 1, wherein: the reaction is carried out in the presence of a solvent, wherein the solvent is one or more of methanol, ethanol, 1, 4-dioxane, water, isopropanol and n-hexane; the dosage ratio of the solvent to the 5-hydroxymethylfurfural is 20-50 mL: 2-10 g.
3. The two-step hydrogenation process for producing 2, 5-tetrahydrofuran dimethanol according to claim 1, wherein: the non-noble metal element in the non-noble metal oxide catalyst is one or more of copper, manganese, nickel, zinc, aluminum and zirconium, preferably one or more of copper, zinc and aluminum.
4. The two-step hydrogenation process for producing 2, 5-tetrahydrofuran dimethanol according to claim 1 or 3, wherein: the non-noble metal oxide catalyst is a copper-zinc-aluminum catalyst; the dosage of the non-noble metal oxide catalyst is 2-15%, preferably 4-12% of that of 5-hydroxymethylfurfural.
5. The two-step hydrogenation process for producing 2, 5-tetrahydrofuran dimethanol according to claim 1, wherein: the supported noble metal catalyst comprises a carrier and an active component, wherein the active component is supported on the carrier, and the mass percentage of the active component is 1-10%;
the support comprises a carbon material;
the active component comprises a noble metal element, the noble metal element is one or more of platinum, gold, palladium and ruthenium, and preferably one or more of platinum, gold and palladium.
6. The two-step hydrogenation method for producing 2, 5-tetrahydrofuran dimethanol according to claim 1 or 5, wherein: the supported noble metal catalyst is a palladium-carbon catalyst; the dosage of the supported noble metal catalyst is 1-10% of that of 5-hydroxymethylfurfural, and preferably 2-6%.
7. The method for preparing 2, 5-tetrahydrofuran dimethanol through two-step hydrogenation according to claim 1, wherein: the method comprises the following steps: dissolving 5-hydroxymethylfurfural in a solvent, adding a first reaction catalyst, transferring the mixture into a high-pressure reaction kettle, replacing gas for multiple times, introducing hydrogen to a first reaction pressure, heating to a first reaction temperature, and carrying out a first-stage reaction; and (3) removing (such as decompressing and filtering the solution after the reaction) the first reaction catalyst after the reaction is finished, adding a second reaction catalyst, replacing the gas for multiple times, introducing hydrogen to a second reaction pressure, heating to a second reaction temperature, and then carrying out a second-stage reaction to obtain the 2, 5-tetrahydrofuran dimethanol.
8. The two-step hydrogenation process for producing 2, 5-tetrahydrofuran dimethanol according to claim 7, wherein: the first reaction temperature of the first-stage reaction is 150-;
preferably, the first reaction temperature is 160 ℃, the first reaction pressure is 2MPa, and the first reaction time is 4 h.
9. The two-step hydrogenation process for producing 2, 5-tetrahydrofuran dimethanol according to claim 7, wherein: the second reaction temperature of the second stage reaction is 150-170 ℃, the second reaction pressure is 2.5-3.5MPa, and the second reaction time is 4-10 h;
preferably, the second reaction temperature is 160 ℃, the second reaction pressure is 3MPa, and the second reaction time is 7 h.
10. The two-step hydrogenation process for producing 2, 5-tetrahydrofuran dimethanol according to claim 1 or 7, wherein: the reaction conditions of the first stage reaction and the second stage reaction further include a rotation speed, and the rotation speed is controlled to be 400-800rpm, preferably 600 rpm.
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| CN116813574A (en) * | 2023-06-07 | 2023-09-29 | 中国科学院大连化学物理研究所 | A kind of preparation method of 2,5-tetrahydrofurandimethanol |
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