CN114230437A - Method for preparing 1, 14-tetradecanediol from biomass derivative - Google Patents
Method for preparing 1, 14-tetradecanediol from biomass derivative Download PDFInfo
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- CN114230437A CN114230437A CN202111549874.9A CN202111549874A CN114230437A CN 114230437 A CN114230437 A CN 114230437A CN 202111549874 A CN202111549874 A CN 202111549874A CN 114230437 A CN114230437 A CN 114230437A
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- tetradecanediol
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- furfural
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- biomass derivatives
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- XLKZJJVNBQCVIX-UHFFFAOYSA-N tetradecane-1,14-diol Chemical compound OCCCCCCCCCCCCCCO XLKZJJVNBQCVIX-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002028 Biomass Substances 0.000 title claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 59
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 25
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 5
- 238000005580 one pot reaction Methods 0.000 claims abstract description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 20
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 239000000543 intermediate Substances 0.000 description 15
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 150000002009 diols Chemical group 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 229910020057 NbOPO4 Inorganic materials 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 238000006392 deoxygenation reaction Methods 0.000 description 7
- 238000005216 hydrothermal crystallization Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- GAGSVOVTFFOFFX-UHFFFAOYSA-D [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O Chemical compound [Nb+5].[Nb+5].OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O.OC(C(O)C([O-])=O)C([O-])=O GAGSVOVTFFOFFX-UHFFFAOYSA-D 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000007791 dehumidification Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production method for preparing 1, 14-tetradecanediol from biomass derivatives. The method comprises the steps of taking furfural, 5-hydroxymethyl furfural and acetone in a certain proportion as raw materials, carrying out aldol condensation reaction in an alkali solution for a certain time, adding acid for neutralization to obtain C14An oxygen-containing intermediate; then, directly reacting under the action of a selective hydrodeoxygenation catalyst at a certain reaction temperature under hydrogen pressure without separation to obtain the 1, 14-tetradecanediol by a one-pot method. The method has the advantages of cheap and easily available raw materials, reproducibility, mild reaction, simple separation and low production cost, and 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 1, 14-tetradecanediol from biomass derivatives.
Background
Long chain terminal diols generally refer to saturated, straight chain diols containing 10 or more carbon atoms. The 1, 14-tetradecanediol is one of long-chain end diols, the two ends of the diol have hydroxyl functional groups, and the diol can be used for synthesizing various chemical products such as polyester, spice, cosmetics, paint, plasticizer, high-grade lubricating oil and the like, and plays an important role in national economy. Because the chain segment contains long alkane chain segments, the long alkane chain segments have the property superior to short chain dihydric alcohol, so that the corresponding synthetic material has excellent performance. The current industrial production methods of long chain end diols including 1, 14-tetradecanediol are all based on petrochemical routes and are obtained by catalytic reduction of dibasic acids with the same carbon chain. For example: patent CN1410405A discloses a method for producing α, ω -long-chain dihydric alcohol, which comprises esterifying long-chain dibasic acid and low-carbon alcohol, and then performing catalytic hydrogenation reduction on the generated corresponding ester to obtain corresponding long-chain dihydric alcohol; patent CN103449971A discloses that alpha, omega-long chain end diol is obtained by directly catalyzing and hydrogenating corresponding long chain dibasic acid in a fixed bed filled with Pd, Ru, Pt composite catalyst by using ultrasonic technology. The production method of the long-chain-end diol takes the corresponding dibasic acid as the raw material, and is directly limited by the production cost of the long-chain dibasic acid, and the long-chain dibasic acid can be obtained by various ways such as traditional organic synthesis, biological fermentation, olefin metathesis, isomerization-hydrogen-oxygen carbonylation and the like, but the production cost is still higher, and a plurality of problems still need to be solved (the synthesis of the long-chain aliphatic dibasic acid and the application thereof in the polycondensation reaction, the chemical development, 2019, 31(1): 70-82). In summary, the current 1, 14-tetradecanediol mainly faces to multiple production steps and high cost, so that the price is high and the industrial application is limited. Therefore, it is of great significance to develop a relatively inexpensive process for producing 1, 14-tetradecanediol.
The biomass resource is a renewable organic carbon source and has the characteristics of wide distribution, low price, easy obtainment and the like. Furfural and 5-hydroxymethyl furfural are two important biomass platform compounds, can be prepared by dehydrating agricultural and forestry wastes such as straws and corncobs, are industrially produced at present, and can also be obtained by fermenting biomass. The method for producing the 1, 14-tetradecanediol by using the biomass-derived furfural, 5-hydroxymethyl furfural and acetone as reaction raw materials can overcome the defect of high production cost of the existing process, is favorable for comprehensive utilization of agricultural and forestry wastes, realizes green sustainable development, and has good industrial application prospect.
Disclosure of Invention
The invention aims to solve the technical problems of multiple steps and high cost of the existing preparation method of 1, 14-tetradecanediol and provides a production method for preparing 1, 14-tetradecanediol from a biomass derivative. The method has the advantages of cheap and easily available raw materials, reproducibility, mild reaction, simple separation and low production cost, 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 of producing 1, 14-tetradecanediol from a biomass derivative, comprising: taking furfural, 5-hydroxymethyl furfural and acetone in a certain proportion as raw materials, carrying out aldol condensation reaction in an aqueous solution of alkali for a certain time, adding inorganic acid for neutralization to obtain C14An oxygen-containing intermediate; then, directly reacting under the action of a selective hydrodeoxygenation catalyst at a certain reaction temperature under hydrogen pressure without separation to obtain the 1, 14-tetradecanediol by a one-pot method. The reaction process is shown in the reaction formula 1.
The molar ratio of the furfural to the 5-hydroxymethylfurfural to the acetone is 1:1: 1.
The feeding mode of the aldol condensation is as follows: adding acetone, slowly dropwise adding 5-hydroxymethylfurfural, controlling the dropwise adding time to be 0.5-2 h, and finally adding furfural.
The molar concentration of furfural in the alkali water solution is 0.25-1 mol/L.
The alkali in the alkali water solution is at least one of sodium hydroxide and potassium hydroxide, and the molar concentration of the alkali is 0.1-0.8 mol/L.
The condensation reaction temperature is 10-40 ℃.
The condensation reaction time is 8-24 h.
The inorganic acid is at least one of hydrochloric acid, sulfuric acid and phosphoric acid.
The selective hydrodeoxygenation catalyst is a supported catalyst and comprises a carrier and active metal loaded on the carrier, wherein the active metal is at least one of Ni, Pd, Ru and Pt, and the carrier is at least one of niobium pentoxide, tungsten trioxide, niobium phosphate, niobic acid and tungstic acid or a composite material of any proportion of the niobium pentoxide, the tungsten trioxide, the niobium phosphate, the niobic acid and the tungstic acid.
The loading amount of the active metal in the supported catalyst is 1.0-5.0 wt%.
The hydrodeoxygenation reaction temperature is 150-210 ℃.
The hydrogen pressure of the hydrodeoxygenation reaction is 2.0-4.0 MPa.
The hydrodeoxygenation reaction time is 8-30 h.
The preparation method of the supported catalyst comprises the following steps: dissolving a certain amount of hexadecyl trimethyl ammonium bromide in deionized water to form a solution, slowly dropping a certain amount of niobium tartrate, ammonium metatungstate and diammonium hydrogen phosphate into the solution under stirring to form a suspension, carrying out hydrothermal crystallization at 160 ℃ for 24 hours, cooling, carrying out suction filtration, washing, drying and roasting to obtain the carrier, loading active metal on the surface of the carrier by an isometric impregnation method, and drying and roasting to obtain the supported catalyst.
Preferably, the active metal is Pd, and the support is a mixture of niobium phosphate and tungsten trioxide; further preferably, the mass ratio of the niobium phosphate to the tungsten trioxide is 1: 1.
The invention has the beneficial effects that:
(1) the furfural, 5-hydroxymethyl furfural and acetone derived from biomass resources are used for replacing fossil raw materials to produce 1, 14-tetradecanediol, and the raw materials are cheap, easy to obtain and renewable.
(2) The aldol condensation reaction can be carried out at normal temperature and normal pressure, the hydrodeoxygenation reaction is carried out at 150-210 ℃ and 2.0-4.0 MPa, the reaction is mild, and the requirements on equipment and operation are low.
(3) The aldol condensation reaction is not required to be separated, the 1, 14-tetradecanediol can be produced by direct hydrodeoxygenation reaction after neutralization, the product is not mutually soluble with water, an organic phase can be separated by extraction and liquid separation, and a water phase containing the catalyst and inorganic salt can be recycled. Therefore, the whole process is simple in separation and free of pollution emission.
(4) Inorganic salt generated after neutralization can be used as a cocatalyst in the hydrodeoxygenation reaction, so that the polarity of a solvent is enhanced, the separation of glycol and water is enhanced, excessive hydrodeoxygenation is prevented, and the selectivity of a target product 1, 14-tetradecanediol is improved. The whole process has few production steps, low cost and good industrial application prospect.
Detailed Description
According to the invention, biomass-derived furfural, 5-hydroxymethyl furfural and acetone are used as raw materials, and the molar ratio of furfural to 5-hydroxymethyl furfural to acetone is controlled to be 1:1: 1. Preparing a certain amount of 0.1-0.8 mol/L alkali solution, controlling the reaction temperature to be 10-40 ℃, adding acetone under full stirring, slowly dropping 5-hydroxymethylfurfural for 0.5-2 h, adding furfural, continuing aldol condensation reaction, reacting for 8-24 h, and neutralizing with acid to obtain C14An oxygen-containing intermediate; and then directly reacting under the action of a selective hydrodeoxygenation catalyst, controlling the reaction temperature to be 150-210 ℃, the reaction pressure to be 2.0-4.0 MPa, and the reaction time to be 8-30 h, cooling, extracting and separating liquid, and obtaining the 1, 14-tetradecanediol in an organic phase.
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 endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values.
Examples 1 to 10: the invention relates to a method for producing 1, 14-tetradecanediol, C, from furfural, 5-hydroxymethyl furfural and acetone by a one-pot two-step method14The oxygen-containing intermediate can be directly subjected to the hydrodeoxygenation of the next step after being obtained, and the two steps do not need to be separated. But for the sake of clarityThe course of the reaction is illustrated by the aldol condensation reaction in this example, i.e.C14And (4) synthesizing an oxygen-containing intermediate.
Preparing 200mL of aqueous solution of 0.1-0.8 mol/L sodium hydroxide or potassium hydroxide, placing the aqueous solution in a 500mL reactor, adding acetone under full stirring, slowly dropping 5-hydroxymethylfurfural, controlling the dropping time to be 0.5-2 h, finally adding furfural, controlling the molar ratio of furfural to 5-hydroxymethylfurfural to acetone to be 1:1:1, and stirring and reacting for 8-24 h at 10-40 ℃. After the reaction, the reaction mixture was neutralized with an acid, and sampled for analysis. Conversion rate of furfural, 5-hydroxymethyl furfural and acetone and C obtained under different aldol condensation reaction conditions14The yields of oxygenated intermediates are shown in table 1.
TABLE 1 summary of the condensation reaction results of furfural, 5-hydroxymethylfurfural and acetone aldol under different reaction conditions
The above examples illustrate that the process of the present invention can efficiently produce C14The oxygen-containing intermediate has high conversion rate of 5-hydroxymethylfurfural, furfural and acetone. Examples 1,8 illustrate that the drop rate of 5-hydroxymethylfurfural significantly affects C14Selectivity of oxygenated intermediates, if added directly, C14The yield of oxygenated intermediates is significantly reduced.
Examples 11 to 20 this example illustrates a method for preparing a hydrodeoxygenation catalyst.
Example 11Pd/Nb2O5Preparation method of (1)
Dissolving 1.0g of hexadecyl trimethyl ammonium bromide in 20mL of deionized water, slowly dropping 20mL of 0.5mol/L niobium tartrate solution under stirring to form a suspension, carrying out hydrothermal crystallization at 160 ℃ for 24 hours, cooling, carrying out suction filtration, washing, drying, and roasting at 550 ℃ for 5 hours to obtain Nb2O5And (3) a carrier. According to the amount of supported and Nb2O5Calculating the mass and concentration of the needed palladium nitrate solution by water absorption, and dripping the palladium nitrate into the Nb2O5Stirring in carrier until it is just in dehumidification state, drying at 90 deg.C overnight, and calcining at 400 deg.C for 3 hr to obtain Pd/Nb2O5A deoxygenation hydrogenation catalyst, wherein the loading of Pd was 3.0 wt%.
Example 12Pd/Nb2O5-WO3Preparation method of (1)
Dissolving 1.0g of hexadecyl trimethyl ammonium bromide in 20mL of deionized water, slowly dropping 20mL of 0.5mol/L niobium tartrate solution and 1.42g of ammonium metatungstate under stirring to form a suspension, carrying out hydrothermal crystallization at 160 ℃ for 24 hours, cooling, carrying out suction filtration, washing, drying, and roasting at 550 ℃ for 5 hours to obtain Nb2O5-WO3Composite oxide of Nb2O5And WO3The mass ratio of (A) to (B) is 1: 1. According to the amount of supported and Nb2O5-WO3Calculating the mass and concentration of the needed palladium nitrate solution by water absorption, and dripping the palladium nitrate into the Nb2O5-WO3Stirring in carrier until it is just in dehumidification state, drying at 90 deg.C overnight, and calcining at 400 deg.C for 3 hr to obtain Pd/Nb2O5-WO3A deoxygenation hydrogenation catalyst, wherein the loading of Pd was 2.9 wt%.
Example 13Pd/NbOPO4Preparation method of (1)
Dissolving 1.0g of hexadecyl trimethyl ammonium bromide in 20mL of deionized water, slowly dropping 20mL of 0.5mol/L niobium tartrate solution (0.5mol/L) and 20mL of 0.5mol/L diammonium hydrogen phosphate solution under stirring to form a suspension, carrying out hydrothermal crystallization at 160 ℃ for 24 hours, cooling, carrying out suction filtration, washing, drying, and roasting at 550 ℃ for 5 hours to obtain NbOPO4And (3) a carrier. According to the amount of supported and NbOPO4Calculating the mass and concentration of the required palladium nitrate solution by water absorption, and dripping NbOPO4Stirring in carrier until reaching dehumidifying state, oven drying at 90 deg.C overnight, and calcining at 400 deg.C for 3 hr to obtain Pd/NbOPO4A deoxygenation hydrogenation catalyst, wherein the loading of Pd was 3.2 wt%.
Example 14Pt/WO3System of (1)Preparation method
Dissolving 1.0g of hexadecyl trimethyl ammonium bromide in 20mL of deionized water, slowly dripping 1.42g of ammonium metatungstate under stirring to form a suspension, carrying out hydrothermal crystallization at 160 ℃ for 24 hours, cooling, carrying out suction filtration, washing, drying, and roasting at 550 ℃ for 5 hours to obtain WO3And (3) a carrier. According to the amount of supported and WO3Calculating the mass and concentration of the platinum nitrate solution required by water absorption, and dripping the platinum nitrate into WO3Stirring in carrier until it is just dehumidified, oven drying at 90 deg.C overnight, and calcining at 400 deg.C for 3 hr to obtain Pt/WO3A deoxygenating hydrogenation catalyst wherein the loading of Pt was 2.0 wt%.
Example 15Ru/NbOPO4Preparation method of (1)
The preparation process was substantially the same as in example 13, except that in example 13, palladium nitrate was replaced with ruthenium chloride and the loading of Ru was 4.5% by weight.
Example 16Pd/NbOPO4-WO3Preparation method of (1)
NbOPO prepared as in example 134Support, WO was obtained as in example 143A carrier of NbOPO4And WO3Physical mixing according to the ratio of 1:1 to obtain NbOPO4-WO3And (3) mixing. According to the amount of supported and NbOPO4-WO3Calculating the mass and concentration of the required palladium nitrate solution by water absorption, and dripping NbOPO4-WO3Stirring in carrier until reaching dehumidifying state, oven drying at 90 deg.C overnight, and calcining at 400 deg.C for 3 hr to obtain Pd/NbOPO4-WO3Deoxygenated hydrogenation catalyst with a pd loading of 2.9 wt%.
Example 17Pd/WO3Preparation method of (1)
The preparation method was substantially the same as in example 14, except that platinum nitrate was replaced with palladium nitrate and the loading amount of Pd was 3.3 wt% in example 14.
Implementation of 18Ni/NbOPO4-WO3Preparation method of (1)
The preparation method was substantially the same as in example 16, except that palladium nitrate was replaced with nickel nitrate and the loading amount of Ni was 5.0 wt%.
Example 19Pd/WO3·nH2Process for producing O
Dissolving 1.0g of hexadecyl trimethyl ammonium bromide in 20mL of deionized water, slowly dripping 1.42g of ammonium metatungstate under stirring to form a suspension, carrying out hydrothermal crystallization at 160 ℃ for 24 hours, cooling, carrying out suction filtration, washing, drying, and roasting at 300 ℃ for 5 hours to obtain WO3·nH2And O. According to the amount of supported and WO3·nH2Calculating the mass and concentration of the needed palladium nitrate solution by O water absorption, and dripping the palladium nitrate into WO3·nH2Stirring in O carrier until it is in dehumidification state, oven drying at 90 deg.C overnight, and calcining at 300 deg.C for 3 hr to obtain Pd/WO3·nH2O-deoxygenation hydrogenation catalyst, wherein the loading of Pd was 3.2 wt%.
Example 20Pd/Nb2O5·nH2Process for producing O
Dissolving 1.0g of hexadecyl trimethyl ammonium bromide in 20mL of deionized water, slowly dripping 20mL of 0.5mol/L niobium tartrate solution under stirring to form a suspension, then carrying out hydrothermal crystallization at 160 ℃ for 24 hours, cooling, carrying out suction filtration, washing, drying, and roasting at 300 ℃ for 5 hours to obtain Nb2O5·nH2And O. According to the amount of supported and Nb2O5·nH2Calculating the mass and concentration of the needed palladium nitrate solution by O water absorption, and dripping the palladium nitrate into Nb2O5·nH2Stirring in O carrier until it is in dehumidification state, oven drying at 90 deg.C overnight, and calcining at 300 deg.C for 3 hr to obtain Pd/Nb2O5·nH2O-deoxygenation hydrogenation catalyst, wherein the loading of Pd was 3.1 wt%.
Examples 21 to 31: this example is for C14Description of the Process for hydrodeoxygenation of oxygenated intermediates
Preparing 200mL of 0.3mol/L aqueous solution of sodium hydroxide, placing the aqueous solution in a 500mL reactor, adding 5.8g of acetone under full stirring, slowly dropping 12.6g of 5-hydroxymethylfurfural, controlling the dropping time to be 2h, finally adding 9.6g of furfural, and continuing to react for 14h at 20 ℃. After the reaction is finished, neutralizing with hydrochloric acid, adding 4.0g of hydrodeoxygenation catalyst, reacting for 8-30 h at 150-210 ℃ and under the hydrogen pressure of 2.0-4.0 MPa, and performing selective hydrodeoxygenation. Reaction ofImmediately after completion of the reaction, the reaction mixture was cooled in a water bath, extracted with 3X 20mL of diethyl ether, and the diethyl ether was removed by rotary evaporation to obtain a mixture containing the objective 1, 14-tetradecanediol. Under different hydrodeoxygenation reaction conditions, C14The conversion rates of the oxygen-containing intermediates were all 100%, and the yields of 1, 14-tetradecanediol are shown in Table 2.
TABLE 2 summary of the reaction results under different reaction conditions
Examples 21 to 31 illustrate that C is reacted under the preferred reaction conditions of the present invention14Selective hydrodeoxygenation of oxygenated intermediates can result in yields of up to 50.9% 1, 14-tetradecanediol.
Comparative example 1A method for preparing 1, 14-tetradecanediol from a Biomass derivative
Preparing 200mL of 0.3mol/L aqueous solution of sodium hydroxide, placing the aqueous solution in a 500mL reactor, adding 5.8g of acetone under full stirring, slowly dropping 12.6g of 5-hydroxymethylfurfural, controlling the dropping time to be 2h, finally adding 9.6g of furfural, and continuing to react for 14h at 20 ℃. Neutralizing with hydrochloric acid after the reaction is finished, filtering, washing with water, and drying to obtain C14An oxygen-containing intermediate. 20.0g C14Oxygen-containing intermediate, 4.0g Pd/NbOPO4-WO32.5g NaCl and 200mL deionized water are put into a 500mL reaction kettle, the reaction temperature is controlled at 190 ℃, the reaction pressure is 3.0MPa, the reaction time is 20 hours, the reaction kettle is immediately cooled in a water bath after the reaction is finished, 3 x 20mL diethyl ether is used for extracting reaction liquid, the diethyl ether is removed by rotary evaporation to obtain a mixture containing the target product 1, 14-tetradecanediol, and the mixture is analyzed by gas chromatography. The conversion rates of furfural, 5-hydroxymethylfurfural and acetone were all 100%, and the yield of 1, 14-tetradecanediol was 48.7%.
The difference from example 26 is that 1, 14-tetradecanediol is prepared by a stepwise method while adding inorganic salts during the deoxygenation hydrogenation reaction.
Comparative example 2A method for preparing 1, 14-tetradecanediol from a Biomass derivative
Preparing 200mL of 0.3mol/L aqueous solution of sodium hydroxide, placing the aqueous solution in a 500mL reactor, adding 5.8g of acetone under full stirring, slowly dropping 12.6g of 5-hydroxymethylfurfural, controlling the dropping time to be 2h, finally adding 9.6g of furfural, and continuing to react for 14h at 20 ℃. Neutralizing with hydrochloric acid after the reaction is finished, filtering, washing with water, and drying to obtain C14An oxygen-containing intermediate. 20.0g C14Oxygen-containing intermediate, 4.0g Pd/NbOPO4-WO3And 200mL of deionized water are put into a 500mL reaction kettle, the reaction temperature is controlled to be 190 ℃, the reaction pressure is 3.0MPa, the reaction time is 20 hours, the reaction kettle is immediately cooled in a water bath after the reaction is finished, 3 x 20mL of diethyl ether is used for extracting the reaction solution, the diethyl ether is removed by rotary evaporation to obtain a mixture containing the target product 1, 14-tetradecanediol, and the mixture is analyzed by gas chromatography. The conversion rates of furfural, 5-hydroxymethylfurfural and acetone were all 100%, and the yield of 1, 14-tetradecanediol was 21.3%.
The difference from example 26 is that 1, 14-tetradecanediol is prepared by a stepwise method without adding inorganic salts during the deoxygenation hydrogenation reaction.
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