CN110669254B - Method for preparing epoxy plasticizer from waste grease - Google Patents
Method for preparing epoxy plasticizer from waste grease Download PDFInfo
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- CN110669254B CN110669254B CN201911075367.9A CN201911075367A CN110669254B CN 110669254 B CN110669254 B CN 110669254B CN 201911075367 A CN201911075367 A CN 201911075367A CN 110669254 B CN110669254 B CN 110669254B
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- fatty acid
- reaction
- alkyl ester
- acid alkyl
- lipase
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 66
- 239000002699 waste material Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000004014 plasticizer Substances 0.000 title claims abstract description 45
- 239000004519 grease Substances 0.000 title claims abstract description 43
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 98
- 229930195729 fatty acid Natural products 0.000 claims abstract description 98
- 239000000194 fatty acid Substances 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 102000004882 Lipase Human genes 0.000 claims abstract description 73
- 108090001060 Lipase Proteins 0.000 claims abstract description 72
- 239000004367 Lipase Substances 0.000 claims abstract description 71
- 235000019421 lipase Nutrition 0.000 claims abstract description 71
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 35
- 238000005886 esterification reaction Methods 0.000 claims abstract description 33
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 230000032050 esterification Effects 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 95
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 71
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 24
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003925 fat Substances 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 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
- 150000002191 fatty alcohols Chemical class 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 235000011054 acetic acid Nutrition 0.000 claims description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 8
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 8
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005639 Lauric acid Substances 0.000 claims description 6
- 239000005642 Oleic acid Substances 0.000 claims description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 235000021313 oleic acid Nutrition 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000008117 stearic acid Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 235000021314 Palmitic acid Nutrition 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000007039 two-step reaction Methods 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 8
- 235000013311 vegetables Nutrition 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 85
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 36
- 150000004665 fatty acids Chemical class 0.000 description 30
- 239000002253 acid Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 24
- 230000007935 neutral effect Effects 0.000 description 17
- 239000004800 polyvinyl chloride Substances 0.000 description 17
- 229920000915 polyvinyl chloride Polymers 0.000 description 16
- 235000015112 vegetable and seed oil Nutrition 0.000 description 13
- 239000008158 vegetable oil Substances 0.000 description 13
- 108090000790 Enzymes Proteins 0.000 description 12
- 102000004190 Enzymes Human genes 0.000 description 12
- 235000019197 fats Nutrition 0.000 description 12
- -1 unsaturated fatty acid methyl ester Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000003549 soybean oil Substances 0.000 description 9
- 235000012424 soybean oil Nutrition 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 108010093096 Immobilized Enzymes Proteins 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 235000019626 lipase activity Nutrition 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 4
- 235000021588 free fatty acids Nutrition 0.000 description 4
- 239000010806 kitchen waste Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DKWWWNAJHCKBST-UHFFFAOYSA-N [O].CC(O)=O Chemical compound [O].CC(O)=O DKWWWNAJHCKBST-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
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- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Zoology (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Fats And Perfumes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention provides a method for preparing an epoxy plasticizer by using waste grease, in particular to a method for converting waste vegetable grease into an epoxy fatty acid alkyl ester epoxy plasticizer, which comprises the following steps: providing a waste oil raw material or selectively pretreating the waste oil to obtain pretreated oil; performing transesterification and esterification reaction on grease to obtain a fatty acid alkyl ester mixture; distilling and washing the obtained fatty acid alkyl ester mixture to obtain fatty acid alkyl ester; and (3) epoxidizing the obtained fatty acid alkyl ester to obtain an epoxidized fatty acid alkyl ester mixture, and further removing impurities, washing and drying to obtain the epoxy plasticizer. In the method provided by the invention, the transesterification, esterification and epoxidation of the waste oil and fat all adopt lipase as a catalyst, so that the method has the advantages of wide raw material adaptability and mild reaction conditions, can avoid the use of inorganic acid, alkali and other catalysts, and is environment-friendly.
Description
Technical Field
The invention relates to the field of biochemical engineering, in particular to a method for preparing an epoxy plasticizer by using waste grease, especially waste vegetable oil, such as frying waste oil, hogwash oil, acidified oil and other grease raw materials.
Background
Polyvinyl chloride (PVC) has the excellent characteristics of good mechanical property, fire resistance, flame retardance, chemical corrosion resistance, low price and the like, is widely applied to various industries such as packaging materials and the like, and is a universal plastic with the second largest amount in the world. However, the interaction force between the PVC molecular chains is strong, and the temperature required for softening and melting of pure PVC resin is high, so that the processing is very inconvenient. The plasticizer is an assistant which is used in the PVC product in the largest amount, and the addition of the plasticizer is beneficial to reducing the interaction force among PVC molecules so as to enhance the plasticity of the PVC resin, thereby improving the fluidity during the molding processing of the PVC resin so as to facilitate the processing of the PVC resin and improving the flexibility of the product. The phthalate plasticizer has the advantages of good compatibility, high plasticizing efficiency and the like, and is a product with the largest use amount in the plasticizer for a long time. In recent years, with the progress of research on the toxicity of plasticizers, it has been found that phthalate plasticizers not only pollute the environment but also have a potential carcinogenic and teratogenic effect on human bodies. Therefore, considerable countries and organizations have legislation or adopted policy-related to restrict the use of phthalate plasticizers. Therefore, the development of nontoxic and environment-friendly plasticizers is one of the key problems to be solved urgently in the PVC industry.
The existing environment-friendly plasticizer mainly comprises citric acid esters, aliphatic dibasic acid esters, polyols, polyesters, epoxy resins and the like. The epoxy plasticizer refers to a compound containing an epoxy group in a molecular structure. In the processing process of PVC resin, the epoxy plasticizer has a plasticizing effect on PVC, and the epoxy group in the epoxy plasticizer can absorb hydrogen chloride generated by degradation of PVC resin, so that continuous catalytic decomposition of PVC is inhibited, and the effects of stabilizing PVC products and prolonging service life are achieved. In the preparation process of PVC products, the characteristic of photo-thermal stability of the PVC products is also utilized to improve the weather resistance of the products. Compared with phthalate plasticizers, epoxy plasticizers are almost nontoxic, have the advantages of heat resistance, light resistance, low price and the like, and are approved to be applied to packaging materials of medicines and foods in many countries and regions. The epoxy plasticizer can be mainly divided into epoxy neutral grease obtained by using unsaturated vegetable grease as a raw material through epoxidation and epoxy fatty acid methyl ester obtained by using unsaturated fatty acid methyl ester as a raw material through epoxidation according to different raw materials. Compared with epoxy vegetable oil such as epoxy soybean oil, the epoxy fatty acid methyl ester has the following advantages: firstly, fatty acid methyl ester can be obtained by ester exchange reaction of a grease raw material and also can be obtained by esterification reaction of fatty acid, so that the source of the reaction raw material is wider, and even waste grease can be used as the raw material; secondly, the epoxy plasticizer prepared by epoxidizing the fatty acid methyl ester can improve the additional value of the biodiesel and increase the potential benefit of the biodiesel industry; thirdly, compared with the epoxy vegetable oil, the epoxy fatty acid methyl ester has better lubricity, better dispersion effect in PVC products, larger addition proportion and more unique plasticizing performance in the synthesis of cellulose resin and synthetic rubber; in addition, the epoxy fatty acid methyl ester can also obtain more excellent stretching performance and longer aging time by being added as a plasticizer.
A method for preparing an epoxy fatty acid ester plasticizer by using waste grease as a raw material is disclosed. CN 100590188C discloses a method for producing epoxy plasticizer by using waste oil, which comprises the steps of using waste oil as raw material, pretreating to obtain glyceride, carrying out ester exchange reaction with methanol under the catalysis of alkali to obtain fatty acid methyl ester, directly carrying out epoxidation reaction with peroxy organic acid which is a reaction product of hydrogen peroxide and organic acid to obtain epoxy fatty acid methyl ester crude product, washing with water to remove acid, distilling and dehydrating to obtain epoxy fatty acid methyl ester finished product. CN201010245634.5 discloses a method for producing epoxidized fatty acid methyl ester by using waste vegetable oil, which is to remove impurities from waste vegetable oil such as mixed catering swill oil and the like, and then to enter a distillation tower to directly carry out molecular distillation to remove fatty acid, so that the acid value of the vegetable oil is neutral oil with the value of 1 +/-0.2; adding 1-3% of sodium methoxide and 20-25% of methanol, slowly heating to 68 +/-2 ℃ during stirring, reacting for 40-50 minutes, standing for 25-35 minutes, discharging crude glycerol to obtain fatty acid methyl ester, adding 2-4% of formic acid, slowly heating to 45-55 ℃ during stirring, and beginning to dropwise add 20-30% of hydrogen peroxide for reacting for 7 +/-0.5 hours to obtain epoxy fatty acid methyl ester; and adding 15-25% of sodium hydroxide liquid for neutralization to ensure that the pH of the material is 7 +/-0.5, washing with water, and distilling to obtain the epoxy fatty acid methyl ester plasticizer. Therefore, the existing research on the preparation of epoxy fatty acid ester plasticizers from waste oil is mainly to remove fatty acid in the waste oil by a pretreatment process, obtain neutral oil and then convert the neutral oil into fatty acid alkyl ester by alkali catalysis, which not only needs a complex pretreatment process, but also causes resource waste, and the discharge of alkali catalyst in the alkali catalysis process also causes pollution problems. On the other hand, the current epoxidation process mostly uses organic acids, such as formic acid and acetic acid, as oxygen carriers and sulfuric acid as a catalyst, and the problem of acid pollution is also avoided. Therefore, there is a need to develop a new method suitable for various waste vegetable oil raw materials, which can realize transesterification, esterification and epoxidation of the oil raw materials under mild conditions, so as to improve the utilization of raw materials and the environmental benefits of the process.
Disclosure of Invention
The invention aims to provide a method for preparing an epoxy plasticizer from waste oil, which converts waste oil vegetable oil into an environment-friendly epoxy plasticizer and realizes high-value and resource utilization of the waste oil.
The inventor finds that the waste vegetable oil still has higher unsaturation degree, and the epoxy plasticizer can be obtained through epoxidation. However, waste vegetable oils and fats also tend to have a high free fatty acid content. To effect conversion of waste oils and fats to epoxidized fatty acid alkyl ester plasticizers, one of the primary precursor conditions is to first convert the neutral oils and fatty acids therein to fatty acid alkyl esters, such as fatty acid methyl esters or fatty acid ethyl esters. However, the conventional alkaline conversion process requires sufficient pretreatment of the raw material to remove free fatty acids, which not only requires a complicated pretreatment process but also causes waste of resources (fatty acids). Therefore, it is required to develop a method for simultaneously converting both neutral fats and oils and fatty acids into fatty acid alkyl esters, which avoids the complicated pretreatment process and makes full use of resources.
Therefore, the invention provides a method for preparing an epoxy plasticizer from waste grease, which comprises the following steps:
step (1): providing a waste grease raw material or selectively pretreating waste grease to remove inorganic acid to obtain pretreated grease;
step (2): performing transesterification and esterification on the grease in the step (1) to obtain a fatty acid alkyl ester mixture;
and (3): distilling and washing the fatty acid alkyl ester mixture obtained in the step (2) to obtain fatty acid alkyl ester;
and (4): epoxidizing the fatty acid alkyl ester obtained in the step (3) to obtain an epoxidized fatty acid alkyl ester mixture;
and (5): and (4) removing impurities from the epoxidized fatty acid alkyl ester mixture obtained in the step (4), washing and drying to obtain the epoxy plasticizer.
According to a specific embodiment of the present invention, the waste oil and fat raw material in the step (1) needs to be pretreated if it contains a large amount of inorganic acid (for example, when the content of inorganic acid is 0.5% or more).
In a preferred embodiment of the present invention, the pretreatment in step (1) is performed using one or more agents selected from the group consisting of calcium carbonate, calcium hydroxide, calcium oxide; optionally, the pretreatment is to add the waste oil raw material into a pretreatment reagent, and then treat the mixed system at 20-80 ℃ for 10-120 min; optionally, the amount of the pretreatment agent is 0.5-10% of the weight of the grease. Optionally, the pretreatment mixed system also contains water, and the content of the water is 10-100% of the weight of the grease.
In a preferred embodiment of the present invention, in the step (2), the transesterification and esterification of the fats and oils to obtain fatty acid alkyl esters are carried out by reacting with low-chain fatty alcohols under lipase catalysis; optionally, the lipase is a free lipase and/or an immobilized lipase; optionally, the low-chain fatty alcohol is selected from one of methanol and ethanol; preferably, the transesterification and esterification reactions are carried out in a solvent-free system.
In a preferred embodiment of the present invention, the lipase-catalyzed transesterification and esterification reaction of the fats and oils in the step (2) is a two-step reaction, wherein the first step is catalyzed by free lipase, and the second step is catalyzed by immobilized lipase.
Optionally, the first step reaction conditions in step (2) of the present invention are: the dosage of the free lipase is 0.5 to 5 percent of the weight of the grease, and the water content is 1 to 20 percent of the weight of the oil; the dosage of the low-chain alcohol is 15-30% of the weight of the oil, the temperature is 30-50 ℃, the stirring speed is 200-800rpm, and the reaction time is 6-12 hours. Generally, the yield of the reaction product is 85% or more of the theoretical yield.
Optionally, the second reaction condition in step (2) of the present invention is: the dosage of the immobilized lipase is 0.5 to 5 percent of the weight of the oil phase after the first step of reaction, and the dosage of the low-chain alcohol is 2 to 8 percent of the weight of the oil phase after the first step of reaction; the temperature is 40-50 ℃; the reaction time is 1-5 hours. The second reaction step may be carried out under stirring, if necessary. In general, the reaction results in a conversion of residual neutral fats and fatty acids of 90% or more.
In a preferred embodiment of the invention, the low-chain alcohol in the first step of the lipase-catalyzed transesterification and esterification reaction of the fats and oils in the step (2) is added into the reactor in a multi-step adding manner; preferably, the low-chain alcohol is added into the reactor in 10-5 steps in 10% -20% of the total volume of the used amount within the first 10-5 hours of the reaction; further preferably, the time interval for the addition of the low-chain alcohol is 30 to 120 minutes.
In a preferred embodiment of the present invention, the lipase-catalyzed transesterification of fats and oils in the step (2) and the second reaction in the esterification reaction are carried out in an airlift loop reactor; preferably, the reactor is coupled to an in-line dehydration device to remove water from the reaction system in-line.
In a preferred embodiment of the present invention, the distillation treatment of the fatty acid alkyl ester mixture to obtain fatty acid alkyl esters in step (3) is carried out at a temperature of 40 to 80 ℃ and an absolute pressure of 1 to 80 kpa.
In a preferred embodiment of the present invention, the epoxidation of the fatty acid alkyl ester in the step (4) is performed under lipase catalysis; optionally, the lipase is selected from one of free lipase and immobilized lipase; optionally, the epoxidation reaction is carried out in an organic solvent system, and the organic solvent is selected from one of toluene, tert-butyl alcohol, ethyl acetate, cyclohexane and petroleum ether; optionally, the oxygen carrier used in the epoxidation reaction is selected from one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, lauric acid, palmitic acid, oleic acid and stearic acid.
In a preferred embodiment of the present invention, the epoxidation reaction conditions in the step (4) are: 5 to 25 percent of oxygen carrier based on the weight of the fatty acid alkyl ester, 5 to 20 percent of hydrogen peroxide based on the weight of the fatty acid alkyl ester, 1.5 to 20 percent of lipase based on the weight of the fatty acid alkyl ester, 1 to 6 times of solvent based on the weight of the fatty acid alkyl ester, 30 to 50 ℃ of temperature and 500rpm of stirring speed; the reaction time is 2-24 hours; preferably, the hydrogen peroxide is added into the reaction system in a stepwise manner, and the hydrogen peroxide is preferably added in the first 150 minutes of the reaction, the time interval of each addition is 5-15 minutes, and each addition is 1/30-1/10 of the total dosage.
In a preferred embodiment of the present invention, the conditions for washing, removing impurities and drying the epoxidized fatty acid alkyl ester mixture to obtain the epoxy plasticizer in step (5) are as follows: distilling the oil phase at 70-100 deg.C under 10-50kpa absolute for 30-120 min, washing with 3-5% sodium chloride solution at 50-80 deg.C for 1-3 times, and distilling at 70-100 deg.C under 20-80kpa absolute for 30-120 min.
Waste vegetable oil resources, such as frying waste oil, hogwash oil, and the like, are potential biomass resources. In addition to being useful for the production of biodiesel, these grease resources may also be useful for the preparation of epoxy plasticizers, such as epoxy fatty acid methyl esters or epoxy fatty acid ethyl esters. However, the waste oil and fat has high fatty acid content, and how to effectively convert the waste oil and fat into fatty acid alkyl ester is the key for preparing the epoxy fatty acid alkyl ester plasticizer. The conventional grease transesterification process usually uses alkali as a catalyst, but the presence of fatty acid requires that waste grease must be pretreated to remove or convert free fatty acid into alkyl ester form before the alkali-catalyzed transesterification. Alternative pretreatment methods include caustic washing, molecular distillation, etc., but these pretreatment methods are not only complicated to operate, but also the removed fatty acids are not well converted and utilized. One advantage of the process provided by the present invention is that the lipase catalyst has good catalytic effect on both neutral fats and oils, which undergo transesterification with low-chain fatty alcohols, such as methanol or ethanol, to produce fatty acid methyl esters or ethyl esters, and free fatty acids, which undergo esterification with methanol or ethanol to produce fatty acid methyl esters or ethyl esters.
According to some embodiments of the present invention, when the waste oil raw material is mixed with inorganic acids, such as sulfuric acid, phosphoric acid, and low-chain fatty acids, the waste oil may be pretreated with one or more reagents selected from calcium carbonate, calcium hydroxide, and calcium oxide to remove the acids as much as possible, thereby avoiding the inhibition of the catalytic effect of the lipase in the method of the present invention by the inorganic acids. The amount, temperature, time, water content, etc. of the reagents used in the pretreatment process may vary depending on the source of the waste oil raw material. According to the specific embodiment of the invention, the best inhibitor removal effect can be obtained when the used waste grease raw material is treated for 10-120 minutes under the conditions that the dosage of the pretreatment reagent is 0.5-10% of the weight of the grease, the temperature is 20-80 ℃, and the dosage of the water is 10-100% of the weight of the grease.
When the pretreated grease is subjected to transesterification and esterification, various catalysts can be selected, including chemical catalysts such as acid or alkali, and biological catalysts including various lipases including free lipase, immobilized lipase, and lipase-containing bacteria or immobilized bacteria. The alkali catalyst generally has better neutral oil conversion than the acid catalyst, but the content of fatty acid in the raw material needs to be strictly controlled to avoid saponification. The lipase catalyst has the advantages of wide raw material adaptability, mild reaction conditions and the like, and is particularly suitable for transesterification and esterification reaction of high-acid-value waste oil. The free lipase is liquid, is relatively low in price, generally has higher moisture content, and has higher reaction rate in catalyzing transesterification and esterification of grease. The low-chain fatty alcohol commonly used in the transesterification and fatty acid esterification processes of neutral oil is methanol and ethanol. However, methanol and ethanol have inhibition effect on lipase catalysis, and the concentration of methanol or ethanol in the system needs to be strictly controlled. Compared with free lipase, the immobilized lipase has the advantages of good stress resistance, easy recovery and the like, but when the reaction system is a solvent-free system, namely no organic solvent is added as a reaction medium, the emulsification of the reaction system can be caused due to the immiscible property of oil and water, and the emulsification can cause the protein of the immobilized lipase prepared by an adsorption method to fall off and be inactivated, so that the apparent enzyme activity is reduced. In a preferred embodiment of the invention, the transesterification and esterification of the fat after lipase catalysis pretreatment are carried out by adopting a two-step reaction, wherein the first step is catalyzed by free lipase, and the second step is catalyzed by immobilized lipase. The first step of reaction is carried out in an organic solvent-free system, namely an oil-water emulsification system, and free lipase can be carried out on an oil-water interface in a catalytic reaction mode. According to the specific embodiment of the invention, the conditions of the first step reaction need to be effectively controlled to obtain higher conversion rate of neutral grease and fatty acid, namely, the dosage of free lipase is 0.5-5% of the weight of the pretreated grease, and the water content is 1-20% of the weight of the oil; the dosage of the low-chain alcohol is 15-30% of the weight of the oil, the temperature is 30-50 ℃, the stirring speed is 200-800rpm, and the reaction time is 6-12 hours. In addition, methanol or ethanol is added into the system in a stepwise manner, so that lipase inactivation can be avoided. According to a specific embodiment of the invention, the low-chain alcohol is added to the reactor in 10-5 steps in 10% -20% of the total volume of the used amount within the first 10-5 hours of the reaction; further preferably, the time interval of the low-chain alcohol addition is 30-120 minutes, so as to obtain a faster reaction rate without inactivation of lipase. After the first-step reaction, most of neutral oil and fatty acid are converted into fatty acid alkyl ester, and the oil phase of the reaction system is further converted into residual neutral oil and fatty acid by adopting immobilized lipase. At the moment, the reaction system is homogeneous, and the emulsification phenomenon in the first-step reaction system does not exist, so that the enzyme activity of the immobilized lipase is well maintained. According to an embodiment of the present invention, the preferred reaction conditions for the second step are: the dosage of the immobilized lipase is 0.5 to 5 percent of the weight of the oil phase after the first step of reaction, and the dosage of the methanol is 2 to 8 percent of the weight of the oil phase after the first step of reaction; the temperature is 40-50 ℃; the reaction time is 1-5 hours, so that the maximum reaction rate and conversion rate can be obtained. It is further preferred that the second reaction is carried out in a gas lift loop reactor to avoid catalyst breakage and pulverization by a stirred reactor. Because the esterification reaction of the fatty acid and the low-chain alcohol generates water, and the esterification reaction is an equilibrium reaction, in order to promote the reaction to the esterification reaction, the reaction system can be connected with an online dehydration device to remove the water in the system online.
The fatty acid alkyl ester mixture obtained after two-step lipase catalytic conversion needs to remove residual low-chain alcohol and other substances before the epoxidation reaction. These substances can be removed by distillation, depending on the difference in boiling point of the low-chain alcohol and the fatty acid alkyl ester. According to the embodiment of the present invention, the optimum removal effect can be obtained under the conditions of the temperature of 40 to 80 ℃ and the absolute pressure of 1 to 80kpa, and relatively pure fatty acid alkyl ester can be obtained.
Fatty acid alkyl esters epoxy fatty acid alkyl ester plasticizers can be prepared by epoxidation. The conventional epoxidation process uses hydrogen peroxide as an oxygen donor, an organic acid, such as formic acid or acetic acid, as an oxygen carrier, and sulfuric acid as a catalyst. The hydrogen peroxide and the organic acid generate organic acid peroxide under the catalysis of sulfuric acid, and the organic acid peroxide and unsaturated double bonds of fatty acid alkyl ester undergo epoxidation reaction at an oil-water interface. The method provided by the invention adopts lipase, particularly immobilized lipase as a catalyst, can catalyze the production of organic peroxyacid under mild conditions, further epoxidize fatty acid alkyl ester, and can realize the integrated integration of transesterification, esterification and epoxidation. However, hydrogen peroxide has a significant toxic effect on lipase, and the commonly used formic acid or acetic acid oxygen carrier also has a significant inhibitory effect on lipase, so that the oxygen carrier needs to be screened again and the reaction conditions need to be strictly controlled. On the other hand, hydrogen peroxide used in the epoxidation process is usually a 30% aqueous solution, and a large amount of hydrogen peroxide solution added into the system inevitably changes the system into a heterogeneous phase, so that an organic solvent system can be adopted to obtain a homogeneous system in order to avoid the problem of falling of immobilized lipase protein caused by a heterogeneous reaction. According to a specific embodiment of the present invention, the oxygen carrier used in the epoxidation reaction is selected from one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, lauric acid, palmitic acid, oleic acid and stearic acid; further preferably, the oxygen carrier is a medium-long chain fatty acid selected from one of heptanoic acid, lauric acid, palmitic acid, oleic acid and stearic acid, so as to avoid negative effects caused by acidity of the fatty acid. According to the embodiment of the invention, one of toluene, tertiary butanol, ethyl acetate, cyclohexane and petroleum ether is used as the organic solvent, so that a good homogeneous reaction system is obtained, and meanwhile, the negative influence on lipase is avoided. In addition, epoxidation reaction conditions are key controlling factors affecting enzyme stability and activity as well as epoxidation efficiency. According to the specific embodiment provided by the invention, the oxygen carrier is used in an amount of 5-25% based on the weight of the fatty acid alkyl ester, the hydrogen peroxide is used in an amount of 5-20% based on the weight of the fatty acid alkyl ester, the lipase is used in an amount of 1.5-20% based on the weight of the fatty acid alkyl ester, the solvent is used in an amount of 1-6 times based on the weight of the fatty acid alkyl ester, the temperature is 30-50 ℃, and the stirring speed is 100-; higher epoxy values can be obtained at reaction times of 2 to 24 hours. More importantly, 30% hydrogen peroxide needs to be added into the reaction system in a stepwise manner, according to the specific embodiment provided by the invention, the hydrogen peroxide is preferably added within the first 150 minutes of the reaction, the time interval of each addition is 5-15 minutes, and each addition is 1/30-1/10 of the total dosage, so as to avoid lipase inactivation caused by overhigh hydrogen peroxide concentration.
The epoxidized fatty acid alkyl mixture produced by the above process requires further purification to obtain an acceptable epoxidized fatty acid alkyl ester plasticizer. According to the embodiment provided by the present invention, the washing, impurity removal and drying treatment of the epoxidized fatty acid alkyl ester mixture can remove impurities such as residual hydrogen peroxide, water and the like. Preferred purification conditions are: distilling the oil phase at 70-100 deg.C under 10-50kpa absolute for 30-120 min, washing with 3-5% sodium chloride solution at 50-80 deg.C for 1-3 times, and distilling at 70-100 deg.C under 20-80kpa absolute for 30-120 min. Thus, impurities such as residual hydrogen peroxide, water, etc. can be effectively removed without causing a significant decrease in the epoxy value.
In conclusion, the method provided by the invention can simultaneously convert neutral oil and fatty acid in the waste vegetable oil into fatty acid alkyl ester and further into the environment-friendly epoxy plasticizer, so that the complex oil pretreatment process is avoided, the fatty acid component in the waste oil is fully utilized, and the lipase can catalyze the epoxidation of the fatty acid alkyl ester under mild conditions, so that the epoxy plasticizer can be integrally prepared from the transesterification of the neutral oil and the esterification of the fatty acid into the epoxidation of the fatty acid alkyl ester.
Drawings
FIG. 1 is a technical process for preparing an epoxy plasticizer from waste grease provided by the invention.
The reference numbers in the figures illustrate:
1. pre-treating; 2. a first transesterification/esterification step; 3. liquid-liquid separation; 4. second step transesterification/esterification; 5. solid-liquid separation; 6. epoxidation; 7. solid-liquid separation; 8. purifying and impurity removing
Detailed Description
In order to illustrate the present invention in more detail, the following examples are given. Although the scope of the invention is not limited in this respect.
Example 1: transesterification and esterification for preparing epoxy fatty acid ethyl ester by using methanol as low-chain alcohol
Referring to fig. 1, this embodiment provides a method for converting waste vegetable oil into epoxy fatty acid alkyl ester epoxy plasticizer. The method is mainly carried out according to the following operations:
the method comprises the following steps: waste oil feedstock and pretreatment thereof
The waste kitchen oil is purchased from Hunan province, and the water content is as follows: 0.9%, acid value: 121.1, saponification value: 199.2, triglyceride: 18.1%, diglyceride: 1.3%, monoglyceride: 18.1 percent. After 30 minutes of treatment at 60 ℃ with 1% calcium carbonate based on the weight of the oil and 10% water based on the weight of the oil, the oil layer was analyzed by centrifugal filtration, and the water content was 1.2%, the acid value: 118.3, saponification value: 195.2, triglycerides: 17.9%, diglyceride: 1.4%, monoglyceride: 18.4 percent. It can be seen that the calcium carbonate treatment can slightly reduce the acid value of the kitchen waste oil, but the reduction is not obvious.
The acidified waste oil was purchased from Guangdong province and had a water content of: 1.5%, acid value: 140 (inorganic acid-containing), saponification number: 160.2. after treating the oil layer for 30 minutes at 60 ℃ with 5% calcium oxide based on the weight of the oil and 20% water based on the weight of the oil, the oil layer was analyzed to have a water content of 2.1%, an acid value: 110.3, saponification value: 155.2. therefore, the calcium carbonate treatment can obviously reduce the acid value of the acidified oil. This is because the acidified oil also contains a portion of inorganic and organic acids which can be removed by reaction with calcium oxide during pretreatment.
Step two: catalytic conversion of free lipase from pretreated waste oil feedstock
The used waste oil raw material is the kitchen waste oil pretreated in the step one. After 2000g of the pretreated waste oil was charged in a 5L reactor, and 200g of water (10% based on the weight of the oil), 30g of liquid lipase (1.5% based on the weight of the oil), and 400ml of anhydrous methanol (20% by volume based on the weight of the oil) were added, the yield of fatty acid methyl esters was found to be 10% after 8 hours of reaction at 500rpm and 45 ℃. It can be seen that when methanol is added to the reactor at a time in the early stage of the reaction, the yield of fatty acid methyl esters is low due to the inhibitory effect of methanol. When methanol is gradually added in six batches, 35 percent, 20 percent, 15 percent, 10 percent and 5 percent of the total amount of the methanol are respectively added in 0h, 1h, 2h, 3h, 4h and 5h, the yield of the fatty acid methyl ester reaches 85 percent after 8 hours, and the acid value of the oil phase is 12. Therefore, the methanol can obviously reduce the inhibition effect of the methanol by a step-by-step addition mode, and the yield of the fatty acid methyl ester is improved.
Step three: immobilized lipase catalyzed fatty acid methyl ester mixture acid value reduction
Since the first reaction is carried out in an aqueous system and the esterification reaction of fatty acid and alcohol is an equilibrium reaction, hydrolysis of neutral oil and fat and incomplete conversion of fatty acid are inevitable. And (3) in order to further convert the residual oil and fatty acid into fatty acid methyl ester, namely reduce the acid value, carrying out centrifugal separation on the fatty acid methyl ester mixture obtained in the step two, and taking an oil phase for carrying out catalytic conversion on the immobilized lipase. 180g of oil phase, 2g of immobilized lipase and 20g of methanol were added to a 200ml airlift loop reactor, and after 2 hours of reaction at 40 ℃, the oil phase was analyzed to obtain a fatty acid methyl ester content of 97%, a glycerol content of 0.035%, an acid value of 0.98mgKOH/g and an iodine value of 72. The immobilized lipase is recycled for 100 batches without obvious reduction of enzyme activity. Therefore, residual neutral oil and fatty acid in the fatty acid methyl ester mixture after the first-step enzymolysis conversion can be effectively converted into fatty acid methyl ester in the second-step immobilized enzyme catalytic conversion process, and the immobilized enzyme has good stability.
The reaction of catalyzing the acid value reduction of the fatty acid methyl ester mixture by the immobilized lipase is influenced by factors such as water content, the dosage of the immobilized enzyme, the molar ratio of alcohol to oil and the like. The water content affects the balance of the esterification reaction of fatty acid and alcohol in the system, and when the water content is reduced from 2% to 400ppm, the acid value of the oil phase is 2.5mgKOH/g and 0.8 mgKOH/g respectively after reacting for 2 hours under the reaction conditions. Thus in combination with an in-line dehydration, such as molecular sieve adsorption or an in-line membrane dehydration process, the acid value reduction, i.e. the further conversion of fatty acids into fatty acid methyl esters, can be facilitated. When the amount of the immobilized enzyme is increased from 0.5% to 2.0%, the acid value is 3.8, 2.0, 1.2 and 0.9mgKOH/g, respectively, after reacting for 2 hours under the above reaction conditions, and therefore, in order to obtain a higher acid value reduction effect, the amount of the immobilized enzyme is preferably 1.5% to 2.0%. The amount of methanol affects the reaction balance and further affects the effect of reducing the acid value. When the alcohol-oil molar ratio is decreased from 2.2:1 to 0.18:1, the acid value of the oil phase after 2 hours of reaction under the above conditions is 1.0 to 4.0mgKOH/g, and the preferred alcohol-oil molar ratio is 1:1, i.e., methanol is used in an amount of about 10% to 15% based on the weight of the oil phase.
Step four: preparation of epoxy fatty acid methyl ester by using immobilized lipase to catalyze fatty acid methyl ester
And (3) rotationally evaporating the oil-phase fatty acid methyl ester obtained in the third step in vacuum at the temperature of 80 ℃ for 30 minutes at 20kpa, and cooling to room temperature for epoxidation. Since heterogeneous reaction can cause the shedding of immobilized lipase protein and the loss of enzyme activity, the epoxidation reaction is selected to be carried out in an organic solvent system. The effect of different organic solvents on the epoxy value was compared as shown in table 1. It is known that ethyl acetate, cyclohexane and petroleum ether as solvents give low epoxy values. T-butanol and toluene are preferred solvents and relatively high epoxy values can be obtained. Toluene is a preferred solvent for the epoxidation process because it is more toxic and has a higher boiling point than t-butanol, which is less toxic and has a lower boiling point than t-butanol. Further optimizing the influence of the dosage of the tert-butyl alcohol on the epoxy value, and finding that the best epoxidation effect can be obtained when the dosage of the tert-butyl alcohol is 5ml/g of grease.
TABLE 1 Effect of different solvents on epoxidation
High concentrations of hydrogen peroxide can impair the activity of the lipase, and the manner of addition of hydrogen peroxide during the reaction can influence the magnitude of the epoxy value. In order to compare the influence of different hydrogen peroxide on the lipase activity, 10g of soybean oil, 0.1g of oleic acid and 100mL of tert-butyl alcohol are mixed in a conical flask, 2.0g of immobilized lipase is added, the mixture is placed in a constant-temperature shaking table at 40 ℃ and 300rpm for oscillation, hydrogen peroxide with the same total amount is added into the mixture in a one-time adding and step-by-step adding mode (1/20 of the total amount is added each time) after 15min, the immobilized enzyme is filtered and separated, and the lipase activity is measured. The result shows that the lipase activity is reduced by 90% after one batch of reaction when the hydrogen peroxide is added at one time, the lipase activity is completely lost after the lipase is continuously reused for epoxidation, and the reduction degree of the lipase activity can be obviously reduced when the hydrogen peroxide is added step by step. To further compare the impact of different hydrogen peroxide addition strategies, three addition strategies were compared, namely (method 1: 1/28 is added every 10min, and 280min is finished; method 2: 1/14 is added every 10min, and 140min is added; ③ method 3: 1/9 was added every 10min for 90 min. The result shows that the adding mode of adding the total 1/28 every 10min can prolong the effective reaction time, so that the action time of lipase and hydrogen peroxide is prolonged, the enzyme activity is not kept favorably, and the epoxy value is reduced to be below 2.5 percent during the third reaction; the addition mode of adding the total amount of 1/9 every 10min can lead the accumulation concentration of hydrogen peroxide in the system to be higher, influence the retention of enzyme activity, and reduce the epoxy value to below 1 percent in the fourth reaction. The best hydrogen peroxide addition strategy among the three step addition regimes was to add 1/14 in total every 10min to complete all hydrogen peroxide over 140min, when the epoxy value of the fifth batch was above 2.5%. Further optimizing the effect of the total amount of 30% hydrogen peroxide, it was found that an epoxy value of 6.0% was obtained after 12 hours of reaction when the amount of 30% hydrogen peroxide was 0.32g/g fatty acid methyl ester.
The preparation method of epoxidized soybean oil has the advantages that fatty acid is used as an oxygen carrier in the preparation process of epoxidized soybean oil, formic acid or acetic acid is generally used as the oxygen carrier in the preparation process of epoxidized soybean oil by a chemical method, and the formic acid or the acetic acid has strong acidity and can easily inactivate enzyme, so that long-chain fatty acid is generally used as the oxygen carrier by a biological enzyme method. Under the enzyme catalysis, long-chain fatty acid reacts with hydrogen peroxide to generate peroxy fatty acid, and the peroxy fatty acid oxidizes double bonds to obtain the epoxidized soybean oil. However, if the carbon chain is too long, steric hindrance is enhanced, which is not favorable for the reaction of fatty acid and hydrogen peroxide to generate peroxy fatty acid. Therefore, comparing the effects of fatty acids with different carbon chain lengths on the epoxidation process, including formic acid, acetic acid, propionic acid, n-butyric acid, n-valeric acid, n-caproic acid, n-enanthic acid, lauric acid, oleic acid and stearic acid, it was found that lauric acid can obtain the best epoxy value (4.5%), and the lipase can still obtain an epoxy value of 4.0% after three batches of recycling.
Reaction condition parameters are further optimized by adopting a response surface center composite design, variables comprise 30% of hydrogen peroxide dosage (g/g soybean oil), immobilized enzyme dosage (g/g soybean oil), solvent tert-butyl alcohol dosage (ml/g soybean oil) and reaction temperature (DEG C), and results show that at 45 ℃, the solvent addition is 3.75ml/g fatty acid methyl ester, the enzyme dosage is 0.075g/g fatty acid methyl ester, the 30 wt% of hydrogen peroxide dosage is 0.32 g/fatty acid methyl ester, and the optimal epoxy value is 5.28%.
Example 2: transesterification and esterification are carried out to prepare epoxy fatty acid ethyl ester by taking ethanol as low-chain alcohol
In a similar way to the case of methanol, in this example, ethanol is used as a low-chain alcohol reactant, after the kitchen waste oil described in example 1 is pretreated as described in example 1, the kitchen waste oil is subjected to the first-step liquid lipase catalytic conversion, the second-step immobilized lipase catalytic conversion and the immobilized lipase catalytic epoxidation respectively as described in example 1, and the product is washed and evaporated under reduced pressure to obtain an epoxy value of 5.5%. Therefore, ethanol can also be used as a low-chain alcohol reactant to effectively convert the waste grease into the epoxy plasticizer. One significant advantage of using ethanol is: ethanol is mainly from starch or cellulose fermentation, and starch and cellulose are carbohydrate biomass which is the most abundant in nature, so that the epoxy plasticizer raw material which is produced is completely from biomass, and the net emission of carbon dioxide is further reduced.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A method for preparing an epoxy plasticizer from waste grease, comprising:
step (1): providing a waste grease raw material or selectively pretreating waste grease to remove inorganic acid to obtain pretreated grease;
step (2): performing transesterification and esterification on the grease in the step (1) to obtain a fatty acid alkyl ester mixture;
and (3): distilling and washing the fatty acid alkyl ester mixture obtained in the step (2) to obtain fatty acid alkyl ester;
and (4): epoxidizing the fatty acid alkyl ester obtained in the step (3) to obtain an epoxidized fatty acid alkyl ester mixture;
and (5): removing impurities from the epoxidized fatty acid alkyl ester mixture obtained in the step (4), washing and drying to obtain an epoxy plasticizer;
the transesterification and esterification reaction of the grease in the step (2) is carried out by reacting with low-chain fatty alcohol under the catalysis of lipase, the transesterification and esterification reaction in the step (2) is a two-step reaction, wherein the first step is catalyzed by free lipase, and the second step is catalyzed by immobilized lipase;
the first step reaction conditions are as follows: the dosage of the free lipase is 0.5 to 5 percent of the weight of the grease, and the water content is 1 to 20 percent of the weight of the oil; the dosage of the low-chain fatty alcohol is 15-30% of the weight of the oil, the temperature is 30-50 ℃, the stirring speed is 200-800rpm, and the reaction time is 6-12 hours;
the second step reaction conditions are as follows: the dosage of the immobilized lipase is 0.5 to 5 percent of the weight of the oil phase after the first step of reaction, and the dosage of the low-chain alcohol is 2 to 8 percent of the weight of the oil phase after the first step of reaction; the temperature is 40-50 ℃; the reaction time is 1-5 hours.
2. The method according to claim 1, wherein the pretreatment in the step (1) is carried out by adding a pretreatment agent to the waste grease, wherein the pretreatment agent is one or more selected from calcium carbonate, calcium hydroxide and calcium oxide;
the pretreatment is to add the waste oil raw material into a pretreatment reagent, and then treat the mixed system at the temperature of 20-80 ℃ for 10-120 min;
the dosage of the pretreatment reagent is 0.5-10% of the weight of the grease;
the pretreatment mixed system also contains water, and the content of the water is 10-100% of the weight of the grease.
3. The process according to claim 1 or 2, wherein the low-chain fatty alcohol is selected from one of methanol and ethanol;
the transesterification and esterification reactions are carried out in a solvent-free system.
4. The method according to claim 3, wherein in the transesterification and esterification reaction of the fats and oils in the step (2), the low-chain fatty alcohol in the first step is added to the reaction in a multi-step manner; adding the low-chain fatty alcohol into a reactor within 10-5 hours before the reaction in 10-5 steps according to 10-20 percent of the total volume dosage; the time interval for the addition of the low-chain fatty alcohol is 30-120 minutes.
5. The process according to claim 3, wherein in the transesterification and esterification of fats and oils in the step (2), the second reaction is carried out in an airlift loop reactor; the reactor is coupled with an online dehydration device to remove the water in the reaction system online.
6. The process according to claim 1, wherein the distillation treatment of the fatty acid alkyl ester mixture in the step (3) is carried out at a temperature of 40 to 80 ℃ and an absolute pressure of 1 to 80 kpa.
7. The method according to claim 1, wherein the epoxidation of the fatty acid alkyl ester in the step (4) is carried out under lipase catalysis;
the lipase is selected from one of free lipase and immobilized lipase;
the epoxidation reaction is carried out in an organic solvent system, and the organic solvent is selected from one of toluene, tert-butyl alcohol, ethyl acetate, cyclohexane and petroleum ether;
the oxygen carrier used in the epoxidation reaction is selected from one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, lauric acid, palmitic acid, oleic acid and stearic acid.
8. The process of claim 7, wherein the epoxidation reaction conditions in step (4) are: 5 to 25 percent of oxygen carrier based on the weight of the fatty acid alkyl ester, 5 to 20 percent of hydrogen peroxide based on the weight of the fatty acid alkyl ester, 1.5 to 20 percent of lipase based on the weight of the fatty acid alkyl ester, 1 to 6 times of solvent based on the weight of the fatty acid alkyl ester, 30 to 50 ℃ of temperature and 500rpm of stirring speed; the reaction time is 2-24 hours;
adding hydrogen peroxide into the reaction system by adopting a step-by-step adding mode, wherein the hydrogen peroxide is added within the first 150 minutes of the reaction, the time interval of each addition is 5-15min, and the addition amount of each addition is 1/30-1/10 of the total dosage.
9. The method according to claim 1, wherein the washing, removing impurities and drying treatment of the epoxidized fatty acid alkyl ester mixture in the step (5) are carried out under the conditions of: distilling the oil phase at 70-100 deg.C under 10-50kpa absolute pressure for 30-120 min, washing with 3-5% sodium chloride solution at 50-80 deg.C for 1-3 times, and distilling at 70-100 deg.C under 20-80kpa absolute pressure for 30-120 min.
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| CN102925287A (en) * | 2012-11-19 | 2013-02-13 | 北京化工大学 | Method for preparing biodiesel by biological-chemical catalytic coupling |
| CN103740471A (en) * | 2014-01-02 | 2014-04-23 | 北京化工大学 | Method for preparing epoxy resin fatty acid short-chained alcohol ester in biological catalytic method |
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