CN113061122A - Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran - Google Patents
Preparation method of 2, 5-dihydroxymethyl tetrahydrofuran Download PDFInfo
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- CN113061122A CN113061122A CN202110277384.1A CN202110277384A CN113061122A CN 113061122 A CN113061122 A CN 113061122A CN 202110277384 A CN202110277384 A CN 202110277384A CN 113061122 A CN113061122 A CN 113061122A
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- catalyst
- transition metal
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- hydroxymethylfurfural
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- YCZZQSFWHFBKMU-UHFFFAOYSA-N [5-(hydroxymethyl)oxolan-2-yl]methanol Chemical compound OCC1CCC(CO)O1 YCZZQSFWHFBKMU-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 32
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 26
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 23
- 150000003624 transition metals Chemical group 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- -1 alcohol compound Chemical class 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000011156 evaluation Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- C07D307/04—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The application discloses a preparation method of 2, 5-dihydroxymethyl tetrahydrofuran, which comprises the following steps: in a hydrogen-containing atmosphere, reacting a material containing 5-hydroxymethylfurfural in the presence of a catalyst to obtain the 2, 5-dihydroxymethyltetrahydrofuran; the catalyst comprises an active component and a carrier; the active component is loaded on the carrier; the active component is selected from transition metals; the transition metal is selected from nickel. The method takes 5-hydroxymethylfurfural as a raw material, realizes the high-efficiency preparation of the 2, 5-dihydroxymethyltetrahydrofuran by adjusting the temperature and the pressure, and has good industrial application prospect.
Description
Technical Field
The application relates to a preparation method of 2, 5-dihydroxymethyl tetrahydrofuran, belonging to the technical field of chemical production.
Background
Along with the development and progress of society, the demand of human beings on non-renewable fossil resources is increasing, so that the environmental pollution, the energy crisis and the like caused by the increasing demand are more severe, and the green sustainable development provided by the new era is challenged. In order to solve the above problems, it is necessary to find a substitute for non-renewable fossil resources. The biomass is used as a raw material, various platform-based compounds can be obtained through treatment, and various valuable chemicals can be obtained through the easy conversion of the platform-based compounds.
2, 5-dimethyloltetrahydrofuran is commonly used as a precursor for the processing of polyols or some polymers, and since 2, 5-dimethyloltetrahydrofuran is liquid at room temperature, it is also used as a solvent for some interconversion between carbohydrates (Renewable and stable Energy Reviews 74(2017) 230-. The liquid obtained by esterifying 2, 5-dihydroxymethyl tetrahydrofuran with acid has good lubricating effect, can be used on heavy equipment such as trucks, tanks and the like, and the solid has the characteristic of good toughness. 2, 5-dihydroxymethyl tetrahydrofuran can obtain various etherification products through the reaction with alcohol, and the etherification products can effectively improve the ignition point of gasoline when used as an additive in gasoline. In addition, the 2, 5-dihydroxymethyl tetrahydrofuran has certain application potential in the pharmaceutical, sanitary and textile energy industries.
Starting from 5-hydroxymethylfurfural as a raw material, it is difficult to reduce aldehyde groups in the 5-hydroxymethylfurfural into hydroxyl groups and fully reduce double bonds in furan rings, and further hydrogenation reactions such as dehydroxylation, ring opening and the like cannot occur. In order to reduce the aldehyde group in 5-hydroxymethylfurfural to hydroxyl group and completely reduce the double bond in furan ring, noble metal supported carbon carrier or oxide is often used as catalyst in literature, but the yield is not very high, mainly because the noble metal catalyst is very easy to destroy the hydroxymethyl group in 2, 5-dihydroxymethyltetrahydrofuran in the hydrogenation reduction process.
Disclosure of Invention
According to one aspect of the application, the preparation method of the 2, 5-dihydroxymethyl tetrahydrofuran is provided, the catalyst with the transition metal nickel as the active component can efficiently catalyze 5-hydroxymethylfurfural to prepare the 2, 5-dihydroxymethyl tetrahydrofuran by reduction, and the cost of the catalyst is greatly reduced.
The non-noble metal developed in the invention is used as the active component of the catalyst, and can realize the high-efficiency hydrogenation reduction of the 5-hydroxymethylfurfural by directional catalysis to prepare the 2, 5-dihydroxymethyltetrahydrofuran.
According to a first aspect of the present application, there is provided a method for producing 2, 5-dimethyloltetrahydrofuran, the method comprising:
in a hydrogen-containing atmosphere, reacting a material containing 5-hydroxymethylfurfural in the presence of a catalyst to obtain the 2, 5-dihydroxymethyltetrahydrofuran;
the catalyst comprises an active component and a carrier; the active component is loaded on the carrier;
the active component is selected from transition metals; the transition metal is selected from nickel.
Alternatively, the reaction i is carried out under anhydrous conditions.
Optionally, the initial 5-hydroxymethylfurfural concentration is an initial reaction concentration of 1g to 30g of feedstock in 500mL of anhydrous ethanol.
Optionally, the support is selected from oxides; the oxide is at least one of silicon dioxide, magnesium oxide, zirconium dioxide, cerium dioxide and aluminum oxide.
Optionally, the silica is selected from at least one of fumed silica and solid phase silica.
Optionally, in the catalyst, the mass content of the active component is 5-30%.
Optionally, in the catalyst, the upper limit of the mass content of the active component is independently selected from 30%, 25%, 20%, 15%, 10%, 8%, and the lower limit is independently selected from 5%, 25%, 20%, 15%, 10%, 8%.
Optionally, the conditions of reaction I are: the temperature is 70-130 ℃; the time is 3-12 h; the pressure is 3-8 MPa.
Alternatively, the upper temperature limit of reaction I is independently selected from 130 ℃, 120 ℃, 110 ℃, 100 ℃, 90 ℃, 80 ℃, and the lower temperature limit is independently selected from 70 ℃, 120 ℃, 110 ℃, 100 ℃, 90 ℃, 80 ℃.
Alternatively, the upper time limit of the reaction I is independently selected from 12h, 10h, 8h, 6h, 4h, and the lower time limit is independently selected from 1h, 10h, 8h, 6h, 4h, 3 h.
Alternatively, the upper pressure limit of reaction I is independently selected from 8MPa, 7MPa, 6MPa, 5MPa, 4MPa and the lower limit is independently selected from 3MPa, 7MPa, 6MPa, 5MPa, 4 MPa.
Optionally, a solvent is also included in the material; the solvent is selected from alcohol compounds.
Optionally, the alcohol compound is selected from at least one of ethanol, methanol and isopropanol.
Optionally, the ethanol is anhydrous ethanol.
Optionally, the mass-to-volume ratio of the 5-hydroxymethylfurfural to the solvent in the material is (1-30) g:500 mL.
Optionally, the upper limit of the mass to volume ratio of the 5-hydroxymethylfurfural and the solvent is independently selected from 30 g:500mL, 20 g:500mL, 10 g:500mL, 5 g:500 mL; the lower limit is independently selected from 1: 500mL, 20 g:500mL, 10 g:500mL, 5 g:500 mL.
Optionally, the mass ratio of the catalyst to the 5-hydroxymethylfurfural is 0.5-4.8: 1-30;
wherein the mass of the catalyst is based on the mass of the transition metal contained therein.
Optionally, the preparation method of the catalyst comprises:
(1) reacting II and roasting a mixture containing a transition metal source, a carrier and a precipitator to obtain a catalyst precursor;
(2) and reducing the catalyst precursor in a hydrogen-containing atmosphere to obtain the catalyst.
Optionally, the transition metal source is selected from at least one of transition metal salts;
the precipitant is selected from urea.
Alternatively, in the step (1), the conditions of the reaction II are: the temperature is 80-90 ℃; the time is 5-15 h;
the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 2-12 h;
in the step (2), the reduction conditions are as follows: the temperature is 300-600 ℃; the time is 2-10 h.
Optionally, the mass ratio of the transition metal source to the carrier to the precipitant is 2-45: 4-6: 2-25;
wherein the mass of the transition metal source is based on the mass of the transition metal.
Alternatively, the catalyst is prepared by adopting the following method:
(1) uniformly mixing 500mL of solution containing a nickel source with an oxide carrier;
(2) adding 100mL of precipitator water solution, and decomposing to obtain hydroxide precipitate;
(3) roasting nickel-containing powder to obtain a precursor;
(4) and reducing the precursor by adopting hydrogen to obtain the catalyst.
Optionally, in the step (1), the mass ratio of the carrier to the nickel in the 100mL of aqueous solution is 0.4-15.
Optionally, in the step (2), the mass ratio of the carrier to the urea in the 100mL of aqueous solution is 0.2-2.
Optionally, the transition metal nickel salt is selected from at least one of nickel nitrate, nickel chloride and nickel sulfate.
Optionally, the mass ratio of the catalyst to the 5-hydroxymethylfurfural is 0.5-4.8: 1-30;
wherein the mass of the catalyst is based on the mass of the transition metal contained therein.
Alternatively, the preparation method of the catalyst comprises the following steps:
s100: the solution containing the nickel source is mixed with the oxide support uniformly.
S200: adding urea aqueous solution, and mixing uniformly.
S300: and roasting the powder containing the nickel to obtain a precursor.
S400: and reducing the precursor by adopting hydrogen.
Optionally, the nickel sources in step S100 are derived from different nickel salts.
Optionally, the urea aqueous solution is added in step S200, and the uniform nickel hydroxide precipitation can be obtained by uniform stirring.
Optionally, the step S300 of calcining the powder containing nickel hydroxide and the carrier to obtain uniformly mixed nickel oxide and oxide.
Optionally, in step S400, the precursor is reduced under high-temperature hydrogen to obtain the catalyst.
The beneficial effects that this application can produce include:
1) the catalyst used in the method takes nickel as an active center, can efficiently catalyze 5-hydroxymethylfurfural to reduce and prepare 2, 5-dimethyloltetrahydrofuran, and greatly reduces the cost of the catalyst.
2) The preparation method of the catalyst provided by the application has the advantages of high catalyst activity, long service life and easiness in separation from a product after use.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the conversion of the reactants and the yield of the product were quantified by means of a High Performance Liquid Chromatograph (HPLC) model Agilent Technologies 1260 Infinity II equipped with a UV-absorption photodetector and an extended-C18 USP L1 column (4.6 mm. times.250 mm). The liquid chromatograph adopts a mixed solution of methanol and an aqueous ammonium formate solution as a mobile phase, the concentration of the aqueous ammonium formate solution is 5.0mM, and the volume ratio of the methanol to the aqueous ammonium formate solution is 1: 9, the total flow rate of the mobile phase was 0.8 mL/min.
The actual loading of the elements was quantitatively analyzed using inductively coupled plasma optical emission spectroscopy (ICP-OES) with SPECTRA ARCCOS II.
Due to the limitation of the prior art, the inventor finally provides a technical scheme through a large number of theoretical and practical analyses. The implementation of this solution is partially explained as follows.
The calculation formula of the conversion rate of the 5-hydroxymethylfurfural is as follows:
conversion rate of 5-hydroxymethylfurfural (1-molar concentration of 5-hydroxymethylfurfural after reaction)/molar concentration of initial 5-hydroxymethylfurfural
The yield of 2, 5-dimethyloltetrahydrofuran is calculated as follows:
yield of 5-hydroxymethylfurfural (i.e. molar concentration of 2, 5-dimethyloltetrahydrofuran/initial molar concentration of 5-hydroxymethylfurfural after reaction)
The nickel salts used in the examples of this application are all hexahydrate.
Example 1
Preparation of catalyst # 1
(1) Into the flask were added 4g of fumed silica and 500mL of an aqueous solution to dissolve nickel nitrate containing 6g of nickel, and the mixture was stirred at 80 ℃ for 1 hour until the dispersion became uniform.
(2) 100mL of an aqueous solution containing 10g of urea dissolved therein was added to (1), the temperature was raised to 90 ℃ and vigorously stirred for 12 hours, followed by uniform mixing.
(3) The mixture obtained by filtering in the step (2) and drying the mixture at 110 ℃ for 12 hours is calcined in a muffle furnace at 500 ℃ for 10 hours.
(4) And (4) reducing the calcined material obtained in the step (3) in a tubular furnace by using hydrogen at 450 ℃ for 5 hours. Is described as Ni/F-SiO2。
The actual loading of the catalyst was 22.3 wt% as determined by ICP-OES.
Example 2
Preparation of catalyst # 2-4 #
The preparation of catalyst # 2-4 # was different from that of catalyst # 1 in that nickel nitrate containing 10g, 3g and 0.8g of nickel was dissolved in 500mL of the aqueous solution in step (1), respectively, and the other preparation was completely identical to that of catalyst # 1. The actual loading of the catalyst was 25.6 wt%, 14.6 wt% and 6.0 wt%, respectively, as determined by ICP-OES.
Example 3
Preparation of catalyst # 5-6 #
The preparation of catalysts # 5-6 # differs from catalyst # 1 in that the nickel source in step (1) was changed to nickel chloride and nickel sulfate, respectively, and the others were completely identical to the preparation of catalyst # 1.
Example 4
Preparation of catalyst # 7-9
The preparation of catalysts 7# -9# differs from catalyst 1# in that the support in step (1) was changed from fumed silica to solid silica, zirconia and ceria, respectively, and otherwise is identical to the preparation of catalyst 1 #.
Example 5
Preparation of catalyst # 10-12 #
The preparation of catalyst # 10-12 # was different from that of catalyst # 1 in that the 100mL aqueous solution in which 10g of urea was dissolved in step (2) was changed to 18g, 13g and 5g of urea, respectively, and the other preparation was completely identical to that of catalyst # 1.
Example 6
Preparation of catalyst # 13-15 #
The preparation of catalyst # 13-15 # was different from that of catalyst # 1 in that the calcination temperatures in the muffle furnace in step (3) were changed to 700 deg.C, 600 deg.C and 400 deg.C, respectively, and the other preparation was completely identical to that of catalyst # 1.
Example 7
Preparation of catalyst # 16-18 #
The preparation of catalyst # 16-18 # was different from that of catalyst # 1 in that the hydrogen reduction temperature in the tube furnace in step (4) was changed to 600 deg.C, 500 deg.C and 360 deg.C, respectively, and the other preparation was completely identical to that of catalyst # 1.
Example 8
Evaluation of catalyst # 1 Performance
(1) 500mL of absolute ethanol and 10g of 5-hydroxymethylfurfural are added into a high-pressure reaction kettle, and after the mixture is uniformly stirred, a No. 1 catalyst containing 1g of nickel is added.
(2) And (3) introducing hydrogen, adjusting the pressure of the hydrogen to 5MPa, and introducing stirring and refluxing.
(3) The temperature rise was suspended when the temperature rose to 80 ℃.
(4) After 10 hours of reaction, the 5-hydroxymethylfurfural was completely converted, and the yield of 2, 5-dimethyloltetrahydrofuran was 94.2%.
Example 9
Evaluation of catalyst # 1 Performance
Example 9 differs from example 8 in the reaction pressure of catalyst evaluation. Other conditions were the same as in example 8. The evaluation results are shown in table 1 below:
TABLE 1
Example 10
Example 10 evaluates catalyst # 5 and differs from example 8 in the reaction temperature. Other conditions were the same as in example 8. The evaluation results are shown in table 2 below:
TABLE 2
Example 11
Example 11 evaluates catalyst # 10 and differs from example 8 also in the quality of the initial charge of 5-hydroxymethylfurfural. Other conditions were the same as in example 8. The evaluation results are shown in table 3 below:
TABLE 3
Example 12
Example 12 evaluated the catalyst # 10 and also had a difference in reaction length from example 8. Other conditions were the same as in example 8. The evaluation results are shown in table 4 below:
TABLE 4
Example 13
Example 13 the catalyst # 7-9 was evaluated under otherwise identical conditions as in example 8. The evaluation results are shown in table 5 below:
TABLE 5
Example 14
Example 14 evaluated catalyst # 17 and differed from example 8 in the content of metallic nickel. Other conditions were the same as in example 8. The evaluation results are shown in table 6 below:
TABLE 6
Example 15
Example 15# 13-15 # catalyst was evaluated and the other conditions were consistent with example 8. The evaluation results are shown in table 7 below:
TABLE 7
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing 2, 5-dihydroxymethyl tetrahydrofuran, which is characterized by comprising the following steps:
in a hydrogen-containing atmosphere, reacting a material containing 5-hydroxymethylfurfural in the presence of a catalyst to obtain the 2, 5-dihydroxymethyltetrahydrofuran;
the catalyst comprises an active component and a carrier; the active component is loaded on the carrier;
the active component is selected from transition metals; the transition metal is selected from nickel.
2. The production method according to claim 1, wherein the support is selected from the group consisting of oxides; the oxide is at least one of silicon dioxide, magnesium oxide, zirconium dioxide, cerium dioxide and aluminum oxide.
3. The method according to claim 1, wherein the active component is contained in the catalyst in an amount of 5 to 30% by mass.
4. The method according to claim 1, wherein the conditions of reaction I are: the temperature is 70-130 ℃; the time is 3-12 h; the pressure is 3-8 MPa.
5. The method according to claim 1, wherein in the material, a solvent is further included; the solvent is selected from alcohol compounds.
6. The method according to claim 5, wherein the alcohol compound is at least one selected from the group consisting of ethanol, methanol and isopropanol.
7. The preparation method according to claim 5, wherein the mass-to-volume ratio of the 5-hydroxymethylfurfural to the solvent in the material is (1-30) g:500 mL.
8. The preparation method according to claim 1, wherein the mass ratio of the catalyst to the 5-hydroxymethylfurfural is 0.5-4.8: 1-30;
wherein the mass of the catalyst is based on the mass of the transition metal contained therein.
9. The method according to claim 1, wherein the method for preparing the catalyst comprises:
(1) reacting II and roasting a mixture containing a transition metal source, a carrier and a precipitator to obtain a catalyst precursor;
(2) and reducing the catalyst precursor in a hydrogen-containing atmosphere to obtain the catalyst.
10. The production method according to claim 9, wherein the transition metal source is selected from at least one of transition metal salts;
the precipitating agent is selected from urea;
preferably, in the step (1), the conditions of the reaction II are: the temperature is 80-90 ℃; the time is 5-15 hours;
the roasting conditions are as follows: the temperature is 300-700 ℃; the time is 2-12 h;
in the step (2), the reduction conditions are as follows: the temperature is 300-600 ℃; the time is 2-10 h;
preferably, the mass ratio of the transition metal source to the carrier to the precipitant is 2-45: 4-6: 2-25;
wherein the mass of the transition metal source is based on the mass of the transition metal.
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| CN113773284A (en) * | 2021-09-16 | 2021-12-10 | 厦门大学 | Method for preparing 2, 5-dihydroxymethyl tetrahydrofuran by hydrogenation of 5-hydroxymethylfurfural |
| CN116571263A (en) * | 2023-05-15 | 2023-08-11 | 厦门大学 | Preparation method of silicon dioxide supported nickel-based catalyst and application of catalyst in hydrogenation of5-hydroxymethylfurfural |
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