CN110078588A - A kind of preparation method of 1,3- propylene glycol - Google Patents
A kind of preparation method of 1,3- propylene glycol Download PDFInfo
- Publication number
- CN110078588A CN110078588A CN201910381561.3A CN201910381561A CN110078588A CN 110078588 A CN110078588 A CN 110078588A CN 201910381561 A CN201910381561 A CN 201910381561A CN 110078588 A CN110078588 A CN 110078588A
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- Prior art keywords
- tert
- glycerol
- butyl ether
- reaction
- catalyst
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 209
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000006722 reduction reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 238000005694 sulfonylation reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 45
- 239000003638 chemical reducing agent Substances 0.000 claims description 21
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- IVZAIGFRIOMAIK-UHFFFAOYSA-N 2-methyl-2-[2-[(2-methylpropan-2-yl)oxy]propoxy]propane Chemical compound CC(C)(C)OC(C)COC(C)(C)C IVZAIGFRIOMAIK-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 14
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 12
- 229940035437 1,3-propanediol Drugs 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- -1 sulfonate ester Chemical class 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006266 etherification reaction Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 229910000085 borane Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 6
- 239000011964 heteropoly acid Substances 0.000 claims description 6
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000011973 solid acid Substances 0.000 claims description 6
- 239000003930 superacid Substances 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011831 acidic ionic liquid Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011968 lewis acid catalyst Substances 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 235000015096 spirit Nutrition 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- GVEOHMXXNFKHOT-UHFFFAOYSA-N 4-(nitromethyl)morpholine Chemical compound [N+](=O)([O-])CN1CCOCC1 GVEOHMXXNFKHOT-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 125000006239 protecting group Chemical group 0.000 abstract description 2
- 230000006103 sulfonylation Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 61
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 10
- 238000006757 chemical reactions by type Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000007327 hydrogenolysis reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003459 sulfonic acid esters Chemical class 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- WLWXEDJMZHONIG-UHFFFAOYSA-N 4-methylbenzenesulfonate;1-methyl-1h-imidazol-1-ium Chemical compound C[NH+]1C=CN=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 WLWXEDJMZHONIG-UHFFFAOYSA-N 0.000 description 1
- FFNCEXOZZTUYQX-UHFFFAOYSA-N 4-methylmorpholin-3-amine Chemical compound CN1CCOCC1N FFNCEXOZZTUYQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of 1,3-PD, are related to technical field of chemical synthesis.This programme prepares 1,3 propylene glycol by raw material functional group's directional protection method of glycerol: i.e. by sloughing secondary hydroxyl at ether reaction selectivity protection terminal hydroxy group, then by sulfonylation and reduction reaction, then sloughing protecting group again.The features such as technique of the invention has high income, and by-product is few, at low cost, easily separated, is a kind of route of environment friendly and economical, overcomes prior art operation complexity, the low defect of yield, and development prospect is wide.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of 1, 3-propylene glycol.
Background
1, 3-propylene glycol is an important chemical raw material, is mainly used for the synthesis of plasticizers, detergents, preservatives and emulsifiers, and is also used in the industries of food, cosmetics, pharmacy and the like. 1, 3-propanediol is the main raw material for synthesizing PTT material. PTT is formed by directly esterifying 1, 3-propylene glycol and refined terephthalic acid and then melting, and PTT fibers are in a special configuration connected by odd carbon chains, so the PTT fibers have special properties different from PET and PA6 fibers, and have wide application potential in the fields of clothing industry, engineering plastics and the like. The key to the synthesis of PTT is the synthesis of the monomeric 1, 3-propanediol.
Currently, there are two synthetic routes for the industrial production of 1, 3-propanediol realized in the world: one is ethylene oxide carbonylation process; another process is the acrolein hydrohydration process. In addition, DuPont is developing a method for producing 1, 3-propanediol by microbial fermentation, which is currently under laboratory research. However, the ethylene oxide carbonylation method has large equipment investment, high technical difficulty, quite complex catalyst system, rigorous and unstable preparation process and extremely toxic ligand. The acrolein hydration and hydrogenation process is relatively expensive, and particularly acrolein itself is a highly toxic, flammable and explosive material, and is difficult to store and transport. In addition, the last step of the microbiological method needs acrolein hydration, the process is complex and long in period, and most importantly, the product and the strain are difficult to separate, so that the industrial production is difficult.
Glycerol is a by-product in the biodiesel production process, and 10% of crude glycerol by-product is associated with each 1 ton of biodiesel produced. Wherein, the 1, 3-propylene glycol is generated by the selective hydrogenolysis reaction of the glycerol, and the method can simultaneously have the quick and high-efficiency effects of the acrolein hydration method and the clean and sustainable effects of the biological method.
The hydrogenolysis reaction of glycerol generally employs a noble metal catalyst, such as platinumRhodium, iridium. SiO 22、ZrO2、Al2O3And SiO2-ZrO2Is used as catalyst carrier, and further sulfuric acid, phosphotungstic acid, silicotungstic acid, WO3Etc. are used as key cocatalysts. Especially loaded on WO3/ZrO2The platinum catalyst has better chemical and thermal stability, and is widely applied to the hydrogenolysis reaction of the glycerol.
At present, the catalyst for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol is mainly a noble metal catalyst, but the noble metal has the following problems: the catalyst has high preparation cost, low glycerin conversion rate, low 1, 3-propylene glycol selectivity and harsh reaction conditions. Therefore, the industrial application of the hydrogenolysis reaction of glycerol to 1, 3-propanediol is limited.
Patent 201610923442.2 discloses a process for synthesizing 1, 3-propanediol, which comprises protecting two terminal hydroxyl groups of glycerol with aldehyde, removing the middle hydroxyl group, and finally deprotecting to obtain 1, 3-propanediol. However, this method is complicated in operation and low in yield.
Disclosure of Invention
The invention aims to solve the technical problems of complex operation and low yield in the prior art and provides a preparation method for synthesizing 1, 3-propylene glycol by using glycerol as a raw material.
In order to solve the above problems, the present invention proposes the following technical solutions:
a preparation method of 1, 3-propylene glycol comprises the following steps:
A. performing etherification reaction, namely performing etherification reaction on glycerol and a tert-butyl donor according to the mass ratio of 1:2-10 under the action of an acid catalyst to obtain glycerol 1, 3-di-tert-butyl ether, wherein the reaction temperature is 40-120 ℃, the reaction time is 6-24 hours, and the reaction pressure is 1-10 MPa;
B. a sulfonylation reaction, namely reacting glycerol 1, 3-di-tert-butyl ether with a sulfonyl chloride compound in an organic alkali solution at the temperature of 0-60 ℃ to convert the secondary hydroxyl of the glycerol 1, 3-di-tert-butyl ether into a sulfonate group to obtain a sulfonate ester of the glycerol 1, 3-di-tert-butyl ether, wherein the mass ratio of the glycerol 1, 3-di-tert-butyl ether, the sulfonyl chloride compound and the organic alkali solution is 1:1-1.2: 1-1.2;
C. b, reduction reaction, namely adding a reduction catalyst, a sufficient amount of solvent and a sufficient amount of reducing agent into the sulfonic ester of the glycerol 1, 3-di-tert-butyl ether obtained in the step B, reacting, removing the sulfonic ester, and obtaining the propylene glycol di-tert-butyl ether, wherein the mass of the reduction catalyst is 0.00001-20% of that of the sulfonic ester of the glycerol 1, 3-di-tert-butyl ether;
D. removing tert-butyl, namely removing tert-butyl from the propylene glycol di-tert-butyl ether and an acidic resin catalyst at the reaction temperature of 100 ℃ and 110 ℃ to obtain 1, 3-propylene glycol, wherein the mass of the acidic resin catalyst is 0.1-20% of that of the propylene glycol di-tert-butyl ether; wherein the acidic catalyst is a Bronst acid catalyst, a Lewis acid catalyst or a solid acid catalyst.
The further technical scheme is that the tertiary butyl donor in the step A is at least one of isobutene, methyl tertiary butyl ether and tertiary butyl alcohol.
The further technical scheme is that the solid acid catalyst comprises alkyl substituted benzene sulfonic acid, alkyl substituted naphthalene sulfonic acid, non-alkyl substituted benzene sulfonic acid, non-alkyl substituted naphthalene sulfonic acid, polysulfonic resin, polyperfluorosulfonic resin, heteropoly acid and heteropoly acid salt, molecular sieve, acidic ionic liquid and SO of a single composite carrier4 2-/MXOYSolid superacid, S2O8 2-/MXOYAt least one of solid super acids, wherein, MXOYIs NiO, TiO2，ZrO2，SiO2，SnO2，Fe2O3，Al2O3，WO3And MoO3At least one of (1).
The further technical scheme is that the sulfonyl chloride compound in the step B is aromatic sulfonyl chloride and/or aliphatic sulfonyl chloride.
The further technical scheme is that the reducing agent in the step C is at least one of hydrogen, formic acid, formate compounds and borane.
The further technical scheme is that the reduction catalyst is at least one of Raney Ni, platinum carbon, palladium hydroxide carbon, platinum, ruthenium, rhodium, gold and iridium.
The further technical scheme is that the reducing solvent is at least one of toluene, n-hexane, cyclohexane, petroleum ether, xylene, solvent oil and benzene.
The further technical scheme is that the organic alkali solution comprises at least one of pyridine, triethylamine, triethylene Diamine (DABCO), N-methyl morpholine, tetramethyl ethylene diamine, 4-dimethylamino pyridine (DMAP) and 1, 8-diazabicycloundecen-7-ene (DBU).
In the step A, nitrogen is injected into the system to ensure that the reaction pressure is 1.5 MPa.
Compared with the prior art, the invention can achieve the following technical effects:
the invention provides a method for preparing 1, 3-propanediol by using glycerol as a raw material and using a functional group directional protection method, wherein terminal hydroxyl is selectively protected by an ether forming reaction, secondary hydroxyl is removed by a sulfonylation reaction and a reduction reaction, and then a protecting group is removed.
Detailed Description
The technical solutions in the examples will be clearly and completely described below.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The embodiment of the invention provides a process method for synthesizing 1, 3-propylene glycol, which comprises the following steps:
A. performing etherification reaction, namely performing etherification reaction on glycerol and a tert-butyl donor under the action of a first acid catalyst according to the mass ratio of 1:2-10 to obtain 1, 3-di-tert-butyl ether of glycerol, wherein the reaction temperature is 40-120 ℃, the reaction time is 6-24 hours, and the reaction pressure is 1-10 MPa; specifically, nitrogen gas was injected into the system to make the reaction pressure 1.5 MPa;
B. a sulfonylation reaction, namely reacting glycerol 1, 3-di-tert-butyl ether with a sulfonyl chloride compound in an organic alkali solution at the temperature of 0-60 ℃ to convert secondary hydroxyl of the glycerol 1, 3-di-tert-butyl ether into a sulfonate group to obtain a sulfonate of the glycerol 1, 3-di-tert-butyl ether, wherein the mass ratio of the glycerol 1, 3-di-tert-butyl ether to the sulfonyl chloride compound to the organic alkali solution is 1:1-1.2: 1-1.2;
C. b, reduction reaction, namely adding a sufficient amount of reducing agent, a sufficient amount of reduction catalyst and a sufficient amount of reduction solvent into the sulfonic ester of the glycerol 1, 3-di-tert-butyl ether obtained in the step B under preset reaction conditions, and reacting to remove the sulfonic ester to obtain the propylene glycol di-tert-butyl ether, wherein the mass of the reduction catalyst is 0.00001-20% of the mass of the sulfonic ester of the glycerol 1, 3-di-tert-butyl ether;
D. removing tert-butyl, namely removing tert-butyl from the propylene glycol di-tert-butyl ether and an acidic resin catalyst at the reaction temperature of 100 ℃ and 110 ℃ to obtain 1, 3-propylene glycol, wherein the mass of the acidic resin catalyst is 1-20% of that of the propylene glycol di-tert-butyl ether; wherein,
the acidic catalyst is a Bronst acid catalyst, a Lewis acid catalyst or a solid acid catalyst.
The solid acid catalyst includes alkyl-substituted benzenesulfonic acid, alkyl-substituted naphthalenesulfonic acid, non-alkyl-substituted benzenesulfonic acid, non-alkyl-substituted naphthalenesulfonic acid, polysulfonic resin, polyperfluorosulfonic resin, heteropoly acid and heteropoly acid salt, molecular sieve, acidic ionic liquid, and SO on a single composite carrier4 2-/MXOYSolid superacid, S2O8 2-/MXOYAt least one of solid super acids, wherein, MXOYIs NiO, TiO2，ZrO2，SiO2，SnO2，Fe2O3，Al2O3，WO3And MoO3At least one of (1).
It should be noted that the amount of the acidic catalyst is 1-20% of the mass of the glycerol, and in the specific implementation, the glycerol in the step a is refined glycerol, so that other impurities are not introduced.
In a specific implementation, the tert-butyl donor in the step A is at least one of isobutene, methyl tert-butyl ether and tert-butyl alcohol.
The sulfonyl chloride compound in the step B is aromatic sulfonyl chloride and/or aliphatic sulfonyl chloride.
And the reducing agent in the step C is at least one of hydrogen, formic acid, formate compounds and borane.
In certain embodiments, the reduction catalyst is at least one of raney ni, platinum carbon, palladium hydroxide carbon, platinum, ruthenium, rhodium, gold, iridium. For example,
in one embodiment, the reduction catalyst is 0.0001% gold of the sulfonate mass of glycerol 1, 3-di-tert-butyl ether.
In one embodiment, the reduction catalyst is 0.01% of iridium of the sulfonate mass of glycerol 1, 3-di-tert-butyl ether.
In one embodiment, the reduction catalyst is a 5% sulfonate mass of glycerol 1, 3-di-tert-butyl ether platinum on charcoal catalyst.
In one example, the reduction catalyst is ruthenium 10% of the sulfonate mass of glycerol 1, 3-di-tert-butyl ether.
In one embodiment, the reduction catalyst is a mixture of palladium on carbon and palladium on carbon hydroxide in a mass of 15% sulfonate ester of glycerol 1, 3-di-tert-butyl ether.
In one example, the reduction catalyst is Raney Ni at 20% of the sulfonate mass of glycerol 1, 3-di-tert-butyl ether.
In certain embodiments, the reducing solvent is at least one of toluene, n-hexane, cyclohexane, petroleum ether, xylene, mineral spirits, benzene. For example,
in one embodiment, the reducing solvent is a mixture of toluene and xylene.
In one embodiment, the reducing solvent is n-hexane and cyclohexane.
In one embodiment, the reducing solvent is mineral spirits.
In the specific implementation, the reaction temperature and the reaction pressure in step C are set to be different according to different types of reducing agents, and it should be noted that in order to ensure that the sulfonate ester of glycerol 1, 3-di-tert-butyl ether is completely reduced to propylene glycol di-tert-butyl ether, the amount of the reducing agent is sufficient or excessive; the reducing solvent can be added in a proper amount, a sufficient amount or an excess amount as required by those skilled in the art to ensure the normal progress of the reduction reaction.
In some embodiments, the reducing agent is an excess or sufficient amount of hydrogen at a temperature of 120 ℃ to 140 ℃ and a pressure of 1.8 to 10 MPa. For example:
in one embodiment, the reducing agent is an excess of hydrogen and the reduction is carried out at 120 ℃ and 10 MPa.
In one embodiment, the reducing agent is hydrogen in sufficient quantity to effect the reduction at 130 deg.C and 6 MPa.
In one embodiment, the reducing agent is an excess of hydrogen and the reduction is carried out at 140 ℃ and 1.8 MPa.
In certain embodiments, the reducing agent is an excess or sufficient amount of formic acid and formate compound, the reaction temperature is from room temperature to 60 ℃, and the reaction pressure is atmospheric. For example:
in one embodiment, the reducing agent is sufficient formic acid and formate compound at 60 deg.C and atmospheric pressure.
In one embodiment, the reducing agent is sufficient formic acid and formate compound, the reaction temperature is room temperature, and the reaction pressure is normal pressure.
In one embodiment, the reducing agent is sufficient formic acid and formate compound at 40 deg.C and atmospheric pressure.
In one embodiment, the reducing agent is an excess of formic acid and formate compound, the reaction temperature is 50 ℃, and the reaction pressure is atmospheric.
In certain embodiments, the reducing agent is sufficient borane at a reaction temperature of 0 to 25 ℃ and at a reaction pressure of atmospheric pressure. For example:
in one embodiment, the reducing agent is sufficient borane at 15 ℃ and at atmospheric pressure.
In one embodiment, the reducing agent is sufficient borane at 25 ℃ and at atmospheric pressure.
In one embodiment, the reducing agent is sufficient borane at 0 ℃ and at atmospheric pressure.
In certain embodiments, the organic base solution comprises at least one of pyridine, triethylamine, triethylenediamine (DABCO), aminomethylmorpholine, tetramethylethylenediamine, 4-Dimethylaminopyridine (DMAP), 1, 8-diazabicycloundecen-7-ene (DBU). For example:
in one embodiment, the organic base solution is 4-Dimethylaminopyridine (DMAP).
In one embodiment, the organic base solution is 1, 8-diazabicycloundecen-7-ene (DBU).
In one embodiment, the organic base solution is tetramethylethylenediamine.
In the examples of the present invention, the room temperature was 25 ℃ and the normal pressure was 0.1 MPa.
The first embodiment is as follows:
the first step is as follows: etherification reaction (reaction scheme 1)
92 g of refined glycerol and 200 g of isobutene are introduced into a fixed bed reactor loaded with an A35 resin acid catalyst with the mass of 10% of that of the glycerol, nitrogen is injected to enable the system pressure to reach 1.5MPa, the temperature is raised to 75 ℃, and the reaction is carried out for 20 hours. The reaction product composition was analyzed by gas chromatography, wherein the conversion of glycerol was 92%, and wherein the yield of the product B (glycerol 1, 3-di-t-butyl ether) was 82%. 164 g of glycerol 1, 3-di-tert-butyl ether was obtained by rectification in a yield of 80%.
The second step is that: sulfonylation reaction (reaction scheme 2)
102 g of glycerol 1, 3-di-tert-butyl ether and 225 g of p-toluenesulfonyl chloride were each charged into a 500mL flask, and 200mL of pyridine was poured in, and magnetic stirring was started until p-toluenesulfonyl was completely dissolved. The temperature was raised to 40 ℃ and the reaction was continued for 10 hours. After the reaction was completed, the temperature was lowered to room temperature, and impurities were removed by filtration, and the reaction solution was poured into 1000mL of ice water, washed with 3X 50mL of ice water, and dried under vacuum to obtain product C (sulfonic acid ester of glycerol 1, 3-di-t-butyl ether) with a yield of 98%.
The third step: reduction reaction (reaction type 3)
Adding 180g of reactant C (sulfonic ester of glycerol 1, 3-di-tert-butyl ether), 10% of palladium-carbon catalyst based on the mass of the reactant C and 400mL of tetrahydrofuran as a solvent into a hydrogenation reaction kettle, stirring and heating to 130 ℃, introducing hydrogen into the hydrogenation reaction kettle until the pressure is 2MPa after the temperature is stabilized, reacting for 4 hours at the temperature, cooling to room temperature after the reaction is finished, and performing suction filtration and rectification to obtain 85 g of propylene glycol di-tert-butyl ether with the yield of 90%.
The fourth step: de-tert-butyl (reaction type 4)
Introducing 85 g of propylene glycol di-tert-butyl ether obtained in the third step into a fixed bed reactor added with an A35 resin acid catalyst, wherein the mass of the A35 resin acid catalyst is 10% of that of the propylene glycol di-tert-butyl ether, heating to 100 ℃, reacting for 2 hours, cooling to room temperature, adjusting the pH value to be neutral, rectifying by using a rectifying column, and collecting the fraction at 214 ℃ to obtain 34 g of 1, 3-propylene glycol with the yield of 98%.
Example two:
the first step is as follows: tertiary butyl Ether reaction (reaction type 5)
92 g of refined glycerol and 88 g of methyl tert-butyl ether are introduced into a reaction kettle which is loaded with an A15 resin acid catalyst with the mass of 10 percent of that of the glycerol, nitrogen is injected to ensure that the system pressure reaches 1.5MPa, the temperature is raised to 70 ℃, and the reaction is carried out for 24 hours. The reaction product composition was analyzed by gas chromatography with a conversion of glycerol of 82% and a yield of glycerol 1, 3-di-t-butyl ether of 72%. 120 g of glycerol 1, 3-di-tert-butyl ether can be obtained by rectification with a yield of 60%.
The second step is that: sulfonylation reaction (reaction scheme 6)
120 g of glycerol 1, 3-di-tert-butyl ether and 264 g of p-toluenesulfonyl chloride were each added to a 500mL flask, and 200mL of pyridine was poured in, and magnetic stirring was started until p-toluenesulfonyl was completely dissolved. The temperature was raised to 30 ℃ and the reaction was continued for 10 hours. After cooling to room temperature, the reaction mixture was filtered to remove impurities, poured into 1000mL of ice water, washed with 3X 50mL of ice water, and then dried under vacuum to give 206 g of product C (sulfonic acid ester of glycerol 1, 3-di-t-butyl ether) in 98% yield.
The third step: reduction reaction (reaction type 7)
Adding 180g of reactant C (sulfonic ester of glycerol 1, 3-di-tert-butyl ether) and 400mL of tetrahydrofuran as a solvent into a hydrogenation reaction kettle, stirring and heating to 100 ℃, dropping 60.5 g of formic acid/triethylamine (formic acid: triethylamine: 5: 2) when the temperature is reduced to room temperature, reacting for 6 hours at the temperature, performing suction filtration, and then rectifying to obtain 76 g of propylene glycol di-tert-butyl ether with the yield of 81%.
The fourth step: de-tert-butyl (reaction type 8)
76 g of propylene glycol di-tert-butyl ether was introduced into a reactor containing SO3Fixed bed reactor for H-SBA-15 catalyst, SO3The mass of the H-SBA-15 catalyst is 20% of that of the propylene glycol di-tert-butyl ether, the temperature is raised to 110 ℃, the reaction is carried out for 3 hours, then the temperature is reduced to room temperature, the pH value is adjusted to be neutral, the distillation column is used for carrying out rectification, the fraction at 214 ℃ is collected, 28 g of 1, 3-propylene glycol is obtained, and the yield is 92%.
Example three;
the first step is as follows: etherification reaction (reaction type 9)
92 g of refined glycerol and 74 g of tert-butyl alcohol are introduced into a reaction kettle which is loaded with an ionic liquid N-methylimidazole p-toluenesulfonate catalyst which is equivalent to 1 percent of the mass of the glycerol, nitrogen is injected to ensure that the system pressure reaches 1.5MPa, the temperature is raised to 100 ℃, and the reaction is carried out for 24 hours. The reaction product composition was analyzed by gas chromatography, wherein the conversion of glycerol was 77% and the chromatographic yield of glycerol 1, 3-di-t-butyl ether was 70%. 130 g of glycerol 1, 3-di-tert-butyl ether can be obtained by rectification with a yield of 65%.
The second step is that: sulfonylation (reaction formula 10)
120 g of glycerol 1, 3-di-tert-butyl ether and 264 g of p-toluenesulfonyl chloride were each added to a 500mL flask, and 200mL of triethylamine was poured in, and magnetic stirring was started until p-toluenesulfonyl was completely dissolved. The temperature was raised to 50 ℃ and the reaction was continued for 10 hours. After cooling to room temperature, the reaction mixture was filtered to remove impurities, poured into 1000mL of ice water, washed with 3X 50mL of ice water, and then dried under vacuum to give 206 g of product C (sulfonic acid ester of glycerol 1, 3-di-t-butyl ether) in 98% yield.
The third step: reduction reaction (reaction type 11)
Adding 180g of reactant C (sulfonic ester of glycerol 1, 3-di-tert-butyl ether) and 400mL of tetrahydrofuran as a solvent into a hydrogenation reaction kettle, stirring and adding NaBH in batches4When the reaction temperature is reduced to room temperature and the reaction is carried out for 6 hours at the temperature, 1N diluted HCl is added into the reaction, the solvent is removed by rotary evaporation, the mixture is extracted by 3X 50mL of ethyl acetate for three times, and the mixture is distilled under reduced pressure to obtain 83 g of propylene glycol di-tert-butyl ether with the yield of 88 percent.
The fourth step: de-tert-butyl (reaction type 12)
76 g of propylene glycol di-tert-butyl ether was introduced into a reactor containing SO3H-SiO2Fixed bed reactor for catalyst, SO3H-SiO2The mass of the catalyst is 1 percent of that of the propylene glycol di-tert-butyl ether, the temperature is raised to 100 ℃, the reaction is carried out for 5 hours, then the temperature is lowered to room temperature, the pH value is adjusted to be neutral, the rectification is carried out by using a rectification column, the fraction at 214 ℃ is collected, 23.7 g of 1, 3-propylene glycol is obtained, and the yield is 77 percent.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The preparation method of the 1, 3-propylene glycol is characterized by comprising the following steps:
A. performing etherification reaction, namely performing etherification reaction on glycerol and a tert-butyl donor according to the mass ratio of 1:2-10 under the action of an acid catalyst to obtain glycerol 1, 3-di-tert-butyl ether, wherein the reaction temperature is 40-120 ℃, the reaction time is 6-24 hours, and the reaction pressure is 1-10 MPa;
B. a sulfonylation reaction, namely reacting glycerol 1, 3-di-tert-butyl ether with a sulfonyl chloride compound in an organic alkali solution at the temperature of 0-60 ℃ to convert the secondary hydroxyl of the glycerol 1, 3-di-tert-butyl ether into a sulfonate group to obtain a sulfonate ester of the glycerol 1, 3-di-tert-butyl ether, wherein the mass ratio of the glycerol 1, 3-di-tert-butyl ether, the sulfonyl chloride compound and the organic alkali solution is 1:1-1.2: 1-1.2;
C. b, reduction reaction, namely adding a reduction catalyst, a sufficient amount of solvent and a sufficient amount of reducing agent into the sulfonic ester of the glycerol 1, 3-di-tert-butyl ether obtained in the step B, reacting, removing the sulfonic ester, and obtaining the propylene glycol di-tert-butyl ether, wherein the mass of the reduction catalyst is 0.00001-20% of that of the sulfonic ester of the glycerol 1, 3-di-tert-butyl ether;
D. removing tert-butyl, namely removing tert-butyl from the propylene glycol di-tert-butyl ether and an acidic resin catalyst at the reaction temperature of 100 ℃ and 110 ℃ to obtain 1, 3-propylene glycol, wherein the mass of the acidic resin catalyst is 0.1-20% of that of the propylene glycol di-tert-butyl ether; wherein the acidic catalyst is a Bronst acid catalyst, a Lewis acid catalyst or a solid acid catalyst.
2. The method of claim 1, wherein the tert-butyl donor in step A is at least one of isobutylene, methyl tert-butyl ether and tert-butyl alcohol.
3. The process according to claim 1, wherein the solid acid catalyst comprises an alkyl-substituted benzenesulfonic acid, an alkyl-substituted naphthalenesulfonic acid, a non-alkyl-substituted benzenesulfonic acid, a non-alkyl-substituted naphthalenesulfonic acid, a polysulfonic resin, a polyperfluorosulfonic resin, a heteropoly acid and heteropoly acid salt, a molecular sieve, an acidic ionic liquid, and SO on a single composite carrier4 2-/MXOYSolid superacid, S2O8 2-/MXOYAt least one of solid super acids, wherein, MXOYIs NiO, TiO2，ZrO2，SiO2，SnO2，Fe2O3，Al2O3，WO3And MoO3At least one of (1).
4. The method according to claim 1, wherein the sulfonyl chloride compound in step B is an aromatic sulfonyl chloride and/or an aliphatic sulfonyl chloride.
5. The method of claim 1, 3-propanediol, wherein the reducing agent in step C is at least one of hydrogen, formic acid, formate compounds, and borane.
6. The method of claim 1, 3-propanediol, wherein the reducing catalyst is at least one of Raney Ni, platinum carbon, palladium hydroxide carbon, platinum, ruthenium, rhodium, gold, iridium.
7. The process according to claim 1, wherein the reducing solvent is at least one of toluene, n-hexane, cyclohexane, petroleum ether, xylene, mineral spirits and benzene.
8. The method of claim 1, 3-propanediol, wherein the organic base solution comprises at least one of pyridine, triethylamine, triethylenediamine, nitromethylmorpholine, tetramethylethylenediamine, 4-dimethylaminopyridine, and 1, 8-diazabicycloundecen-7-ene.
9. The process for producing 1, 3-propanediol according to claim 1, wherein in the step A, nitrogen gas is injected into the system to make the reaction pressure 1.5 MPa.
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| CN106565420A (en) * | 2016-10-29 | 2017-04-19 | 湖北绿色家园材料技术股份有限公司 | New technology for synthesizing 1,3-propylene glycol from glycerin through dehydroxylation method |
| CN106986753A (en) * | 2016-04-20 | 2017-07-28 | 深圳市前海博扬研究院有限公司 | A kind of preparation method of glycerine tertbutyl ether |
| CN107207389A (en) * | 2015-01-30 | 2017-09-26 | 沙特基础工业全球技术有限公司 | Method for preparing glycerine tertbutyl ether |
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| CN107207389A (en) * | 2015-01-30 | 2017-09-26 | 沙特基础工业全球技术有限公司 | Method for preparing glycerine tertbutyl ether |
| CN106986753A (en) * | 2016-04-20 | 2017-07-28 | 深圳市前海博扬研究院有限公司 | A kind of preparation method of glycerine tertbutyl ether |
| CN106565420A (en) * | 2016-10-29 | 2017-04-19 | 湖北绿色家园材料技术股份有限公司 | New technology for synthesizing 1,3-propylene glycol from glycerin through dehydroxylation method |
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