CN104326911B - A kind of waste grease prepares method and the application of polyhydric alcohol - Google Patents
A kind of waste grease prepares method and the application of polyhydric alcohol Download PDFInfo
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- CN104326911B CN104326911B CN201410468577.5A CN201410468577A CN104326911B CN 104326911 B CN104326911 B CN 104326911B CN 201410468577 A CN201410468577 A CN 201410468577A CN 104326911 B CN104326911 B CN 104326911B
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- methyl ester
- fatty acid
- acid
- catalyst
- oil
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- 239000002699 waste material Substances 0.000 title claims abstract description 100
- 239000004519 grease Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 64
- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 83
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims abstract description 75
- 239000011973 solid acid Substances 0.000 claims abstract description 57
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 50
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 38
- 230000005661 hydrophobic surface Effects 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 27
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 25
- 239000006227 byproduct Substances 0.000 claims abstract description 22
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 230000006837 decompression Effects 0.000 claims abstract description 11
- 238000007171 acid catalysis Methods 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 150000002148 esters Chemical group 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000012075 bio-oil Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000013067 intermediate product Substances 0.000 claims abstract description 3
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 51
- 235000019198 oils Nutrition 0.000 claims description 51
- 230000008569 process Effects 0.000 claims description 43
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 32
- 235000014593 oils and fats Nutrition 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 23
- 235000011187 glycerol Nutrition 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 235000013305 food Nutrition 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 17
- 238000005886 esterification reaction Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 12
- 239000011496 polyurethane foam Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 239000011527 polyurethane coating Substances 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 230000000977 initiatory effect Effects 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 8
- 241001465754 Metazoa Species 0.000 claims description 8
- 241000283898 Ovis Species 0.000 claims description 8
- 238000004061 bleaching Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 239000003925 fat Substances 0.000 claims description 8
- 235000019197 fats Nutrition 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008157 edible vegetable oil Substances 0.000 claims description 7
- 150000003460 sulfonic acids Chemical class 0.000 claims description 7
- 238000012719 thermal polymerization Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 241000196324 Embryophyta Species 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- -1 hydroxy ethyl sulphonic acid ester Chemical class 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000010985 leather Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 238000003307 slaughter Methods 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
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- 238000003860 storage Methods 0.000 claims description 4
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 3
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 2
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 2
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 2
- 241000287828 Gallus gallus Species 0.000 claims description 2
- 241000282894 Sus scrofa domesticus Species 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000008439 repair process Effects 0.000 claims description 2
- 230000011218 segmentation Effects 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 13
- 239000008158 vegetable oil Substances 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 9
- 238000007142 ring opening reaction Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- 238000012805 post-processing Methods 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 241000131329 Carabidae Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000008162 cooking oil Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 235000019737 Animal fat Nutrition 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NKZQKINFDLZVRY-UHFFFAOYSA-N n-butylbutan-1-amine;toluene Chemical compound CC1=CC=CC=C1.CCCCNCCCC NKZQKINFDLZVRY-UHFFFAOYSA-N 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- 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
-
- 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
- C11C3/10—Ester interchange
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fats And Perfumes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses a kind of method that waste grease prepares polyhydric alcohol, comprise the steps: to adopt the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalysis waste grease and methanol carry out being esterified and ester exchange reaction, and waste grease is converted into fatty acid methyl ester and by-product glycerol; Then the polyunsaturated fatty acid ester in fatty acid methyl ester is separated; Then proceeding under bisgallic acid central solid acid catalysis, utilize the collaborative of bisgallic acid center, fatty acid methyl ester is carried out epoxidation by the hydrogen peroxide of direct catalysis 30%, and intermediate product is without separation, after directly heating up, adds by-product glycerol and carries out alkoxide open loop; Catalyst is finally recovered by filtration, and namely decompression distillation obtains bio oil polylol after dewatering. The inventive method is with waste grease for raw material, it is achieved that turn waste into wealth, and gained polyol product biological degradability is good, and preparation process is green, and three industrial wastes discharge is little, and product structure and hydroxyl value are adjustable, applied range, the feature that the level that affects of environment is low.
Description
Technical field
The present invention relates to a kind of waste grease and prepare method and the application of polyhydric alcohol, belong to organic chemical synthesis technical field.
Background technology
Polyurethane material excellent performance, of many uses, China has become the market that polyurethane is with fastest developing speed in the world, and research and development of products, production, application etc. obtain marked improvement. In all kinds of polyurethane products, the purposes of polyurethane foam is the widest, has huge development space in fields such as building energy conservation, solar water heater, imitation wood furniture, pipe insulation, embeddings, and the market demand is vigorous. Conventional urethane polyhydric alcohol is generally the polyoxyalkylene hydrocarbon polyols of high functionality, high hydroxyl value (low-molecular-weight), i.e. " polyether polyol ". Polyether polyol is usually by the small molecule alcohol of high functionality or amine initiator, under catalyst action, prepare with ring-opening polymerisations such as expoxy propane (PO), oxirane (EO), synthesis material mostly derives from oil, the net importation amount of the oil of China in 2012 is up to 2.84 hundred million tons, along with the quickening of economic development, the paces that improve and build a well-off society in an all-round way of social life, external oil interdependency improves constantly so that oil supply becomes safely the problem not allowing to avoid. It addition, the relatively difficult degradation in its natural state of petroleum base hard polyurethane foam product, become white pollution source. Therefore, find green reproducible polyol masses and just become an important directions of current polyhydric alcohol industry development.The fatty acid triglyceride structure of bio oil has good hydrophobicity, and the polyurethane material of preparation has good physical and chemical performance, especially in hydrolytic resistance and heat stability. the environmental influence research of the biomass polyalcohol that American National Standard and technological associations (MST) are recently completed shows, compared with petroleum-based polyols, vegetable oil polyol overall energy consumption reduces by 23%, nonrenewable resources consumption reduces by 61%, reduce 36% to airborne release greenhouse gases, can substantially alleviate the problems such as global warming, smog formation, ecological degeneration. alcoholysis method is prepared vegetable oil polyol and has been carried out systematic study by Mount Huang etc. (CN200710037248.5), selects vegetable oil and Epoxy oil mixture respectively, with fatty amine and fatty alcohol for alcoholysis agent, prepares vegetable oil polyol under base catalyst exists. BeneckeHP(CPI-Polyurethanes2009TechnicalConference, 2009,5/10-7/10) prepare vegetable oil polyol by ozone oxidation mode, under acidic catalyst effect, by ozone oxidation vegetable oil, Animal fat, then, with small molecular alcohol, the carboxylic acid of fatty acid derived is esterified, thus obtaining vegetable oil polyol. PetrovicZ etc. (US6433121) disclose a kind of method adopting vegetable oil to prepare vegetable oil polyol by hydroxylating after first epoxidation. peroxy acid first joins formation epoxidized vegetable oil in vegetable oil, and epoxidation conversion ratio is 91%～94%, then adopts water or small molecular alcohol to form vegetable oil-based polyols under fluoboric acid catalytic action. GuoA etc. (JournalofAppliedPolymerScience, 2000,77,467-473) adopt epoxy soybean oil to be raw material, carry out hydroxylating by methanol and are prepared for soybean oil base polyol. Yao Zhihong etc. (CN200610041380.9) select the epoxy rapeseed oil nucleophilic reagent generation epoxy ring-opening reaction under catalyst action and containing active hydrogen, generate the triglyceride of hydroxyl, it is subsequently adding polyhydric alcohol or hydramine carries out alcoholysis reaction, be prepared for degree of functionality and the high vegetable oil polyol product of hydroxyl value. within 2011, China's edible oil aggregate consumption reaches 27,650,000 tons, and wherein the degree of self-sufficiency only has 38.1%, and grain and oil safety has become China and has been presently required the problem of concern, therefore, edible oil is directly used in large-scale industrial production unrealistic. on the other hand, the waste cooking oil that the consumption of a large amount of edible oil produces is always up troubling problem, and national multiple cities occurred food and beverage waste oil and grease to back flow back into the pernicious waste oil event of dining table once. waste cooking oil is seriously polluted, and oily waste water frequently results in the blocking of blowdown pipe network, brings difficulty to environmental sanitation work, if waste oil flows directly into rivers can worsen water body, and environmental ecology is totally unfavorable. therefore, these waste greases are effectively utilized just to be particularly important. in order to solve problem above, the present invention is considered as waste grease raw material, to have the solid acid catalyst having sulfonic group and carboxylic acid group concurrently of big hydrophobic surface, catalysis waste grease carries out esterification respectively, epoxidation series connection alkoxide ring opening synthesis biopolyol, avoid the pollution of waste grease, reduce cost of material, achieve and turn waste into wealth, simultaneously with solid tart flavour catalyst in course of reaction, avoid the loaded down with trivial details post processing of homogeneous catalyst, reaction terminates rear catalyst and is filtered reclaiming, and carry out repetitive cycling use, enormously simplify technological process, reduce the discharge of three industrial wastes.
Summary of the invention
It is an object of the invention to provide a kind of eco-friendly, reproducible waste grease prepares green synthesis method and the application of polyhydric alcohol, the inventive method is with waste grease for raw material, achieving and turn waste into wealth, gained polyol product biological degradability is good, and preparation process is green, three industrial wastes discharge is little, product structure and hydroxyl value are adjustable, applied range, the feature that the level that affects of environment is low.
For reaching above-mentioned purpose, the technical scheme is that
A kind of waste grease prepares the method for polyhydric alcohol, comprise the steps: to adopt the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalysis waste grease and methanol carry out being esterified and ester exchange reaction, and waste grease is converted into fatty acid methyl ester and by-product glycerol; Then lower the temperature, the polyunsaturated fatty acid ester in fatty acid methyl ester is separated by the mode of crystallization, improve the content of double bond in fatty acid methyl ester; Then proceeding under bisgallic acid central solid acid catalysis, utilize the collaborative of bisgallic acid center, fatty acid methyl ester is carried out epoxidation by the hydrogen peroxide of direct catalysis 30%, and intermediate product is without separation, after directly heating up, adds by-product glycerol and carries out alkoxide open loop; Catalyst is finally recovered by filtration, and namely decompression distillation obtains bio oil polylol after dewatering. By selecting different glyceride stock, reaction temperature, response time etc. to control the extent of reaction, Molecular regulator structure, hydroxyl value distribution etc., obtain being suitable for the biopolyol product in different application field.
Described step particularly as follows:
1) prepared by the solid acid having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface
By unsaturated carboxylic acid, sulfonic acid and divinylbenzene containing unsaturated double-bond are dissolved in organic solvent, solution solubility is 20～65%, the hot copolymerization 2～10h of mixed solvent is carried out under the initiation of azodiisobutyronitrile initiator, initiator amount is the 0.1%～1% of reactant gross mass, and solvent thermal polymerization temperature, at 80～180 DEG C, cools down, filtering, namely washing and drying obtains has big hydrophobic surface and has the solid acid catalyst of sulfonic group and carboxylic acid group concurrently;
2) preprocessing process of waste grease
After waste grease is heated to 60 DEG C, carry out core filtration, remove the impurity such as earth therein, food debris, detergent, then adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the waste grease after process;
3) esterification reaction of organic acid process
It is stirred mixing with methanol by waste grease pretreated for step 1), control the mass ratio 1:0.2～1:1.1 of waste grease and methanol, add step 2) solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface prepared, catalyst amount is the 0.5%～3% of reactant gross mass, after being heated stirring 5～21h at 60～80 DEG C, catalyst is recovered by filtration, catalyst can directly be reused, excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, and lower floor is that glycerin by-products is collected respectively;
4) saturated fatty acid methyl ester separation process.
Fatty acid methyl ester step 3) prepared cools to-5～15 DEG C, after carrying out standing 2～14h, is filtered, and separates solid saturated fatty acid methyl ester, obtains the fatty acid methyl ester of high double bond content;
5) epoxidation series connection alkoxide open loop
Fatty acid methyl ester and the solid acid catalyst of recovery after step 4) being separated mix, catalyst amount is the 0.5%～2% of reactant gross mass, stirring it is heated at 50～80 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.2～1:1, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 0.5～8h at such a temperature, complete epoxidation, then, temperature is risen to 80～100 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.1～1:0.5 with the mass ratio of fatty acid methyl ester, continue reaction 0.5～4h, stopped reaction, solid acid catalyst is recovered by filtration, carry out namely obtaining biopolyol product after distillation dewaters.
The described preparation method with the solid acid catalyst that big hydrophobic surface has sulfonic acid and carboxylic acid group concurrently is: by unsaturated carboxylic acid, sulfonic acid and divinylbenzene containing unsaturated double-bond are dissolved in organic solvent, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and divinylbenzene mass ratio be (0.05～0.2): (0.01～0.3): 1, the hot copolymerization 2～10h of mixed solvent is carried out under the initiation of azodiisobutyronitrile initiator, polymerization temperature is at 80～180 DEG C, cooling, filter, namely washing and drying obtains has big hydrophobic surface and has the solid acid catalyst of sulfonic group and carboxylic acid group concurrently, wherein said unsaturated carboxylic acid adopts the one in acrylic acid, butenoic acid, maleic acid, fumaric acid, penetenoic acid, the described sulfonic acid containing unsaturated double-bond adopts the one in styrene sulfonic acid, vinyl sulfonic acid, propene sulfonic acid, hydroxy ethyl sulphonic acid ester, described organic solvent adopts the one in ethyl acetate, n-butyl alcohol, oxolane, isopropanol, acetone.
Described waste grease adopts the animal and plant fat not allowing to eat that food and drink, food processing unit and family produce, animal slaughtering segmentation and leather processing repair the oils and fats that the offal treatment cut is refined, the oils and fats produced in the edible oil and fat refine course of processing, Oil processing or the one in the expired oils and fats of generation in oils and fats storage process. What described food and drink, food processing unit and family produced does not allow the animal and plant fat eaten to adopt the one in swill oil, frying abandoned oil, waste oil and smoke exhaust ventilator condensate; Described animal slaughtering splits the one in the useless Adeps Bovis seu Bubali of oils and fats employing repaiied the offal treatment cut with leather processing and refine, the Adeps Caprae seu ovis that gives up, the Adeps Sus domestica that gives up, useless chicken oil; The oils and fats produced in the described edible oil and fat refine course of processing adopts the one in acidification oil, hargil oil, deodorize distillate oil; The expired oils and fats produced in described Oil processing or oils and fats storage process adopts expired Oleum Brassicae campestris, expired soybean oil, the one in plant produced heat conduction abandoned oil.
The application of polyhydric alcohol prepared by a kind of method utilizing described waste grease to prepare polyhydric alcohol, described waste grease is prepared polyhydric alcohol and is had molecular structure and all adjustable feature of hydroxyl value, can be widely used for various polyurethane coating, polyurethane foam plastics, adhesive, rapid prototyping material, fibre reinforced composites, surfactant field, as the green replacer of conventional polyether polyols or PEPA.
The invention has the beneficial effects as follows: (1), with waste grease for raw material, reduces cost of material, it is to avoid the pollution problem of waste grease, it is achieved that turn waste into wealth. (2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, it is to avoid white pollution. (4) adopt have big hydrophobic surface have concurrently the esterification of solid acid catalysis waste grease of sulfonic group and carboxylic acid group, epoxidation series connection alkoxide ring opening process, simplify technological process, avoid the loaded down with trivial details post processing of homogeneous acid catalyst, reduce the three waste discharge of industry. (5) the biopolyol molecular structure of gained and hydroxyl value are all adjustable, can according to material choice and rate of charge Molecular regulator structure and hydroxyl value. (6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, adhesive, polyurethane coating, surfactants.
Detailed description of the invention
Embodiment 1
The method that a kind of waste grease of the present embodiment prepares polyhydric alcohol, comprises the steps:
1st step has the solid acid having sulfonic group and carboxylic acid group concurrently of big hydrophobic surface and prepares
By acrylic acid, styrene sulfonic acid and divinylbenzene are dissolved in ethyl acetate, solution solubility is 35%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and divinylbenzene mass ratio be 0.1:0.3:1, under the initiation of azodiisobutyronitrile initiator, carry out the hot copolymerization 5h of mixed solvent, initiator amount is the 0.3% of reactant gross mass, solvent thermal polymerization temperature is at 100 DEG C, cooling, filters, and namely washing and drying obtains has big hydrophobic surface and have the solid acid catalyst of sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After swill oil is heated to 60 DEG C, carry out core filtration, remove the impurity such as earth therein, food debris, detergent, then, adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the swill oil after process.
3rd ground beetle esterification reaction process
It is stirred mixing with methanol by pretreated swill oil, controlling the mass ratio 1:0.3 of swill oil and methanol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalyst amount is the 1% of reactant gross mass, after being heated stirring 12h at 70 DEG C, catalyst is recovered by filtration, and catalyst can directly be reused, and excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, yield 98%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester separation process.
Fatty acid methyl ester is cooled to 2 DEG C, after carrying out standing 5h, is filtered, separates solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst amount is the 1% of reactant gross mass, stirring it is heated at 70 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.5, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 4h at such a temperature, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.3 with the mass ratio of fatty acid methyl ester, continue reaction 2h, stopped reaction, solid acid catalyst is recovered by filtration, carry out namely obtaining after distillation dewaters swill oil polylol product, hydroxyl value is 338mgKOH/g.
The present embodiment has a characteristic that (1) the present embodiment, with waste grease for raw material, reduces cost of material, it is to avoid the pollution problem of waste grease, it is achieved that turn waste into wealth. (2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, it is to avoid white pollution. (4) adopt have big hydrophobic surface have concurrently the esterification of solid acid catalysis waste grease of sulfonic group and carboxylic acid group, epoxidation series connection alkoxide ring opening process, simplify technological process, avoid the loaded down with trivial details post processing of homogeneous acid catalyst, reduce the three waste discharge of industry. (5) the biopolyol molecular structure of gained and hydroxyl value are all adjustable, can according to material choice and rate of charge Molecular regulator structure and hydroxyl value. (6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, adhesive, polyurethane coating, surfactants.
Embodiment 2
The method that a kind of waste grease of the present embodiment prepares polyhydric alcohol, comprises the steps:
1st step has the solid acid having sulfonic group and carboxylic acid group concurrently of big hydrophobic surface and prepares
By maleic acid, vinyl sulfonic acid and divinylbenzene are dissolved in n-butyl alcohol, solution solubility is 40%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and divinylbenzene mass ratio be 0.12:0.2:1, under the initiation of azodiisobutyronitrile initiator, carry out the hot copolymerization 8h of mixed solvent, initiator amount is the 0.5% of reactant gross mass, solvent thermal polymerization temperature is at 120 DEG C, cooling, filters, and namely washing and drying obtains has big hydrophobic surface and have the solid acid catalyst of sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After frying abandoned oil is heated to 60 DEG C, carry out core filtration, remove the impurity such as earth therein, food debris, detergent, then, adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the frying abandoned oil after process.
3rd ground beetle esterification reaction process
It is stirred mixing with methanol by pretreated frying abandoned oil, control the mass ratio 1:0.35 of frying abandoned oil and methanol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalyst amount is the 1.5% of reactant gross mass, after being heated stirring 12h at 65 DEG C, catalyst is recovered by filtration, catalyst can directly be reused, excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, yield 97%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester separation process.
Fatty acid methyl ester is cooled to 3 DEG C, after carrying out standing 10h, is filtered, separates solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst amount is the 1.5% of reactant gross mass, stirring it is heated at 70 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.4, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 3h at such a temperature, complete epoxidation, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.2 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, solid acid catalyst is recovered by filtration, carry out after distillation dewaters, namely obtaining frying abandoned oil polylol product, hydroxyl value is 293mgKOH/g.
The present embodiment has a characteristic that (1) the present embodiment, with waste grease for raw material, reduces cost of material, it is to avoid the pollution problem of waste grease, it is achieved that turn waste into wealth. (2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, it is to avoid white pollution. (4) adopt have big hydrophobic surface have concurrently the esterification of solid acid catalysis waste grease of sulfonic group and carboxylic acid group, epoxidation series connection alkoxide ring opening process, simplify technological process, avoid the loaded down with trivial details post processing of homogeneous acid catalyst, reduce the three waste discharge of industry. (5) the biopolyol molecular structure of gained and hydroxyl value are all adjustable, can according to material choice and rate of charge Molecular regulator structure and hydroxyl value. (6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, adhesive, polyurethane coating, surfactants.
Embodiment 3
The method that a kind of waste grease of the present embodiment prepares polyhydric alcohol, comprises the steps:
1st step has the solid acid having sulfonic group and carboxylic acid group concurrently of big hydrophobic surface and prepares
By butenoic acid, propene sulfonic acid and divinylbenzene are dissolved in isopropanol, solution solubility is 40%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and divinylbenzene mass ratio be 0.13:0.25:1, under the initiation of azodiisobutyronitrile initiator, carry out the hot copolymerization 5h of mixed solvent, initiator amount is the 0.6% of reactant gross mass, solvent thermal polymerization temperature is at 120 DEG C, cooling, filters, and namely washing and drying obtains has big hydrophobic surface and have the solid acid catalyst of sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After waste oil is heated to 60 DEG C, carry out core filtration, remove the impurity such as earth therein, food debris, detergent, then, adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the waste oil after process.
3rd ground beetle esterification reaction process
It is stirred mixing with methanol by pretreated waste oil, controlling the mass ratio 1:0.4 of waste oil and methanol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalyst amount is the 1.2% of reactant gross mass, after being heated stirring 17h at 65 DEG C, catalyst is recovered by filtration, and catalyst can directly be reused, and excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, and yield is 95%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester separation process.
Fatty acid methyl ester is cooled to 3 DEG C, after carrying out standing 10h, is filtered, separates solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst amount is the 1% of reactant gross mass, stirring it is heated at 75 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.6, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 5h at such a temperature, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.3 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, solid acid catalyst is recovered by filtration, carry out namely obtaining after distillation dewaters waste oil polylol product, hydroxyl value is 384mgKOH/g.
The present embodiment has a characteristic that (1) the present embodiment, with waste grease for raw material, reduces cost of material, it is to avoid the pollution problem of waste grease, it is achieved that turn waste into wealth. (2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, it is to avoid white pollution. (4) adopt have big hydrophobic surface have concurrently the esterification of solid acid catalysis waste grease of sulfonic group and carboxylic acid group, epoxidation series connection alkoxide ring opening process, simplify technological process, avoid the loaded down with trivial details post processing of homogeneous acid catalyst, reduce the three waste discharge of industry. (5) the biopolyol molecular structure of gained and hydroxyl value are all adjustable, can according to material choice and rate of charge Molecular regulator structure and hydroxyl value. (6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, adhesive, polyurethane coating, surfactants.
Embodiment 4
The method that a kind of waste grease of the present embodiment prepares polyhydric alcohol, comprises the steps:
1st step has the solid acid having sulfonic group and carboxylic acid group concurrently of big hydrophobic surface and prepares
By maleic acid, hydroxy ethyl sulphonic acid ester and divinylbenzene are dissolved in n-butyl alcohol, solution solubility is 35%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and divinylbenzene mass ratio be 0.12:0.22:1, the hot copolymerization 8h of mixed solvent is carried out under the initiation of azodiisobutyronitrile initiator, initiator amount is the 0.5% of reactant gross mass, solvent thermal polymerization temperature is at 140 DEG C, cooling, filtering, namely washing and drying obtains has big hydrophobic surface and has the solid acid catalyst of sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After condensate is heated to 60 DEG C, carry out core filtration, remove the impurity such as earth therein, food debris, detergent, then, adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the condensate after process.
3rd ground beetle esterification reaction process
It is stirred mixing with methanol by pretreated condensate, controlling the mass ratio 1:0.45 of bio oil and methanol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalyst amount is the 1.5% of reactant gross mass, after being heated stirring 14h at 75 DEG C, catalyst is recovered by filtration, and catalyst can directly be reused, and excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, yield 98%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester separation process.
Fatty acid methyl ester is cooled to 2 DEG C, after carrying out standing 7h, is filtered, separates solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst amount is the 1.5% of reactant gross mass, stirring it is heated at 70 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.5, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 5h at such a temperature, complete epoxidation, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.45 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, solid acid catalyst is recovered by filtration, carry out namely obtaining after distillation dewaters condensate polylol product, hydroxyl value is 259mgKOH/g.
The present embodiment has a characteristic that (1) the present embodiment, with waste grease for raw material, reduces cost of material, it is to avoid the pollution problem of waste grease, it is achieved that turn waste into wealth. (2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, it is to avoid white pollution. (4) adopt have big hydrophobic surface have concurrently the esterification of solid acid catalysis waste grease of sulfonic group and carboxylic acid group, epoxidation series connection alkoxide ring opening process, simplify technological process, avoid the loaded down with trivial details post processing of homogeneous acid catalyst, reduce the three waste discharge of industry. (5) the biopolyol molecular structure of gained and hydroxyl value are all adjustable, can according to material choice and rate of charge Molecular regulator structure and hydroxyl value. (6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, adhesive, polyurethane coating, surfactants.
Embodiment 5
The method that a kind of waste grease of the present embodiment prepares polyhydric alcohol, comprises the steps:
1st step has the solid acid having sulfonic group and carboxylic acid group concurrently of big hydrophobic surface and prepares
By unsaturated carboxylic acid such as acrylic acid, styrene sulfonic acid and divinylbenzene are dissolved in acetone, solution solubility is 25%, wherein unsaturated carboxylic acid, unsaturated sulfonic acid and divinylbenzene mass ratio be 0.2:0.2:1, the hot copolymerization 8h of mixed solvent is carried out under the initiation of azodiisobutyronitrile initiator, initiator amount is the 0.8% of reactant gross mass, solvent thermal polymerization temperature is at 160 DEG C, cooling, filtering, namely washing and drying obtains has big hydrophobic surface and has the solid acid catalyst of sulfonic group and carboxylic acid group concurrently.
The preprocessing process of the 2nd step waste grease
After useless Adeps Caprae seu ovis is heated to 60 DEG C, carry out core filtration, remove the impurity such as earth therein, food debris, detergent, then, adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the useless Adeps Caprae seu ovis after process.
3rd ground beetle esterification reaction process
It is stirred mixing with methanol by pretreated useless Adeps Caprae seu ovis, controlling the mass ratio 1:0.45 of useless Adeps Caprae seu ovis and methanol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalyst amount is the 1.5% of reactant gross mass, after being heated stirring 12h at 70 DEG C, catalyst is recovered by filtration, and catalyst can directly be reused, and excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, and yield is 97%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester separation process.
Fatty acid methyl ester is cooled to 0 DEG C, after carrying out standing 12h, is filtered, separates solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst amount is the 1.5% of reactant gross mass, stirring it is heated at 70 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.7, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 6h at such a temperature, then, temperature is risen to 90 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.3 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, solid acid catalyst is recovered by filtration, carry out after distillation dewaters, namely obtaining useless Adeps Caprae seu ovis polylol product, hydroxyl value is 412mgKOH/g.
The present embodiment has a characteristic that (1) the present embodiment, with waste grease for raw material, reduces cost of material, it is to avoid the pollution problem of waste grease, it is achieved that turn waste into wealth. (2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, it is to avoid white pollution. (4) adopt have big hydrophobic surface have concurrently the esterification of solid acid catalysis waste grease of sulfonic group and carboxylic acid group, epoxidation series connection alkoxide ring opening process, simplify technological process, avoid the loaded down with trivial details post processing of homogeneous acid catalyst, reduce the three waste discharge of industry. (5) the biopolyol molecular structure of gained and hydroxyl value are all adjustable, can according to material choice and rate of charge Molecular regulator structure and hydroxyl value. (6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, adhesive, polyurethane coating, surfactants.
Embodiment 6
The method that a kind of waste grease of the present embodiment prepares polyhydric alcohol, comprises the steps:
1st step has the solid acid having sulfonic group and carboxylic acid group concurrently of big hydrophobic surface and prepares
Embodiment 5 is directly used to reclaim catalyst.
The preprocessing process of the 2nd step waste grease
After hargil oil is heated to 60 DEG C, carry out core filtration, remove the impurity such as earth therein, food debris, detergent, then, adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the oil of the hargil after process.
3rd ground beetle esterification reaction process
It is stirred mixing with methanol by pretreated hargil oil, controlling the mass ratio 1:0.3 of hargil oil and methanol, add the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalyst amount is the 1.5% of reactant gross mass, after being heated stirring 13h at 70 DEG C, catalyst is recovered by filtration, and catalyst can directly be reused, and excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, yield 98%, and lower floor is that glycerin by-products is collected respectively;
4th step saturated fatty acid methyl ester separation process.
Fatty acid methyl ester is cooled to 3 DEG C, after carrying out standing 12h, is filtered, separates solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content.
5th step epoxidation series connection alkoxide open loop
The solid acid catalyst of the fatty acid methyl ester after separation and recovery is mixed, catalyst amount is the 1.5% of reactant gross mass, stirring it is heated at 70 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.5, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 5h at such a temperature, then, temperature is risen to 85 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.4 with the mass ratio of fatty acid methyl ester, continue reaction 3h, stopped reaction, solid acid catalyst is recovered by filtration, carry out namely obtaining after distillation dewaters hargil based oil product, hydroxyl value is 403mgKOH/g.
The present embodiment has a characteristic that (1) the present embodiment, with waste grease for raw material, reduces cost of material, it is to avoid the pollution problem of waste grease, it is achieved that turn waste into wealth. (2) biological degradability of the biopolyol of gained is good, can fast degradation at nature, it is to avoid white pollution. (4) adopt have big hydrophobic surface have concurrently the esterification of solid acid catalysis waste grease of sulfonic group and carboxylic acid group, epoxidation series connection alkoxide ring opening process, simplify technological process, avoid the loaded down with trivial details post processing of homogeneous acid catalyst, reduce the three waste discharge of industry. (5) the biopolyol molecular structure of gained and hydroxyl value are all adjustable, can according to material choice and rate of charge Molecular regulator structure and hydroxyl value. (6) of many uses, alternative conventional petroleum polylol, for fields such as polyurethane foam, adhesive, polyurethane coating, surfactants.
Embodiment 7
Polyurethane coating is applied
Equipped with agitator, thermometer, the 250ml four-hole boiling flask of reflux condensing tube and nitrogen conduit adds swill oil polylol by a certain percentage in 100 parts of embodiments 1, 20 parts of dihydromethyl propionic acids and 60 parts of isophorone diisocyanate, it is warming up to 90 DEG C, reaction 4h, it is cooled to 60 DEG C, then, add 20 parts of triethylamines, carry out salt-forming reaction 1h, add 30 parts of acrylic acid methyl ester .s and 0.5 part of azodiisobutyronitrile, it is scattered in 500 parts of water after stirring 20 minutes, add amine chainextender and react 2h at 60 DEG C, it is to slowly warm up to 70 DEG C, reaction 1h, obtain aqueous polyurethane coating.
Embodiment 8
Polyurethane foam is applied
By Adeps Caprae seu ovis polylol useless in 110 parts of embodiments 5,0.57 part of dibutyl tin dilaurate catalyst, 3 parts of silicone oil stabilizers, 4 parts of foaming agent are placed in solvent and are pre-mixed, turn 10 minutes with 1000～1200rpm, then, the polymethylene multi-phenenyl isocyanates of 60 parts are added with in upper container, with hand-held high speed agitator 2500～3000rpm stirring mixing about 30 seconds, mixture at room temperature reacted expansion and forms foam.
Embodiment 9
Adhesive for polyurethane is applied
The waste oil polylol 90 parts of preparation in embodiment 3, join in four-hole boiling flask, it is warmed up to 105 DEG C, evacuation 4h, logical nitrogen concora crush, after bubbling is stable, stops evacuation, it is cooled to about 70 DEG C, 0.4 part of dibutyl tin dilaurate catalyst, adds toluene di-isocyanate(TDI) 50 parts, isophorone diisocyanate 60 parts, have from warming phenomenon, being warmed up to 85 DEG C, insulation is at 85 DEG C of 2h, until it reaches one section of reaction end (toluene di-n-butylamine method titration), add the toluene solvant of 200 parts, obtain adhesive for polyurethane.
Claims (4)
1. the method that a waste grease prepares polyhydric alcohol, it is characterized in that, comprise the steps: to adopt the solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface, catalysis waste grease and methanol carry out being esterified and ester exchange reaction, and waste grease is converted into fatty acid methyl ester and by-product glycerol; Then lower the temperature, the polyunsaturated fatty acid ester in fatty acid methyl ester is separated by the mode of crystallization, improve the content of double bond in fatty acid methyl ester; Then proceeding under bisgallic acid central solid acid catalysis, utilize the collaborative of bisgallic acid center, fatty acid methyl ester is carried out epoxidation by the hydrogen peroxide of direct catalysis 30%, and intermediate product is without separation, after directly heating up, adds by-product glycerol and carries out alkoxide open loop; Catalyst is finally recovered by filtration, and namely decompression distillation obtains bio oil polylol after dewatering;
Described step particularly as follows:
1) prepared by the solid acid having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface
By unsaturated carboxylic acid, sulfonic acid and divinylbenzene containing unsaturated double-bond are dissolved in organic solvent, solution concentration is 20～65%, the hot copolymerization 2～10h of mixed solvent is carried out under the initiation of azodiisobutyronitrile initiator, initiator amount is the 0.1%～1% of reactant gross mass, and solvent thermal polymerization temperature, at 80～180 DEG C, cools down, filtering, namely washing and drying obtains has big hydrophobic surface and has the solid acid catalyst of sulfonic group and carboxylic acid group concurrently;
2) preprocessing process of waste grease
After waste grease is heated to 60 DEG C, carry out core filtration, remove earth therein, food debris, detergent impurity, then adopt the mode of decompression 110 DEG C distillation, remove the moisture in oils and fats, finally, add Emathlite and carry out adsorption bleaching, obtain the waste grease after process;
3) esterification reaction of organic acid process
By step 1) pretreated waste grease is stirred mixing with methanol, control the mass ratio 1:0.2～1:1.1 of waste grease and methanol, add step 2) solid acid catalyst having sulfonic group and carboxylic acid group concurrently with big hydrophobic surface prepared, catalyst amount is the 0.5%～3% of reactant gross mass, after being heated stirring 5～21h at 60～80 DEG C, catalyst is recovered by filtration, catalyst is directly reused, excessive methanol is distilled off, it is layered, upper strata is fatty acid methyl ester, and lower floor is that glycerin by-products is collected respectively;
4) saturated fatty acid methyl ester separation process
By step 3) fatty acid methyl ester prepared cools to-5～15 DEG C, and after carrying out standing 2～14h, it is filtered, separates solid saturated fatty acid methyl ester, obtain the fatty acid methyl ester of high double bond content;
5) epoxidation series connection alkoxide open loop
By step 4) separate after fatty acid methyl ester and the solid acid catalyst of recovery mix, catalyst amount is the 0.5%～2% of reactant gross mass, stirring it is heated at 50～80 DEG C, the hydrogen peroxide of dropping 30%, the mass ratio of hydrogen peroxide and fatty acid methyl ester is 1:0.2～1:1, temperature is controlled lower than 80 DEG C during dropping, after dripping off, continue to react 0.5～8h at such a temperature, complete epoxidation, then, temperature is risen to 80～100 DEG C, add by-product glycerin as alkoxide reagent, it is 1:0.1～1:0.5 with the mass ratio of fatty acid methyl ester, continue reaction 0.5～4h, stopped reaction, solid acid catalyst is recovered by filtration, carry out namely obtaining biopolyol product after distillation dewaters.
2. the method that a kind of waste grease according to claim 1 prepares polyhydric alcohol, it is characterized in that, the described preparation method with the solid acid catalyst that big hydrophobic surface has sulfonic acid and carboxylic acid group concurrently is: by unsaturated carboxylic acid, sulfonic acid and divinylbenzene containing unsaturated double-bond are dissolved in organic solvent, wherein unsaturated carboxylic acid, the mass ratio of unsaturated sulfonic acid and divinylbenzene is (0.05～0.2): (0.01～0.3): 1, the hot copolymerization 2～10h of mixed solvent is carried out under the initiation of azodiisobutyronitrile initiator, polymerization temperature is at 80～180 DEG C, cooling, filter, namely washing and drying obtains has big hydrophobic surface and has the solid acid catalyst of sulfonic group and carboxylic acid group concurrently, wherein said unsaturated carboxylic acid adopts the one in acrylic acid, butenoic acid, maleic acid, fumaric acid, penetenoic acid, the described sulfonic acid containing unsaturated double-bond adopts the one in styrene sulfonic acid, vinyl sulfonic acid, propene sulfonic acid, hydroxy ethyl sulphonic acid ester,Described organic solvent adopts the one in ethyl acetate, n-butyl alcohol, oxolane, isopropanol, acetone.
3. the method that a kind of waste grease according to claim 1 prepares polyhydric alcohol, it is characterized in that: described waste grease adopts the animal and plant fat not allowing to eat that food and drink, food processing unit and family produce, animal slaughtering segmentation and leather processing repair the oils and fats that the offal treatment cut is refined, the oils and fats produced in the edible oil and fat refine course of processing, Oil processing or the one in the expired oils and fats of generation in oils and fats storage process; What described food and drink, food processing unit and family produced does not allow the animal and plant fat eaten to adopt the one in swill oil, frying abandoned oil, waste oil and smoke exhaust ventilator condensate; Described animal slaughtering splits the one in the useless Adeps Bovis seu Bubali of oils and fats employing repaiied the offal treatment cut with leather processing and refine, the Adeps Caprae seu ovis that gives up, the Adeps Sus domestica that gives up, useless chicken oil; The oils and fats produced in the described edible oil and fat refine course of processing adopts the one in acidification oil, hargil oil, deodorize distillate oil; The expired oils and fats produced in described Oil processing or oils and fats storage process adopts expired Oleum Brassicae campestris, expired soybean oil, the one in plant produced heat conduction abandoned oil.
4. the application of the polyhydric alcohol utilizing the method that the waste grease described in claim 1 prepares polyhydric alcohol to prepare, it is characterized in that: waste grease as claimed in claim 1 is prepared polyhydric alcohol and had molecular structure and all adjustable feature of hydroxyl value, it is widely used in various polyurethane coating, polyurethane foam plastics, adhesive, rapid prototyping material, fibre reinforced composites, surfactant field, as the green replacer of conventional polyether polyols or PEPA.
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| CN105567758B (en) * | 2016-01-12 | 2019-06-18 | 华南理工大学 | A kind of method for preparing epoxidized fatty acid methyl ester |
| US10093636B2 (en) | 2016-08-05 | 2018-10-09 | Cpc Corporation, Taiwan | Method for synthesizing bio-plasticizers using acidic ionic liquids as catalysts |
| CN106520381A (en) * | 2016-11-11 | 2017-03-22 | 云南磷化集团有限公司 | Decoloration and deodorization method for drainage oil fatty acid |
| CN108250073A (en) * | 2018-03-10 | 2018-07-06 | 王艺霖 | A kind of preparation method of soybean oil base polyol |
| CN110092882B (en) * | 2019-05-31 | 2021-06-22 | 山东理工大学 | Method for preparing flame-retardant polyurethane foam based on waste paint residue |
| CN116396455B (en) * | 2023-05-26 | 2023-08-11 | 广州艾科新材料股份有限公司 | Method for preparing polyol and polyurethane from reclaimed oil |
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Denomination of invention: A method and application for preparing polyols from discarded oils and fats Granted publication date: 20160615 Pledgee: Zhejiang Shaoxing Hengxin Rural Commercial Bank Co.,Ltd. Dongpu Sub branch Pledgor: ZHEJIANG HENGFENG NEW MATERIAL Co.,Ltd. Registration number: Y2024980024301 |