CN101318892A - Method for preparing sebacic acid with ricinus oil compounds - Google Patents
Method for preparing sebacic acid with ricinus oil compounds Download PDFInfo
- Publication number
- CN101318892A CN101318892A CNA2008100539172A CN200810053917A CN101318892A CN 101318892 A CN101318892 A CN 101318892A CN A2008100539172 A CNA2008100539172 A CN A2008100539172A CN 200810053917 A CN200810053917 A CN 200810053917A CN 101318892 A CN101318892 A CN 101318892A
- Authority
- CN
- China
- Prior art keywords
- acid
- viscotrol
- sebacic acid
- compounds
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 title abstract description 7
- 235000003846 Ricinus Nutrition 0.000 title 1
- 241000322381 Ricinus <louse> Species 0.000 title 1
- 239000011541 reaction mixture Substances 0.000 claims abstract description 26
- 239000004359 castor oil Substances 0.000 claims abstract description 19
- 235000019438 castor oil Nutrition 0.000 claims abstract description 19
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000001953 recrystallisation Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 6
- 229930195729 fatty acid Natural products 0.000 claims abstract description 6
- 239000000194 fatty acid Substances 0.000 claims abstract description 6
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical class CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 70
- 238000006243 chemical reaction Methods 0.000 claims description 44
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 claims description 34
- 229960003656 ricinoleic acid Drugs 0.000 claims description 34
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 24
- 238000005336 cracking Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 230000007017 scission Effects 0.000 claims description 24
- 238000010504 bond cleavage reaction Methods 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 20
- -1 sodium alkyl sulfate Chemical class 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 14
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 12
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical group [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- IJRHDFLHUATAOS-DPMBMXLASA-M sodium ricinoleate Chemical compound [Na+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O IJRHDFLHUATAOS-DPMBMXLASA-M 0.000 claims description 5
- 229960003280 cupric chloride Drugs 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 229940067741 sodium octyl sulfate Drugs 0.000 claims description 4
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 3
- 239000005750 Copper hydroxide Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- XKGDWZQXVZSXAO-ADYSOMBNSA-N Ricinoleic Acid methyl ester Chemical group CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC XKGDWZQXVZSXAO-ADYSOMBNSA-N 0.000 claims description 3
- VJOXQCZUUWMSIH-UHFFFAOYSA-N S(=O)(=O)(O)O.C(CCCCCCCCCCCCCCCCCCCCC)[Na] Chemical compound S(=O)(=O)(O)O.C(CCCCCCCCCCCCCCCCCCCCC)[Na] VJOXQCZUUWMSIH-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000003518 caustics Substances 0.000 claims description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- AZXVZUBIFYQWJK-KWRJMZDGSA-N ethyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCC AZXVZUBIFYQWJK-KWRJMZDGSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- VAKMIIPDYZXBEV-DPMBMXLASA-M potassium;(z,12r)-12-hydroxyoctadec-9-enoate Chemical compound [K+].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O VAKMIIPDYZXBEV-DPMBMXLASA-M 0.000 claims description 3
- WFRKJMRGXGWHBM-UHFFFAOYSA-M sodium;octyl sulfate Chemical compound [Na+].CCCCCCCCOS([O-])(=O)=O WFRKJMRGXGWHBM-UHFFFAOYSA-M 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 230000001360 synchronised effect Effects 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000006386 neutralization reaction Methods 0.000 abstract description 6
- NCXUIEDQTCQZRK-UHFFFAOYSA-L disodium;decanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCCCCCC([O-])=O NCXUIEDQTCQZRK-UHFFFAOYSA-L 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- YJCJVMMDTBEITC-UHFFFAOYSA-N 10-hydroxycapric acid Chemical compound OCCCCCCCCCC(O)=O YJCJVMMDTBEITC-UHFFFAOYSA-N 0.000 abstract 2
- 238000004042 decolorization Methods 0.000 abstract 2
- ZGPVCRPNBPLGDV-UHFFFAOYSA-N 11-oxoundecanoic acid Chemical compound OC(=O)CCCCCCCCCC=O ZGPVCRPNBPLGDV-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000000265 homogenisation Methods 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 37
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 33
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 16
- 229960001777 castor oil Drugs 0.000 description 15
- 239000000126 substance Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003776 cleavage reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000009969 flowable effect Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 150000002632 lipids Chemical class 0.000 description 7
- 150000002989 phenols Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 241000501754 Astronotus ocellatus Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- ANKBOVLKQMUDNQ-UHFFFAOYSA-N [Na].OCCCCCCCCCC(O)=O Chemical compound [Na].OCCCCCCCCCC(O)=O ANKBOVLKQMUDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- FIWQZURFGYXCEO-UHFFFAOYSA-M sodium;decanoate Chemical compound [Na+].CCCCCCCCCC([O-])=O FIWQZURFGYXCEO-UHFFFAOYSA-M 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002732 Polyanhydride Polymers 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 240000000528 Ricinus communis Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- YOURXVGYNVXQKT-UHFFFAOYSA-N oxacycloundecane-2,11-dione Chemical compound O=C1CCCCCCCCC(=O)O1 YOURXVGYNVXQKT-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 239000008031 plastic plasticizer Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing a sebacic acid from a castor oil compound. The method comprises the following steps that: pyrolysis of a castor oil compound, an isomerous carboxylic acid of a thinner, a high-temperature surface active agent for improving homogenization of a reaction mixture and/or high-temperature polymerization inhibitor for inhibiting polymerization of the castor oil compound at a high temperature is performed in a concentrated base solution to give initial pyrolysis product which is mixture of a decanedioic acid disodium salt, 10-hydroxydecanoic acid and a 10-formyldecanoic acid; the mixture is oxidized by a high-temperature strong base to give the decanedioic acid disodium salt. An end pyrolysis product is subjected to neutralization, separation of fatty acid, decolourization by macroporous resin, decolourization by active carbon, acidification, crystallization and recrystallization to produce an industrial sebacic acid and a fine sebacic acid. The method has the advantages of avoidance of pollution caused by phenol contained waste water generated by using a phenol contained thinner, more complete pyrolysis, improvement on yield of sebacic acid and purity of sebacic acid, and reduction in raw material consumption.
Description
Technical field
The present invention relates to the preparation method of Chemicals sebacic acid, especially is the method for feedstock production Chemicals sebacic acid with the Viscotrol C compounds.
Background technology
Along with the aggravation of the whole world to petroleum resource consumption, the manufacturing of biomass Chemicals more and more receives publicity, wherein there are hydroxyl, ester group, three reactable functional groups of two key in the Viscotrol C molecule simultaneously, for a long time always as the industrial plant grease, be one of the important raw and processed materials of the manufacturing of biomass Chemicals.
At present, nearly all be to be that raw material is produced sebacic acid in the world with Viscotrol C.Based on the factor of starting material source and technology two aspects, China has become the country of unique in the world production sebacic acid.Sebacic acid and sec-n-octyl alcohol are the primary products of Viscotrol C alkalescence Pintsch process, and industrial sec-n-octyl alcohol often is taken as by product or coproduction product, and this also is the characteristics that the biomass Chemicals are made, and all have the product of association to exist usually.
Sebacic acid is the important source material of the synthetic and organic synthesis of polymer materials.Sebacic acid is the monomer of synthesizing engineering plastic nylon 410,610,810 and 1010, it also is the monomer of medicament slow release material poly sebacic polyanhydride, or the dibasic acid component of Biodegradable polyester, sebacic anhydride is the linking agent of biodegradable plastic, and sebacic acid ester is widely used as the important intermediate of senior lubricant, cold resistant plasticizer, makeup, medicine, fragrant section, polyester film, tensio-active agent and additive etc.; Sec-n-octyl alcohol is mainly used in synthesizing hexanoic acid or oxidation generates methyl hexyl ketone (spices), also can be used as foam removal (froth breaking) agent, synthetic softening agent, tensio-active agent, farm chemical emulgent, synthetic perfume and solvent etc., especially phthalic acid di-sec-octyl, sebacic acid di-sec-octyl are good plastic plasticizers.
The Viscotrol C of relevant report and the know-why that derivative prepares sebacic acid thereof are that Viscotrol C or castor oil derivative hydro-oxidation sodium water solution in the presence of thinner carry out the cracking of high temperature highly basic at 200-350 ℃ both at home and abroad, generate Decanedioic acid, sodium salt, sec-n-octyl alcohol, hydrogen, the split product dilute with water, neutralization, decolouring, acidifying, crystallization, separate out the sebacic acid crystal after the cooling, dry industrial sebacic acid, while coproduction sec-n-octyl alcohol when cracking, by-product lipid acid or lipid acid and the glycerine of getting.This process can letter be shown as follows with reaction equation:
1, Viscotrol C is produced the chemical equation of sebacic acid
2, castor oil derivative (ricinolic acid is an example) is produced the chemical equation of sebacic acid
In fact, because the high viscosity of soap compounds of saponification reaction generation even the high foam performance of curing and soap class take place in Viscotrol C and castor oil derivative under the highly basic condition, make the scission reaction under the high temperature be difficult to carry out smoothly, great influence often also takes place to the sebacic acid yield in the existence of foam and heterogeneous property in the reaction system.Many investigators have successively carried out a large amount of work for solving this difficult problem, outstanding work is (1) Georges Dupont and Oscar Kostelitz, USP2674608 (1950) highly basic is handled ricinolic acid and derivative thereof, (2) Roger L.Logan and Subhash V.Udeshi, USP 6392074 (2002), prepare the method for sebacic acid and sec-n-octyl alcohol.Wherein Georges Dupont and Oscar Kostelitz with phenolic compound such as ortho-cresol or phenol as thinner, imported the high temperature highly basic scission reaction of Viscotrol C and derivative thereof, the yield of sebacic acid is had increased significantly, this technological line becomes the existing production technique of present domestic sebacic acid manufacturing concern through the multi-faceted improvement of China, and each manufacturing enterprise has their own characteristics each, roughly similar; But, the drawback that this processing technology routine brought is also showed out, one ton of sebacic acid industrial goods of every production can produce 35 tons of the phenolic wastewater of concentration about 2500ppm, and a spot of aldehydes matter mixes the quality that also makes product in sebacic acid and is subjected to a certain degree influence; Along with the enhancing of environmental consciousness, the processing of phenolic wastewater makes enterprise increase production cost, the raising of discharge of wastewater requirement simultaneously, the risk that also makes enterprise might face limited production even stop production.Roger L.Logan and Subhash V.Udeshi have researched and developed the technological line that a non-phenol thinner prepares sebacic acid, the lower characteristics of isomery carboxylate salt fusing point that it adopts the isomery aliphatic carboxylic acid to change under reaction conditions, thinner when making it become Pintsch process, and do not use phenolic compound, appropriateness has solved reaction mixture cured and a large amount of foamy problem simultaneously; Yet, this patent of invention is primarily aimed at the replacement of thinner kind, the repeated experiments demonstration remains in problem: 1) castor oil derivative generation polymerizations such as Viscotrol C or ricinolic acid cause product colourity seriously higher under the high-temperature condition, 2) reaction system can only be kept relative homogeneity under the set higher diluent concentration condition of invention (weight ratio of Viscotrol C or castor oil derivative and thinner is about 1: 1), diluent concentration is higher will to make that the utilization ratio of conversion unit is on the low side, single still efficient is not high, 3) generally speaking, use isomery carboxylic acid or isomery aldehyde, isomery alcohol replaces phenolic compound, sebacic acid yield (2.0-2.05 ton Viscotrol C/ton sebacic acid) when the yield of principal product sebacic acid (2.25-2.4 ton Viscotrol C/ton sebacic acid) all is lower than domestic use phenolic compound, and isomery aldehyde and isomery alcohol during as thinner operation comparatively loaded down with trivial details.
Summary of the invention
Technical problem to be solved by this invention is: in the presence of non-phenol thinner isomery carboxylic acid, by adding pyrometer surface-active agent and elevated temperature heat stopper, make the Viscotrol C compounds produce sebacic acid, the yield of sebacic acid when containing the phenol thinner to meet or exceed in the cracking of high temperature highly basic.
In order to solve the problems of the technologies described above, the present invention prepares the method for sebacic acid by the Viscotrol C compounds, in turn includes the following steps:
(1) with Viscotrol C compounds, thinner isomery carboxylic acid, promote the pyrometer surface-active agent of reaction mixture homogeneity and/or avoid the elevated temperature heat stopper of Viscotrol C compounds thermopolymerization under high temperature action, mix, cracking prepares the cracking head product under 200～230 ℃ of strong alkaline conditions, and sec-n-octyl alcohol is distillated in the process of reaction;
(2) the cracking head product that obtains slowly is warming up to 300-330 ℃, the dehydrogenation oxidation that carries out under the high temperature strong alkaline condition reacts, preparation split product sebacic acid bimetal salt;
(3) split product through water dilution, in and separation of fatty acids and thinner, thinner is reclaimed in underpressure distillation, the aqueous solution is through decolouring, acidifying, growing the grain manufacture sebacic acid, twice refining sebacic acid of recrystallization preparation.
The pyrometer surface-active agent is a kind of in the sodium alkyl sulfate of C6-C30 or the silicone oil that molecular weight is 1500-15000 in the described step (1); With ricinolic acid weight is benchmark, and volume is 0.1-5%.
Described sodium alkyl sulfate is one or more the combination in sodium octyl sulfate, sodium lauryl sulphate, Trombovar or the docosyl sodium sulfate.
The elevated temperature heat stopper is chlorate, vitriol, nitrate or the oxyhydroxide of variable valence transition metal in the described step (1), and a kind of in the S-WAT, Sodium Nitrite, sodium phosphite; With ricinolic acid weight is benchmark, and volume is 0.2-5%.
Described elevated temperature heat stopper is a kind of in cupric chloride, iron(ic) chloride, nitric acid ketone, iron nitrate, blue vitriol, ferric sulfate, copper hydroxide, the ironic hydroxide.
Described Viscotrol C compounds is a kind of in Viscotrol C, ricinolic acid, ricinolic acid methyl esters, ricinolic acid ethyl ester, sodium ricinoleate, potassium ricinoleate, hydrogenated castor oil, 12-oxystearic acid or the 12-acetoxyl group stearic acid.
Described Viscotrol C compounds is hydrolyzed to ricinolic acid or Viscotrol C salt earlier, carries out scission reaction again.
The content of methyln-hexyl ketone makes scission reaction be subjected to accurate control as the middle control index of scission reaction in the quantity of distillate of the middle establishment of described step (1) sec-n-octyl alcohol and the sec-n-octyl alcohol.
Described highly basic is strong caustic.
In the described step (1) the Viscotrol C compounds is carried out first change killing or preheating earlier, feed in raw material by 2: 1 synchronous modes that add of weight ratio of ricinolic acid and alkali with pre-heat alkali liquid again.
The invention has the beneficial effects as follows: adopt the isomery carboxylic acid to substitute the source of pollution that phenolic compound has been eradicated phenolic wastewater, replace the waste water of more tractable fatty acids, environmentally friendly; The use of pyrometer surface-active agent and the reaction process of sectional type can make cracking steadily carry out, and the sec-n-octyl alcohol of coproduction and hydrogen sectional reclaim with the liquids and gases form; The minimizing of thinner consumption can promote still and imitate, and enhances productivity; The interpolation of high temperature stopper has suppressed the generation of the polymkeric substance of raw material Viscotrol C or castor oil derivative, and the yield when making the yield of sebacic acid meet and exceed the phenols thinner has reduced raw materials consumption effectively; The establishment of middle control index, the accurate control when helping to produce.
Description of drawings
Fig. 1 is the present invention is prepared sebacic acid by the Viscotrol C compounds a production technique.
Embodiment
The present invention prepares the method for sebacic acid by the Viscotrol C compounds, in turn includes the following steps:
(1) with Viscotrol C compounds, thinner isomery carboxylic acid, promote the pyrometer surface-active agent of reaction mixture homogeneity and/or avoid the elevated temperature heat stopper of Viscotrol C compounds thermopolymerization under high temperature action, mix, cracking prepares the cracking head product under 200～230 ℃ of strong alkaline conditions, and sec-n-octyl alcohol is distillated in the process of reaction;
(2) the cracking head product that obtains slowly is warming up to 300-330 ℃, the dehydrogenation oxidation that carries out under the high temperature strong alkaline condition reacts, preparation split product sebacic acid bimetal salt;
(3) split product through water dilution, in and separation of fatty acids and thinner, thinner is reclaimed in underpressure distillation, the aqueous solution is through decolouring, acidifying, growing the grain manufacture sebacic acid, twice refining sebacic acid of recrystallization preparation.
The pyrometer surface-active agent is a kind of in the sodium alkyl sulfate of C6-C30 or the silicone oil that molecular weight is 1500-15000 in the described step (1); With ricinolic acid weight is benchmark, and volume is 0.1-5%.
Described sodium alkyl sulfate is one or more the combination in sodium octyl sulfate, sodium lauryl sulphate, Trombovar or the docosyl sodium sulfate.
The elevated temperature heat stopper is chlorate, vitriol, nitrate or the oxyhydroxide of variable valence transition metal in the described step (1), and a kind of in the S-WAT, Sodium Nitrite, sodium phosphite; With ricinolic acid weight is benchmark, and volume is 0.2-5%.
Described elevated temperature heat stopper is a kind of in cupric chloride, iron(ic) chloride, nitric acid ketone, iron nitrate, blue vitriol, ferric sulfate, copper hydroxide, the ironic hydroxide.
Described Viscotrol C compounds is a kind of in Viscotrol C, ricinolic acid, ricinolic acid methyl esters, ricinolic acid ethyl ester, sodium ricinoleate, potassium ricinoleate, hydrogenated castor oil, 12-oxystearic acid or the 12-acetoxyl group stearic acid.
Described Viscotrol C compounds is hydrolyzed to ricinolic acid or Viscotrol C salt earlier, carries out scission reaction again.
The content of methyln-hexyl ketone makes scission reaction be subjected to accurate control as the middle control index of scission reaction in the quantity of distillate of the middle establishment of described step (1) sec-n-octyl alcohol and the sec-n-octyl alcohol.
Described highly basic is strong caustic.
In the described step (1) the Viscotrol C compounds is carried out first change killing or preheating earlier, feed in raw material by 2: 1 synchronous modes that add of weight ratio of ricinolic acid and alkali with pre-heat alkali liquid again.
Following embodiment is described in further detail the present invention.
1) preparation of ricinolic acid: change into ricinolic acid, by-product glycerol water by the hydrolysis under 0.65-0.80MPa, 165-175 ℃ condition of industrial Viscotrol C, water, zinc oxide.Experiment confirm: ricinolic acid or sodium ricinoleate are one of best cracking starting material, generally all need preparation voluntarily during production.
2) the high temperature highly basic cracking of Viscotrol C or castor oil derivative: Viscotrol C or castor oil derivative cracking at high temperature in the strong solution of 5-10%wt thinner (is benchmark with Viscotrol C or castor oil derivative) and alkali.For reacting balance is carried out,, cracking is launched in two steps according to scission reaction mechanism.At first under 200-230 ℃, remove most of sec-n-octyl alcohol (more than 95% of theoretical amount), produce the mixed pyrolysis product of Decanedioic acid, sodium salt, 10-hydroxydecanoic acid sodium, 10-aldehyde radical Sodium decanoic acid simultaneously.
3) cleavage reaction mixture slowly is warming up to 300-330 ℃ and carries out high temperature oxidation reaction and make 10-hydroxydecanoic acid sodium, 10-aldehyde radical Sodium decanoic acid change into Decanedioic acid, sodium salt.
In fact, the reaction of 200-350 ℃ of following Viscotrol C compounds cracking generation sebacic acid is progressively to carry out, and comprises two reactions of alkaline bleach liquor cleavage and high temperature oxidation.
Because the scission reaction temperature is higher, and be reflected under the strong alkaline condition and carry out, it is lower that the sodium salt that used thinner isomery carboxylic acid forms such as the fusing point of Sodium isooctanoate (2 ethyl hexanoic acid sodium) align the structure carboxylic acid mutually, but still more than 300 ℃, although there is a certain amount of water in the reaction system, the high viscosity of the hydrophobicity of the long carbochain of Viscotrol C and derivative thereof and soap compounds and high foaminess, still make cleavage reaction mixture existence heterogeneous characteristic to a certain degree, therefore, in the cracking material, add high temperature resistant surfactant, cracking can be carried out under homogeneous phase condition, thereby improved the cracking degree of Viscotrol C compounds, can compare favourably with the phenols thinner.
Experiment confirm; in so high cracking temperature and very strong alkaline environment; even add Viscotrol C or castor oil derivative in the dropping mode; polymerization to a certain degree still is difficult to avoid; usually the oligopolymer or the multipolymer that have Viscotrol C or castor oil derivative exist; polymkeric substance can be sneaked in crystallisation process influences its colourity and purity in the sebacic acid, therefore, add the generation that high temperature resistant stopper suppresses polyreaction.
In addition, in the two-part scission reaction, the quantity of distillate of liquid sec-n-octyl alcohol and methyln-hexyl ketone content therein can be used as the important measurement index that scission reaction is carried out fine or notly.The degree that scission reaction is carried out can be tentatively judged in the quantity of distillate of sec-n-octyl alcohol and the comparison of theoretical amount, in order to determine the heating-up time; When methyln-hexyl ketone content is higher in the sec-n-octyl alcohol, illustrate that first section cracking temperature is higher, can cause the sebacic acid yield on the low side.
4) subsequent disposal of split product: split product dilute with water, neutralization, decolouring (twice decolouring of macroporous resin and gac), acidifying, crystallization get industrial sebacic acid.
5) preparation of refining sebacic acid: the sebacic acid solution after decolouring and acidifying carries out recrystallization, secondary hot water's recrystallization, and drying must be made with extra care sebacic acid.
Industry sebacic acid and refining sebacic acid production technique are seen Fig. 1, are ordinary method.
Used Viscotrol C is industrial goods among the following embodiment, glycerine three (12-hydroxyl-9-alkene 18 carbonic acid) ester content 90% wherein, and ricinolic acid prepares according to described method.
Embodiment 1 Viscotrol C and 2 ethyl hexanoic acid
Reactor is equipped with mechanical stirring, balance dropping funnel, the water trap that is connected with condenser, thermometer.The 240g Viscotrol C adds dropping funnel, the 120g 2 ethyl hexanoic acid adds in the reactor, start to stir and heating, 50%NaOH 300 g slowly add in the reactor, after temperature rise to 210 in the reactor ℃, water condensation is arranged in the water trap, drip Viscotrol C this moment, in keeping warm 200-220 ℃, distillates along with the adding of Viscotrol C has sec-n-octyl alcohol immediately, reaction mixture is changed to homogeneous phase by heterogeneous gradually simultaneously, added Viscotrol C in 2-3 hour, this moment, the sec-n-octyl alcohol quantity of distillate was the 90-95% of Theoretical Calculation amount.Afterwards, the control heat-up rate avoids hydrogen and moisture, a large amount of effusion of sec-n-octyl alcohol to cause material to overflow, after temperature reaches 300 ℃, keep 300-330 ℃ of continuation reaction and only no longer included condenses in 2 hours, also no longer include gas evolution, reaction mixture is even flowable liquid state.
Cleavage reaction mixture dilute with water, sulfuric acid are neutralized to pH 5.8～6.0 and isolate lipid acid and thinner (2 ethyl hexanoic acid 112g is reclaimed in underpressure distillation), and activated carbon decolorizing, sulfuric acid acidation are to pH 1-2.Be heated to boiling, filtered while hot, filter residue is a colloidal substance, dry back is a pale powder; Filtrate crystallisation by cooling, filtration, drying get sebacic acid, 98g, fusing point 130.5-134 ℃.
Embodiment 2 ricinolic acids and 2 ethyl hexanoic acid
Reactor and operation just substitute Viscotrol C with the 240g ricinolic acid with embodiment 1.
The sec-n-octyl alcohol quantity of distillate is the 95-98% of Theoretical Calculation amount in the scission reaction, the high temperature oxidation reaction mixture is even flowable liquid state, 2 ethyl hexanoic acid 115g is reclaimed in neutralization back underpressure distillation, the acidizing fluid heat filtering, filter residue is colloidal substance (dry back is pale powder), get sebacic acid, 102g, fusing point 131.5-134 ℃.
Embodiment 3 ricinolic acids, 2 ethyl hexanoic acid, pyrometer surface-active agent
Reactor is with embodiment 1.The 240g ricinolic acid, the 80g 2 ethyl hexanoic acid, distilled water 100g, the dispersion liquid of sodium lauryl sulphate preparation adds dropping funnel, 50%NaOH 280g adds in the reactor, start and stir and heating, after temperature rise to 210 in the reactor ℃, water condensation is arranged in the water trap, drip dispersion liquid this moment, keep interior warm 200-220 ℃, along with the adding of dispersion liquid has sec-n-octyl alcohol to distillate immediately, there be the heterogeneous of blink in reaction mixture simultaneously, very promptly by the heterogeneous homogeneous phase that changes into, added dispersion liquid in 2-3 hour, this moment, the sec-n-octyl alcohol quantity of distillate was the 95-98% of Theoretical Calculation amount.Afterwards, the control heat-up rate avoids hydrogen and moisture, a large amount of effusion of sec-n-octyl alcohol to cause material to overflow, after temperature reaches 300 ℃, keep 300-330 ℃ of continuation reaction and only no longer included condenses in 2 hours, also no longer include gas evolution, reaction mixture is even flowable liquid state.
Cleavage reaction mixture dilute with water, sulfuric acid are neutralized to pH 5.8～6.0 and isolate lipid acid and thinner (2 ethyl hexanoic acid 75g is reclaimed in underpressure distillation), and activated carbon decolorizing, sulfuric acid acidation are to pH 1-2.Be heated to boiling, filtered while hot has the insoluble colloid of canescence, is white powder after air-dry; Filtrate crystallisation by cooling, filtration, drying get sebacic acid, fusing point 132-133.5 ℃.The sodium lauryl sulphate add-on is respectively 0.5,2.5, during 7.5g, sebacic acid is followed successively by 104,108,110g.
Embodiment 4 ricinolic acids, 2 ethyl hexanoic acid, high temperature stopper
Reactor and operation just substitute sodium lauryl sulphate with S-WAT with embodiment 3
The sec-n-octyl alcohol quantity of distillate is the 95-98% of Theoretical Calculation amount in the scission reaction, and the high temperature oxidation reaction mixture is even flowable liquid state.2 ethyl hexanoic acid 75g is reclaimed in neutralization back underpressure distillation, and the acidizing fluid heat filtering does not almost have filter residue; Crystallization gets sebacic acid, fusing point 132-133.5 ℃.
The S-WAT add-on is respectively 0.5,2.0, during 7.5g, sebacic acid is followed successively by 110,115,116g.
Embodiment 5 ricinolic acids, 2 ethyl hexanoic acid, pyrometer surface-active agent and high temperature stopper
Reactor is with embodiment 1.The 240g ricinolic acid, the 80g 2 ethyl hexanoic acid, distilled water 100g, the dispersion liquid of sodium lauryl sulphate 2.0g and S-WAT 2.0g preparation adds dropping funnel, 50%NaOH 280g adds in the reactor, start and stir and heating, after temperature rise to 210 in the reactor ℃, water condensation is arranged in the water trap, drip dispersion liquid this moment, keep interior warm 200-220 ℃, along with the adding of dispersion liquid has sec-n-octyl alcohol to distillate immediately, there be the heterogeneous of blink in reaction mixture simultaneously, very promptly by the heterogeneous homogeneous phase that changes into, added dispersion liquid in 2-3 hour, this moment, the sec-n-octyl alcohol quantity of distillate was the 95-98% of Theoretical Calculation amount.Afterwards, the control heat-up rate avoids hydrogen and moisture, a large amount of effusion of sec-n-octyl alcohol to cause material to overflow, after temperature reaches 300 ℃, keep 300-330 ℃ of continuation reaction and only no longer included condenses in 2 hours, also no longer include gas evolution, reaction mixture is even flowable liquid state.
Cleavage reaction mixture dilute with water, sulfuric acid are neutralized to pH 5.8～6.0 and isolate lipid acid and thinner (2 ethyl hexanoic acid 75g is reclaimed in underpressure distillation), and activated carbon decolorizing, sulfuric acid acidation are to pH 1-2.Be heated to boiling, filtered while hot does not almost have filter residue; Filtrate crystallisation by cooling, filtration, drying get sebacic acid, 125g, fusing point 132-133.5 ℃.
Embodiment 6 first change killing ricinolic acids and 2 ethyl hexanoic acid, high temperature stopper and pyrometer surface-active agent
Reactor is with embodiment 1.240g ricinolic acid, 80g 2 ethyl hexanoic acid, distilled water 100g, sodium lauryl sulphate 2.4g and S-WAT 2.4g and 50%NaOH 260g react, and obtain containing the transparent first change killing solution of sodium ricinoleate, 2 ethyl hexanoic acid sodium.First change killing solution adds dropping funnel, 50%NaOH 40 g add in the reactor, start to stir and heating, after temperature rise to 210 in the reactor ℃, water condensation is arranged in the water trap, drip first change killing liquid this moment, have sec-n-octyl alcohol to distillate immediately, keep interior warm 200-220 ℃, reaction mixture is a homogeneous phase, added first change killing liquid in 2-3 hour, this moment, the sec-n-octyl alcohol quantity of distillate was the 95-99% of Theoretical Calculation amount.Afterwards, the control heat-up rate avoids hydrogen and moisture, a large amount of effusion of sec-n-octyl alcohol to cause material to overflow, after temperature reaches 300 ℃, keep 300-330 ℃ of continuation reaction and only no longer included condenses in 2 hours, also no longer include gas evolution, reaction mixture is even flowable liquid state.
Cleavage reaction mixture dilute with water, sulfuric acid are neutralized to pH 5.8～6.0 and isolate lipid acid and thinner (2 ethyl hexanoic acid 76g is reclaimed in underpressure distillation), and activated carbon decolorizing, sulfuric acid acidation are to pH 1-2.Be heated to boiling, filtered while hot does not have obvious solid filter residue and finds; Filtrate crystallisation by cooling, filtration, drying get sebacic acid, 130g, fusing point 132-133.5 ℃.
Embodiment 7 ricinolic acids, 2 ethyl hexanoic acid, pyrometer surface-active agent and high temperature stopper
The 50L reactor is equipped with electrically heated, condenser, thermopair, mechanical stirring, and the viscosity of reaction mass is represented by stir current.
Drop into 50%NaOH 2kg in the reactor in advance, start and stir and heating, after temperature in the kettle rises to 220 ℃, water condensation is arranged in the condenser, dispersion liquid and the 50%NaOH 15kg that be mixed with 15kg ricinolic acid, 2 ethyl hexanoic acid, distilled water 10kg, sodium lauryl sulphate 150g and S-WAT 150g in proportion by two volume pumps this moment respectively squeeze into reactor synchronously, the beginning scission reaction.Along with the adding of material, sec-n-octyl alcohol is distillated immediately, and the viscosity of reaction mixture changes, and regulates feed rate according to the variation of electric current, adds in 3-4 hour, reaches more than 95% of theoretical quantity of distillate until the quantity of distillate of sec-n-octyl alcohol.Afterwards, the control heat-up rate avoids hydrogen and moisture, a large amount of effusion of sec-n-octyl alcohol to cause material to overflow, after temperature reaches 300 ℃, keep 300-330 ℃ of continuation reaction and only no longer included condenses in 2 hours, also no longer include gas evolution, reaction mixture is even flowable thick liquid state.
Cleavage reaction mixture dilute with water, sulfuric acid are neutralized to pH 5.8～6.0 and isolate lipid acid and thinner, and activated carbon decolorizing, sulfuric acid acidation are to pH 1-2.Be heated to boiling, filtrate crystallisation by cooling, filtration, drying get sebacic acid, fusing point 131.5-134 ℃.
When the add-on of 2 ethyl hexanoic acid was respectively 1.5kg, 1.12kg, 0.75kg, industrial sebacic acid yield was followed successively by 7.3kg, 7.2kg, 7.2kg, and 2 ethyl hexanoic acid 1.40kg, 1.05kg, 0.70kg are reclaimed in underpressure distillation respectively.
Reference examples ricinolic acid and phenol
The two-part reactor, 360 ℃ of salt bath heating of last still, 420 ℃ of salt bath heating of still down, mechanical stirring, material viscosity are controlled by stir current.Ricinolic acid, phenol are mixed with the acid solution that contains the phenol thinner, 50%NaOH (aq) squeezes into the two-part reactor by volume pump respectively, change adjusting soda acid ratio according to material viscosity and control the material reaction temperature of still up and down respectively, the reaction times of top layer material at the bottom of the still is 6 hours behind the full still of control material, by screw feeder split product is pulled out at the bottom of the still.Cracking material dilute with water, sulfuric acid neutralization, separation of fatty acids, macroporous resin decolouring, activated carbon decolorizing, acidifying, growing the grain, drying, drying get industrial sebacic acid.Contain phenolic acid liquid by ricinolic acid 2400kg, phenol 120kg preparation, 50%NaOH (aq) 2400kg gets industrial sebacic acid 1250kg.
Embodiment 8 ricinolic acids, 2 ethyl hexanoic acid, pyrometer surface-active agent and high temperature stopper
Reactor and the same reference examples of operation just substitute the acid solution that contains the phenol thinner by the acid solution that contains thinner that ricinolic acid, 2 ethyl hexanoic acid are mixed with.
The acid solution that contains 2 ethyl hexanoic acid is by ricinolic acid 2400kg, 2 ethyl hexanoic acid 120kg, 2.4kg sodium lauryl sulphate, 2.4kg S-WAT and an amount of distilled water preparation, and 50%NaOH (aq) 2400kg gets industrial sebacic acid 1200kg.
Embodiment 9-17
Reactor and operation are with embodiment 6, ricinolic acid 240g, thinner 80g, pyrometer surface-active agent 2.4g, high temperature stopper 2.4g, 50%NaOH 300g, experimental result shows: under pyrometer surface-active agent and high temperature stopper synergy, reaction mixture is homogeneous phase, the thermopolymerization phenomenon is suppressed substantially, and the amount of diluent recovery and sebacic acid is listed in the table below.
| Embodiment | Thinner | The pyrometer surface-active agent | The high temperature stopper | Diluent recovery | Sebacic acid |
| 9 | Isovaleric acid | Sodium lauryl sulphate | S-WAT | 68g | 118g |
| 10 | 2 ethyl hexanoic acid | Sodium octyl sulfate | SODIUMNITRATE | 70g | 116g |
| 11 | 2 ethyl hexanoic acid | Trombovar | S-WAT | 76g | 125g |
| 12 | Different n-nonanoic acid | Sodium lauryl sulphate | Copper sulfate | 75g | 122g |
| 13 | 2 ethyl hexanoic acid | Silicone oil (Mn=1500) | Ironic hydroxide | 73g | 120g |
| 14 | Isodecyl acid | Sodium lauryl sulphate | Iron nitrate | 75g | 115g |
| 15 | 2 ethyl hexanoic acid | Sodium lauryl sulphate | Cupric chloride | 74g | 124g |
| 16 | 2 ethyl hexanoic acid | Docosyl sodium sulfate | Sodium Nitrite | 76g | 126g |
| 17 | 2 ethyl hexanoic acid | Sodium lauryl sulphate | Sodium phosphite | 76g | 130g |
Embodiment 18 refining sebacic acid
Industrial sebacic acid among the above embodiment, distilled water with 15-30 times (weight) carries out twice recrystallization operation, the overheated steam heating, filtered while hot, miscellaneous water-insoluble impurity in the industrial sebacic acid is removed, simultaneously the sodium sulfate that wraps up in the industrial sebacic acid is dissolved in the water crystallisation by cooling, drying, drying must be made with extra care sebacic acid.
In sum, the preparation method who produces sebacic acid from the castor-oil plant compound of the present invention:
1. change the technological line that domestic use contains the phenol thinner, used isomery carboxylic acid such as 2 ethyl hexanoic acid to be thinner, fundamentally stopped the generation of phenolic wastewater, environmental friendliness;
2. improved the technological line of USP6392704 (2002), use the pyrometer surface-active agent to make the reaction system homogeneity better, the generation of heat polymerization at high temperature of Viscotrol C and derivative thereof has been avoided in the use of high temperature stopper simultaneously, has improved the yield of product sebacic acid;
3. the technology of the present invention route is middle control index with the content of methyln-hexyl ketone in the quantity of distillate of sec-n-octyl alcohol and the sec-n-octyl alcohol, is the more accurate reflection of scission reaction completeness and reaction conditions, easily and effectively.
4. feed way also has certain influence to the final yield of scission reaction and even sebacic acid.The Viscotrol C of preheating or castor oil derivative and alkali lye are better by the mode that metering adds synchronously, and the Viscotrol C of first change killing or castor oil derivative and alkali lye are better by the mode that metering adds synchronously.
5. the content of moisture in the maintenance scission reaction, to the homogeneity of keeping reaction mixture and scission reaction is very necessary fully.
6. the technology of the present invention route obtains industrial sebacic acid through recrystallization or secondary recrystallization, can obtain refining sebacic acid, and method is simple, and additional production cost is not high.
Can reach the level of one ton of sebacic acid consumption of every production Viscotrol C below 2 tons or 2 tons from the raw materials consumption of ricinolic acid manufacture sebacic acid by the inventive method, compared with the minimum consumption 2.25 of USP6392704 (2002) significantly and reduced, the consumption when including the phenol thinner with state quite and decrease.
In sum, content of the present invention is not limited in the above-described embodiment, and the knowledgeable people in the same area can propose other embodiment easily within technical director's thought of the present invention, but this embodiment comprises within the scope of the present invention.
Claims (10)
1, a kind ofly prepare the method for sebacic acid, in turn include the following steps by the Viscotrol C compounds:
(1) with Viscotrol C compounds, thinner isomery carboxylic acid, promote the pyrometer surface-active agent of reaction mixture homogeneity and/or avoid the elevated temperature heat stopper of Viscotrol C compounds thermopolymerization under high temperature action, mix, cracking prepares the cracking head product under 200～230 ℃ of strong alkaline conditions, and sec-n-octyl alcohol is distillated in the process of reaction;
(2) the cracking head product that obtains slowly is warming up to 300-330 ℃, the dehydrogenation oxidation that carries out under the high temperature strong alkaline condition reacts, preparation split product sebacic acid bimetal salt;
(3) split product through water dilution, in and separation of fatty acids and thinner, thinner is reclaimed in underpressure distillation, the aqueous solution is through decolouring, acidifying, growing the grain manufacture sebacic acid, twice refining sebacic acid of recrystallization preparation.
2, according to claim 1ly prepare the method for sebacic acid by the Viscotrol C compounds, it is characterized in that, the pyrometer surface-active agent is a kind of in the sodium alkyl sulfate of C6-C30 or the silicone oil that molecular weight is 1500-15000 in the described step (1); With ricinolic acid weight is benchmark, and volume is 0.1-5%.
3, according to claim 2ly prepare the method for sebacic acid by the Viscotrol C compounds, it is characterized in that, described sodium alkyl sulfate is a kind of in sodium octyl sulfate, sodium lauryl sulphate, Trombovar or the docosyl sodium sulfate.
4, the method for preparing sebacic acid by the Viscotrol C compounds according to claim 1, it is characterized in that, the elevated temperature heat stopper is chlorate, vitriol, nitrate or the oxyhydroxide of variable valence transition metal in the described step (1), and a kind of in the S-WAT, Sodium Nitrite, sodium phosphite; With ricinolic acid weight is benchmark, and volume is 0.2-5%.
5, the method for preparing sebacic acid by the Viscotrol C compounds according to claim 4, it is characterized in that described elevated temperature heat stopper is the one or more combination in cupric chloride, iron(ic) chloride, nitric acid ketone, iron nitrate, blue vitriol, ferric sulfate, copper hydroxide, the ironic hydroxide.
6, the method for preparing sebacic acid by the Viscotrol C compounds according to claim 1, it is characterized in that described Viscotrol C compounds is a kind of in Viscotrol C, ricinolic acid, ricinolic acid methyl esters, ricinolic acid ethyl ester, sodium ricinoleate, potassium ricinoleate, hydrogenated castor oil, 12-oxystearic acid or the 12-acetoxyl group stearic acid.
7, according to claim 6ly prepare the method for sebacic acid, it is characterized in that described Viscotrol C compounds is hydrolyzed to ricinolic acid or Viscotrol C salt earlier, carry out scission reaction again by the Viscotrol C compounds.
8, the method for preparing sebacic acid by the Viscotrol C compounds according to claim 1, it is characterized in that: the content of methyln-hexyl ketone makes scission reaction be subjected to accurate control as the middle control index of scission reaction in the quantity of distillate of the middle establishment of described step (1) sec-n-octyl alcohol and the sec-n-octyl alcohol.
9, according to claim 1ly prepare the method for sebacic acid by the Viscotrol C compounds, it is characterized in that: described highly basic is strong caustic.
10, the method for preparing sebacic acid by the Viscotrol C compounds according to claim 1, it is characterized in that, in the described step (1) the Viscotrol C compounds is carried out first change killing or preheating earlier, feed in raw material by 2: 1 synchronous modes that add of weight ratio of ricinolic acid and alkali with pre-heat alkali liquid again.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826991A (en) * | 2012-07-24 | 2012-12-19 | 山东天兴生物科技有限公司 | Process and device for continuous acidification of acidification section in production of sebacic acid |
| CN111850596A (en) * | 2020-07-13 | 2020-10-30 | 万华化学集团股份有限公司 | Continuous production method for electrochemically synthesizing sebacate compounds |
| CN112299997A (en) * | 2020-11-20 | 2021-02-02 | 河南大学 | Method for separating and extracting chain ester compounds from Nigella sativa seeds |
| CN113512172A (en) * | 2021-06-02 | 2021-10-19 | 茂施农业科技有限公司 | Polyester polyol polyurethane controlled-release fertilizer film material synthesized by sebacic acid byproduct fatty acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5952517A (en) * | 1997-02-14 | 1999-09-14 | Caschem, Inc. | Method for preparing cleaved products from castor oil or derivatives thereof |
| US6392074B1 (en) * | 2000-05-12 | 2002-05-21 | Roger L. Logan | Method for preparing sebacic acid and octanol-2 |
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2008
- 2008-07-23 CN CN2008100539172A patent/CN101318892B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826991A (en) * | 2012-07-24 | 2012-12-19 | 山东天兴生物科技有限公司 | Process and device for continuous acidification of acidification section in production of sebacic acid |
| CN102826991B (en) * | 2012-07-24 | 2014-09-24 | 山东天兴生物科技有限公司 | Process and device for continuous acidification of acidification section in production of sebacic acid |
| CN111850596A (en) * | 2020-07-13 | 2020-10-30 | 万华化学集团股份有限公司 | Continuous production method for electrochemically synthesizing sebacate compounds |
| CN111850596B (en) * | 2020-07-13 | 2021-04-20 | 万华化学(四川)有限公司 | Continuous production method for electrochemically synthesizing sebacate compounds |
| CN112299997A (en) * | 2020-11-20 | 2021-02-02 | 河南大学 | Method for separating and extracting chain ester compounds from Nigella sativa seeds |
| CN112299997B (en) * | 2020-11-20 | 2022-12-20 | 河南大学 | Method for separating and extracting chain ester compounds from Nigella sativa seeds |
| CN113512172A (en) * | 2021-06-02 | 2021-10-19 | 茂施农业科技有限公司 | Polyester polyol polyurethane controlled-release fertilizer film material synthesized by sebacic acid byproduct fatty acid |
| CN113512172B (en) * | 2021-06-02 | 2022-02-22 | 茂施农业科技有限公司 | Sebacic acid byproduct fatty acid polyester polyol for polyurethane controlled release fertilizer coating |
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