CN109678654B - Method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural - Google Patents
Method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural Download PDFInfo
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- CN109678654B CN109678654B CN201910069482.9A CN201910069482A CN109678654B CN 109678654 B CN109678654 B CN 109678654B CN 201910069482 A CN201910069482 A CN 201910069482A CN 109678654 B CN109678654 B CN 109678654B
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- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 40
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000012265 solid product Substances 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052755 nonmetal Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 229910020674 Co—B Inorganic materials 0.000 description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 2
- NPWYTMFWRRIFLK-UHFFFAOYSA-N 3,4-dihydro-2h-pyran-2-carbaldehyde Chemical compound O=CC1CCC=CO1 NPWYTMFWRRIFLK-UHFFFAOYSA-N 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
- 229910018058 Ni-Co-Al Inorganic materials 0.000 description 1
- 229910018144 Ni—Co—Al Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 230000009286 beneficial effect 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
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
-
- 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
- B01J23/75—Cobalt
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种5‑羟甲基糠醛加氢直接生产1,2,6‑己三醇的方法，该方法包括在溶剂存在下，采用以5‑羟甲基糠醛为原料，以非晶态合金为催化剂，在一定反应温度、氢压条件下进行加氢反应，一步法生成1,2,6‑己三醇。该方法具有己三醇收率高、反应条件温和、催化剂制备成本低和反应后分离简单的优点，具备良好的工业化应用前景。The invention relates to a method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethyl furfural. The method comprises using 5-hydroxymethyl furfural as a raw material in the presence of a solvent, and using amorphous state The alloy is used as a catalyst, and the hydrogenation reaction is carried out under a certain reaction temperature and hydrogen pressure to generate 1,2,6-hexanetriol in one step. The method has the advantages of high hexanetriol yield, mild reaction conditions, low catalyst preparation cost and simple separation after the reaction, and has good industrial application prospects.
Description
Technical Field
The invention belongs to the technical field of hydrogenation, and particularly relates to a method for directly producing 1,2, 6-hexanetriol by hydrogenating 5-hydroxymethylfurfural.
Background
1,2, 6-hexanetriol has very important application in industry, is an important intermediate for synthesizing polyurethane resin, alkyd resin, plasticizer and lubricant, can be used as an extraction solvent with excellent performance, can be used as a solvent of saccharides such as xylose, arabinose, glucose and the like, is widely applied to extraction of various products, and can also be used as a low-toxicity expanding agent. At present, 1,2, 6-hexanetriol is industrially produced mainly based on a fossil resource path and is mainly prepared by hydrolyzing and hydrogenating acrolein dimer. The process route has the defects of high cost of reaction raw materials, non-regeneration, multiple process steps, high emission and the like.
The biomass resource is a renewable organic carbon source, has the characteristics of wide distribution, low price, easy obtainment, neutral carbon and the like, and is widely concerned by chemical workers at home and abroad in recent years when the biomass and the derivatives thereof are used for preparing liquid fuels and fine chemicals. Biomass-derived furans, typically 5-hydroxymethylfurfural, can be obtained from the dehydration of hexoses. 5-hydroxymethylfurfural has been listed as an important biomass platform compound and can be directionally converted into a variety of Chemical products by catalytic means, including 1,2, 6-hexanetriol, 1, 6-hexanediol, 2, 5-furandicarboxylic acid, 2, 5-dimethylfuran, levulinic acid, etc. (Chemical reviews,2013,113: 1499-1597.). The 5-hydroxymethylfurfural is used as a reaction raw material to directly produce the 1,2, 6-hexanetriol, and the defects of high raw material cost and multiple reaction steps of the existing process can be overcome.
The 1,2, 6-hexanetriol prepared by hydrogenation of 5-hydroxymethylfurfural can be obtained by direct hydrogenolysis of furan ring under the action of a hydrogenation catalyst. The literature reports that 1,2, 6-hexanetriol with the highest concentration of 64.5 percent is obtained by using Ni-Co-Al composite oxide (ACS Sustain. chem. Eng.2014,2:173-180) as a catalyst and methanol as a solvent and reacting for 12 hours under the conditions of 120 ℃ and 4.0 MPa. Patent CN 107001197A discloses a method for obtaining 1,2, 6-hexanetriol by using a multi-step continuous hydrogenation method, under the temperature of 80-180 ℃ and the pressure of 50-2000psi, taking water as a solvent to carry out reaction, firstly, carrying out hydrogenation on 5-hydroxymethylfurfural under the action of Ni, Co, Cu, Ag, Pt, Pd, Fe or Ru hydrogenation metal to obtain 2, 5-hydroxymethylfuran, then, continuously carrying out hydrogenation under the action of Ni, Co, Cu, Ag, Pt, Pd or Ru hydrogenation metal to obtain 2, 5-hydroxymethyltetrahydrofuran, and finally, carrying out hydrogenolysis on the 2, 5-hydroxymethyltetrahydrofuran under the action of a composite hydrogenation catalyst modified by adding Mo, La, Sm, Y, W or Re to obtain 1,2, 6-hexanetriol.
Disclosure of Invention
The invention provides a novel method for directly producing 1,2, 6-hexanetriol by hydrogenating 5-hydroxymethylfurfural, aiming at the problems of low yield of 1,2, 6-hexanetriol, multiple reaction steps and long period in the existing process for preparing 1,2, 6-hexanetriol by hydrogenating 5-hydroxymethylfurfural. The method has the advantages of high yield of target products, mild catalytic reaction conditions, low catalyst preparation cost and simple separation of the catalyst after reaction, and has good industrial application prospect.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for directly producing 1,2, 6-hexanetriol by hydrogenating 5-hydroxymethylfurfural comprises the steps of taking 5-hydroxymethylfurfural as a raw material and amorphous alloy as a catalyst, carrying out hydrogenation reaction at a certain reaction temperature under the condition of hydrogen pressure in the presence of a solvent, and generating 1,2, 6-hexanetriol by a one-step method. The amorphous alloy prepared by the invention has ferromagnetism, and the catalyst can be quickly separated and recovered through magnetic separation after reaction.
The solvent is at least one of water, ethanol, n-propanol, isopropanol, tetrahydrofuran and dioxane.
The reaction temperature is 120-180 ℃.
The reaction hydrogen pressure is 0.5-2.0 MPa.
The reaction was carried out in a batch stainless steel reaction kettle.
The reaction time is 6-24 h.
The amorphous alloy comprises metal elements and non-metal elements, wherein the metal elements are at least one of Fe, Co and Ni, the non-metal elements are at least one of B, P, and the molar ratio of the metal elements to the non-metal elements of the amorphous alloy catalyst is 1: 2-4.
The amorphous alloy is prepared by adopting a chemical reduction method, and the preparation process comprises the following steps:
a. adding water into a certain amount of metal salt, stirring and dissolving, and adding water into a certain amount of boron source and phosphorus source, stirring and dissolving for later use; the metal salt is one or more of ferric salt, cobalt salt and nickel salt.
b. Under the protection of inert gas, slowly and dropwise adding a boron source and a phosphorus source into the metal salt solution in an ice-water bath until no bubbles emerge, and filtering after reaction to obtain a solid product.
c. Washing the solid product obtained in the step b by using distilled water and absolute ethyl alcohol for 3-5 times respectively, and finally storing the obtained solid product in an anhydrous and oxygen-free atmosphere or medium.
In the preparation process of the amorphous alloy, the iron salt is one or more of ferrous chloride, ferrous sulfate and ferrous acetate; the cobalt salt is one or more of cobalt chloride, cobalt sulfate and cobalt acetate; the nickel salt is one or more of nickel chloride, nickel sulfate and nickel acetate.
The boron source is KBH4And NaBH4At least one of (1).
The phosphorus source is KH2PO2And NaH2PO2At least one of (1).
The invention has the beneficial effects that:
(1) the method takes 5-hydroxymethylfurfural as a raw material, takes amorphous alloy consisting of at least one metal element selected from Fe, Co and Ni and at least one non-metal element selected from B and P as a catalyst, controls the molar ratio of the metal element to the non-metal element in the amorphous alloy, and carries out reaction in an intermittent stainless steel reaction kettle, and can directly produce 1,2, 6-hexanetriol by one step through hydrogenation at the reaction temperature of 120-180 ℃, the reaction pressure of 0.5-2.0 MPa and the reaction time of 6-24 h.
(2) The 5-hydroxymethylfurfural derived from cheap renewable biomass resources is used for replacing fossil raw materials to produce 1,2, 6-hexanetriol, and the raw materials are rich in source and low in cost; the amorphous alloy is used as a catalytic material, so that the yield of the target product 1,2, 6-hexanetriol is high, the reaction condition is mild, and the catalyst cost is low.
(3) The amorphous alloy adopted by the invention has ferromagnetism, and the catalyst can be separated magnetically after reaction, so that the method is simple, convenient and quick and has low energy consumption.
Detailed Description
The method takes 5-hydroxymethylfurfural as a raw material, takes amorphous alloy consisting of at least one metal element selected from Fe, Co and Ni and at least one non-metal element selected from B and P as a catalyst, carries out reaction in an intermittent stainless steel reaction kettle, and directly hydrogenates to produce the 1,2, 6-hexanetriol in one step, wherein the reaction temperature is 120-180 ℃, the reaction pressure is 0.5-2.0 MPa, and the reaction time is 6-24 h.
In the invention, the amorphous alloy catalyst is prepared firstly, and the preparation process of the catalyst comprises the following steps:
a. adding water into a certain amount of ferric salt, cobalt salt and nickel salt, stirring and dissolving, and adding water into a certain amount of boron source and phosphorus source, stirring and dissolving for later use.
b. Under the protection of inert gas, slowly and dropwise adding a boron source and a phosphorus source into the metal salt solution at a certain speed in an ice-water bath until no bubbles emerge, and filtering after reaction to obtain a solid product.
c. Washing the solid product obtained in the step b by using distilled water and absolute ethyl alcohol for 3-5 times respectively, and finally storing the sample in an anhydrous and oxygen-free atmosphere or medium.
The present invention is further illustrated in detail by the following specific examples, but the scope of the present invention is not limited thereto.
The first embodiment is as follows: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method comprises the following steps: 11.9g of cobalt chloride hexahydrate and 150mL of water were added to a 500mL round-bottomed flask, dissolved with stirring and placed in an ice-water bath, and 6.75g of KBH was added4Dissolving in 150mL of water, placing in a dropping funnel, slowly and dropwise adding into the round-bottom flask under the protection of nitrogen, reacting rapidly, and discharging a large amount of gas to generate Co-B precipitate. And when no gas is generated, filtering to obtain a solid product, sequentially washing the solid product for 3-5 times by using deionized water and absolute ethyl alcohol respectively, and finally storing the sample in the absolute ethyl alcohol for later use. 0.2g of Co-B amorphous alloy catalyst, 0.5g of 5-hydroxymethylfurfural and 10.0mL of ethanol are put into a 50mL stainless steel reaction kettle with polytetrafluoroethylene and reacted for 12 hours at the temperature of 140 ℃ and the pressure of 1.5 MPa.
Example two: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method comprises the following steps: 5.95g of cobalt chloride hexahydrate, 5.95g of nickel chloride hexahydrate and 150mL of water were added to a 500mL round bottom flask, dissolved with stirring and placed on iceIn a water bath, another 6.75g of KBH was added4Dissolving in 150mL of water, placing in a dropping funnel, slowly and dropwise adding into the round-bottom flask under the protection of nitrogen, reacting rapidly, and discharging a large amount of gas to generate Co-Ni-B precipitate. And when no gas is generated, filtering to obtain a solid product, sequentially washing the solid product for 3-5 times by using deionized water and absolute ethyl alcohol respectively, and finally storing the sample in the absolute ethyl alcohol for later use. 0.2g of Co-Ni-B amorphous alloy catalyst, 0.5g of 5-hydroxymethylfurfural and 10.0mL of ethanol are put into a 50mL stainless steel reaction kettle with polytetrafluoroethylene and reacted for 12 hours at the temperature of 160 ℃ and the pressure of 1.5 MPa.
Example three: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method comprises the following steps: 11.9g of cobalt chloride hexahydrate and 150mL of water were added to a 500mL round-bottomed flask, dissolved with stirring and placed in an ice-water bath, and 4.73g of NaBH was added4And 2.75g NaH2PO2Dissolving in 150mL of water, placing in a dropping funnel, slowly and dropwise adding into the round-bottom flask under the protection of nitrogen, reacting rapidly, and discharging a large amount of gas to generate Co-P-B precipitate. And when no gas is generated, filtering to obtain a solid product, sequentially washing the solid product for 3-5 times by using deionized water and absolute ethyl alcohol respectively, and finally storing the sample in isopropanol for later use. 0.2g of Co-P-B amorphous alloy catalyst, 0.5g of 5-hydroxymethylfurfural and 10.0mL of isopropanol are put into a 50mL stainless steel reaction kettle with polytetrafluoroethylene to react for 24h at the temperature of 120 ℃ and the pressure of 1.0 MPa.
Example four: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method comprises the following steps: 5.95g of cobalt chloride hexahydrate, 3.17g of anhydrous ferrous chloride and 150mL of water were added to a 500mL round-bottomed flask, dissolved with stirring and placed in an ice-water bath, and 6.75g of KBH was added4Dissolving in 150mL of water, placing in a dropping funnel, slowly and dropwise adding into the round-bottom flask under the protection of nitrogen, reacting rapidly, and discharging a large amount of gas to generate Fe-Co-B precipitate. Filtering to obtain solid product when no gas is generated, washing the solid product with deionized water and absolute ethyl alcohol for 3-5 times respectively,and finally, storing the sample in absolute ethyl alcohol for later use. 0.2g of Fe-Co-B amorphous alloy catalyst, 5.0g of 5-hydroxymethylfurfural and 10.0mL of ethanol are put into a 50mL stainless steel reaction kettle with polytetrafluoroethylene and reacted for 20 hours at the temperature of 150 ℃ and the pressure of 1.2 MPa.
Comparative example one: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The preparation method is basically the same as that of the first embodiment, and the difference from the first embodiment is that: the reaction temperature was 100 ℃.
Comparative example two: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method is basically the same as that of the first embodiment, and the difference from the first embodiment is that: the reaction temperature was 200 ℃.
Comparative example three: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method is basically the same as that of the first embodiment, and the difference from the first embodiment is that: the pressure of the reaction was: 0.3 MPa.
Comparative example four: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method is basically the same as that of the first embodiment, and the difference from the first embodiment is that: the pressure of the reaction was 2.5 MPa.
Comparative example five: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method is basically the same as that of the first embodiment, and the difference from the first embodiment is that: KBH4Was used in an amount of 2.7g, and the molar ratio of Co to B was 1: 1.
Comparative example six: method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural
The production method is basically the same as that of the first embodiment, and the difference from the first embodiment is that: KBH4Was used in an amount of 13.5g, and the molar ratio of Co to B was 1: 5.
The conversion of 5-hydroxymethylfurfural and the selectivity of 1,2, 6-hexanetriol produced in the above examples one to five and comparative examples one to six are shown in the following table:
from the experimental data, the method for directly producing 1,2, 6-hexanetriol by hydrogenating 5-hydroxymethylfurfural provided by the invention has the advantages that the conversion rate of 5-hydroxymethylfurfural is high, and the selectivity of 1,2, 6-hexanetriol is high and is higher than that of the first to sixth comparative examples.
Claims (5)
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