CN110092917A - Lignin metal salt and the preparation method and application thereof - Google Patents
Lignin metal salt and the preparation method and application thereof Download PDFInfo
- Publication number
- CN110092917A CN110092917A CN201910456768.2A CN201910456768A CN110092917A CN 110092917 A CN110092917 A CN 110092917A CN 201910456768 A CN201910456768 A CN 201910456768A CN 110092917 A CN110092917 A CN 110092917A
- Authority
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- China
- Prior art keywords
- lignin
- metal salt
- preparation
- solid
- added
- Prior art date
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- Granted
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 178
- 150000003839 salts Chemical class 0.000 title claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 78
- 239000002184 metal Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 51
- 239000005060 rubber Substances 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 229920001587 Wood-plastic composite Polymers 0.000 claims abstract description 9
- 239000011155 wood-plastic composite Substances 0.000 claims abstract description 9
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000006185 dispersion Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 239000004744 fabric Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims 1
- 239000006228 supernatant Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 6
- 239000002023 wood Substances 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 238000000053 physical method Methods 0.000 abstract description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 22
- 239000000835 fiber Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 239000006229 carbon black Substances 0.000 description 17
- -1 methoxyl group Chemical group 0.000 description 17
- 239000004800 polyvinyl chloride Substances 0.000 description 16
- 239000012043 crude product Substances 0.000 description 14
- 238000000227 grinding Methods 0.000 description 14
- 230000001376 precipitating effect Effects 0.000 description 14
- 229920000915 polyvinyl chloride Polymers 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000001868 cobalt Chemical class 0.000 description 10
- 150000002815 nickel Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000005452 bending Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000003801 milling Methods 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 150000003751 zinc Chemical class 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000000748 compression moulding Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 238000002604 ultrasonography Methods 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 241001104043 Syringa Species 0.000 description 2
- 235000004338 Syringa vulgaris Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229960003742 phenol Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011297 pine tar Substances 0.000 description 1
- 229940068124 pine tar Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of lignin metal salts and preparation method thereof, are separated by solid-liquid separation to lignin suspension, obtain lignin black liquor；Then metal salt and dispersing agent is added, is sufficiently stirred, obtains solid-liquid mixing system；It is finally separated by solid-liquid separation, obtained solid is washed, dry, crushing obtains sub-micron or nano lignin metal salt.The invention also discloses the lignin metal salts of preparation as reinforcing agent is added to rubber, the application in wood plastic composite.The present invention prepares sub-micron or nano lignin metal salt using the black liquor that paper industry or biorefinery generate, and physical method and chemical method are combined, the even-grained sub-micron of favorable dispersibility or nano lignin metal salt are obtained.It is added to rubber, in wood plastic composite, rubber, the mechanical property of Wood model compound products, thermal stability and barrier property can be significantly increased.
Description
Technical field
High-valued processing and application field the invention belongs to biomass, and in particular to lignin metal salt and its preparation side
Method and application.
Background technique
Lignin (lignin) be only second in plant kingdom cellulose content second it is abundant, and uniquely contain aromatic ring structure
Natural polymer.The biosynthesis new increment about 6 × 10 of the annual lignin in the whole world according to estimates14t.Lignin is by phenyl-
Propane class monomer is connected by chemical bonds such as alkyl-alkyl, alkyl-aryl-groups.It is different according to the quantity of methoxyl group and position,
Monomer can be divided into para hydroxybenzene fundamental mode (H), guaiaci lignum fundamental mode (G) and lilac fundamental mode (S), basic structural unit such as 1 figure
It is shown.Lignin be it is a kind of the amorphous polymer formed is keyed by ester bond and carbon-to-carbon by phenylpropane units, in phenyl ring
On there are methoxyl groups, phosphorus content about 60%~66%, hydrogen content is lower.It is connected between structural unit with ehter bond or carbon-carbon bond, it is preceding
Person is main connection type.Although structure is complicated for lignin molecule, still contain numerous variety classes functions by its molecular structure
Group's (a plurality of types of active function groups such as aromatic radical, phenolic hydroxyl group, alcoholic extract hydroxyl group, carboxyl, methoxyl group, conjugated double bond) and it is natural can
The advantages that regenerating, be biodegradable, nontoxic, and paper industry byproduct is derived from, there is low-cost advantage.Thus,
Lignin is considered as a kind of excellent renewable biomass raw material, Material Field higher value application always by pass
Note.
Summary of the invention
The object of the present invention is to provide a kind of lignin metal salts and the preparation method and application thereof.
To achieve the above object, The technical solution adopted by the invention is as follows:
The preparation method of lignin metal salt, includes the following steps:
(1) lignin suspension is separated by solid-liquid separation, obtains lignin black liquor；
(2) in the lignin black liquor obtained to step (1), metal salt and dispersing agent is added, is sufficiently stirred, it is mixed to obtain solid-liquid
Zoarium system；
(3) solid-liquid mixing system that step (2) obtains is separated by solid-liquid separation, obtained solid is washed, it is dry, crush
To sub-micron or nano lignin metal salt.
Specifically, in step (1), the lignin suspension is paper industry or the lignin suspension that biorefinery generates
Liquid, pH value are 11~13, and main component includes lignin, cellulose, hemicellulose, polysaccharide and ash content, wherein content of lignin
For 10~300g/L；
The solid-liquid separating method is filtering or centrifugation, and filtering is using 300 mesh and the above nylon-type filter cloth, filter bag to wooden
Plain suspension is filtered.Contain more fiber fines in lignin suspension, size is small, structural form, and chemical property is not
It is uniform, the fiber fines in lignin suspension can be retained using nylon-type filter cloth, filter bag, it is black to obtain lignin
Liquid.The nylon-type filter cloth is preferably polypropylene fibre filter cloth, filter bag.
In step (2), the metal salt includes the sulfate, chlorate, nitric acid of iron, cobalt, nickel, zinc, manganese, copper, calcium etc.
One of salt and metal oxide, hydroxide or a variety of combinations；Amount of metal salts is that lignin is total in lignin black liquor
The 0.1~50% of quality.
The dispersing agent is ethylene glycol, polyethylene glycol, glycerine, polyvinyl alcohol, sodium pyrophosphate, calgon, gathers
Any one in sodium acrylate etc.；Dispersant dosage is 0.1~5% of lignin gross mass in lignin black liquor.Due to wood
Quality particle is easy to reunite, and particle agglomeration can be effectively suppressed in the addition of dispersing agent.
The metal salt is added in the form of metal salt solid, aqueous metal salt or metal salt dispersion liquid；Metal salt
The concentration of aqueous solution or metal salt dispersion liquid is 2~40wt%, and the solvent of metal salt dispersion liquid is methanol, in ethyl alcohol, acetone
The mixing of any one or more.
Further, in step (2), the lignin black liquor is first ultrasonically treated 3~30min at 20~50KHz, then
Metal salt and dispersing agent are added under stirring, stirring uses double-layered stirrer, and bottom is propeller agitator, and upper layer is tooth
Shape dispersion impeller, mixing speed are 200~2000rpm.
After metal salt and dispersing agent is added, system is warming up at 40~60 DEG C and continues 2~3h of stirring.
In step (3), the washing uses one of water, methanol, ethyl alcohol, acetone or a variety of mixed solvents；It is described dry
Dry to use vacuum drying mode, drying temperature is 40~80 DEG C, drying time is 2~for 24 hours, dry 6 at preferably 60~70 DEG C~
8h；The crushing is first crushed using pulverizer, is then ground using ball mill.
Lignin metal salt made from above-mentioned preparation method is also within the protection scope of the present invention.
The basic structure of the existing aromatic rings rigidity of lignin has submissive side chain again, contains numerous functions with reactivity
Group, is a kind of sub- macromolecule of subparticle shape with large specific surface area.Therefore, it can be used as reinforcing agent and be added to rubber
In glue, wood plastic composite, modified function is realized.The exploitation of sub-micron or nano lignin metal salt is lignin-base product
High value added utilization provide a new way.The granular size of lignin metal salt is applied to performance and has a significant impact,
Compared to micron and the lignin metal salt powder of larger particle, sub-micron or nano lignin metal salt have bigger ratio table
Area.The introducing of metal ion, dynamics, rigidity, the particle size of the lignin of change add dispersing agent in salification process,
Sub-micron or nano lignin metal salt are formed, the boundary between rubber, wood plastic composite and inorganic/organic filler can be enhanced
Face effect, makes the firm network of System forming, promotes dispersibility of the filler in rubber, wood plastic composite, compatibility, in turn
Improve rubber, the mechanical property of wood plastic composite, thermal stability and barrier property.
The utility model has the advantages that
1, the present invention provides a kind of black liquor preparation sub-micron or nanometer generated using paper industry or biorefinery
The method of lignin metal salt, physical method and chemical method are combined, and obtain the even-grained sub-micro of favorable dispersibility
Rice or nano lignin metal salt.It is added to rubber, in wood plastic composite, rubber, wood plastics composite can be significantly increased
Mechanical property, thermal stability and the barrier property of product.
2, the present invention prepares sub-micron or nano lignin metal using the black liquor that paper industry or biorefinery generate
The process of salt can be directly added into metal salt, save production cost, improve production efficiency, reduce without adjusting black liquor pH
Treatment cost of waste liquor and environmental pollution.
Detailed description of the invention
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned
And/or otherwise advantage will become apparent.
Fig. 1 is the structure of lignin basic unit para hydroxybenzene fundamental mode (H), guaiaci lignum fundamental mode (G) and lilac fundamental mode (S)
Formula.
Fig. 2 is the outside drawing for the lignin molysite product that embodiment 1 is prepared.
Fig. 3 is the infrared spectrogram for the lignin molysite product that embodiment 1 is prepared.
Fig. 4 is the X-ray diffraction spectra for the lignin molysite product that embodiment 1 is prepared.
Specific embodiment
According to following embodiments, the present invention may be better understood.
Embodiment 1
The lignin suspension for taking 3L paper industry to generate, is pre-processed first, and more tiny fibre is contained in suspension
Dimension, size is small, structural form, and chemical property is inhomogenous, is retained using the polypropylene fibre filter cloth of 300 mesh to its fiber fines,
Obtain lignin black liquor.Black liquor is subjected to ultrasonic treatment 15min, ultrasonic power 30KHz, it is anti-that black liquor is then transferred to glass
It answers in kettle, is mixed and dispersed with bilayer stirring, lower layer's stirring is three blade push type agitating paddles, and upper layer is stainless steel periphery
The diameter of dentation dispersion impeller, lower layer's agitating paddle and upper layer dispersion impeller is suitable, and accounts for about the 0.6~0.7 of glass reactor internal diameter, turns
Speed is adjusted to 800rpm, ferric chloride solution (mass fraction of iron chloride is 5%) is then added then, wood contained by addition system
The ethylene glycol of quality gross mass 0.5% is warming up to 50 DEG C, continues to stir 2h.Heat preservation terminates, and is slowly dropped to room temperature, will react it
Lignin metal salt solid-liquid mixing system afterwards is separated by solid-liquid separation at 8000rpm using ultracentrifuge, and the time is
20min, precipitating are washed with methanol/water solution (methanol v: water v=6:4), then that precipitating merging vacuum oven is dry,
Condition is 60 DEG C, 8h, obtains lignin molysite crude product.Lignin molysite crude product is subjected to pulverization process, the grinding used
Instrument is spherical grinder, and milling time 2h, revolving speed 600rpm, grinding obtains sub-micron after completing or nanometer is wooden
Plain sheet salt particle.
Fig. 2 is the outside drawing for the lignin molysite product being prepared.By scanning electron microscope it is found that nano lignin
Molysite partial size about carries out size distribution detection in 20~110nm and with Malvern ParticleSizer, finds its d10=25nm, d50=
65nm, d90=105nm.
The infrared spectrogram for the lignin molysite product that Fig. 3 is, it is known that: lignin molysite relative to lignin,
In salification process, along with the disappearance of methyl, methylene C-H stretching vibration peak, the flexible vibration of aromatic ring frame vibration performance peak, C-O
The reduction of C-H stretching vibration peak and the appearance of Fe-O stretching vibration peak on dynamic peak, phenyl ring show that lignin and molysite are coordinated
Success, is successfully generated lignin molysite.
The X-ray diffraction spectra for the lignin molysite product that Fig. 4 is, it is known that: lignin molysite relative to lignin,
In salification process, the unformed characteristic diffraction peak intensity of lignin is presented significant decrease trend, and lignin is as parent,
Lignin molysite is simultaneously not apparent from and other characteristic diffraction peaks occurs, the whole unformed characteristic diffraction peak for still showing lignin.
The standby formula of rubber system: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulphur, 5 parts of zinc oxide,
2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent, 1 part of paraffin.By the nano lignin molysite and carbon black of preparation
And other processing aids are proportionally added into open mill and are uniformly mixed to obtain rubber compound, measure rubber compound 180 by vulcameter
Sulfurizing time t90 at DEG C carries out sulfidization molding to rubber compound in compression molding agent according to t90, carries out rubber tensile afterwards
Experiment.Tensile property test is tested based on GB/T 1040-2006.The result shows that the nano lignin molysite/carbon black and benefit
Lignin/carbon black obtained by the technology of preparing provided by CN107722396A is compared, and the tensile strength of rubber increases about
42%~48%.The selected rubber trade mark is N330.
Embodiment 2
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 400 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 20min, ultrasonic power 35KHz, it then will be after filtering ultrasound
Black liquor moves into 5L glass reactor, is mixed and is dispersed using Double-layer stirring paddle, and lower layer's stirring is that four blade push types stir
Mix paddle, upper layer is stainless steel double-sided tooth dispersion impeller, and revolving speed is adjusted to 900rpm, be then pumped into dropwise cobalt chloride solution (cobalt chloride
5%) mass fraction is.Then, the glycerine of lignin gross mass 0.4% contained by addition system, is warming up to 55 DEG C, continues to stir
2h.Heat preservation terminates, and is slowly dropped to room temperature, and by the lignin metal salt solid-liquid mixing system after reaction, lower tank uses centrifuge
Be separated by solid-liquid separation at 12000rpm, time 15min, precipitating use ethyl alcohol v: the ethanol/water mixed solvent of water v=8:2 into
Row washing, then that precipitating merging vacuum oven is dry, condition is 65 DEG C, 6h, obtains lignin cobalt salt crude product.It will be wooden
Plain cobalt salt crude product carries out pulverization process, and the grinding instrument used is spherical grinder, milling time 3h, and revolving speed is
500rpm, grinding obtains sub-micron or nano lignin cobalt salt particle after completing, by scanning electron microscope it is found that sub-micro
Rice lignin cobalt salt partial size carries out size distribution detection with Malvern ParticleSizer about in 200~550nm, finds its d10=
205nm, d50=365nm, d90=545nm.
The standby formula of rubber system: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulphur, 5 parts of zinc oxide,
2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent, 1 part of paraffin.By the sub-micron lignin cobalt salt and charcoal of preparation
Black and other processing aids are proportionally added into open mill and are uniformly mixed to obtain rubber compound, measure rubber compound by vulcameter and exist
Sulfurizing time t90 at 180 DEG C carries out sulfidization molding to rubber compound in compression molding agent according to t90, rear to carry out rubber drawing
Stretch experiment.Tensile property test is tested based on GB/T 1040-2006.The result shows that the sub-micron lignin cobalt salt/carbon black
Compared with using lignin/carbon black obtained by technology of preparing provided by CN107722396A, the tensile strength of rubber increases
About 16%~25%.The selected rubber trade mark is N330.
Embodiment 3
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 300 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 15min, ultrasonic power 40KHz, it then will be after filtering ultrasound
Black liquor moves into 5L glass reactor, is mixed and is dispersed using Double-layer stirring paddle, and lower layer's stirring is that four blade push types stir
Mix paddle, upper layer is stainless steel double-sided tooth dispersion impeller, and revolving speed is adjusted to 1000rpm, be then pumped into dropwise nickel chloride solution (nickel chloride
5%) mass fraction is.Then, the polyethylene glycol of lignin gross mass 0.4% contained by addition system, is warming up to 50 DEG C, continues to stir
Mix 2h.Heat preservation terminates, and is slowly dropped to room temperature, and by the lignin metal salt solid-liquid mixing system after reaction, lower tank uses centrifugation
Machine is separated by solid-liquid separation at 11000rpm, time 20min, precipitating ethyl alcohol v: the ethanol/water mixed solvent of water v=7:3
It is washed, then that precipitating merging vacuum oven is dry, condition is 60 DEG C, 7h, obtains lignin nickel salt crude product.It will be wooden
Quality nickel salt crude product carries out pulverization process, and the grinding instrument used is spherical grinder, and milling time 3h, revolving speed is
500rpm, grinding obtains sub-micron or nano lignin nickel salt particle after completing, by scanning electron microscope it is found that sub-micro
Rice lignin nickel salt partial size carries out size distribution detection with Malvern ParticleSizer about in 150~520nm, finds its d10=
155nm, d50=320nm, d90=510nm.
The standby formula of rubber system: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulphur, 5 parts of zinc oxide,
2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent, 1 part of paraffin.By the sub-micron lignin nickel salt and charcoal of preparation
Black and other processing aids are proportionally added into open mill and are uniformly mixed to obtain rubber compound, measure rubber compound by vulcameter and exist
Sulfurizing time t90 at 180 DEG C carries out sulfidization molding to rubber compound in compression molding agent according to t90, rear to carry out rubber drawing
Stretch experiment.Tensile property test is tested based on GB/T 1040-2006.The result shows that the sub-micron lignin nickel salt/carbon black
Compared with using lignin/carbon black obtained by technology of preparing provided by CN107722396A, the tensile strength of rubber increases
About 18%28%.The selected rubber trade mark is N330.
Embodiment 4
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 300 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 15min, ultrasonic power 40KHz, it then will be after filtering ultrasound
Black liquor moves into 5L glass reactor, is mixed and is dispersed using Double-layer stirring paddle, and lower layer's stirring is that four blade push types stir
Mix paddle, upper layer is stainless steel double-sided tooth dispersion impeller, and revolving speed is adjusted to 1000rpm, be then pumped into dropwise liquor zinci chloridi (zinc chloride
4%) mass fraction is.Then, the ethylene glycol of lignin gross mass 0.5% contained by addition system, is warming up to 45 DEG C, continues to stir
3h.Heat preservation terminates, and is slowly dropped to room temperature, and by the lignin metal salt solid-liquid mixing system after reaction, lower tank uses centrifuge
Be separated by solid-liquid separation at 10000rpm, time 20min, precipitating use ethyl alcohol v: the ethanol/water mixed solvent of water v=6:4 into
Row washing, then that precipitating merging vacuum oven is dry, condition is 60 DEG C, 6h, obtains lignin zinc salt crude product.It will be wooden
Plain zinc salt crude product carries out pulverization process, and the grinding instrument used is spherical grinder, milling time 2h, and revolving speed is
800rpm, grinding obtains sub-micron or nano lignin zinc salt particle after completing, by scanning electron microscope it is found that sub-micro
Rice lignin zinc salt partial size carries out size distribution detection with Malvern ParticleSizer about in 40~180nm, finds its d10=
45nm, d50=120nm, d90=175nm.
The standby formula of rubber system: 100 parts of NBR, 20 parts of lignin metal salt, 20 parts of carbon black, 1.5 parts of sulphur, 5 parts of zinc oxide,
2 parts of stearic acid, 1.5 parts of TMTD, 1.5 parts of CZ, 2 parts of anti-aging agent, 1 part of paraffin.By the sub-micron lignin zinc salt and charcoal of preparation
Black and other processing aids are proportionally added into open mill and are uniformly mixed to obtain rubber compound, measure rubber compound by vulcameter and exist
Sulfurizing time t90 at 180 DEG C carries out sulfidization molding to rubber compound in compression molding agent according to t90, rear to carry out rubber drawing
Stretch experiment.Tensile property test is tested based on GB/T 1040-2006.The result shows that the sub-micron lignin zinc salt/carbon black
Compared with using lignin/carbon black obtained by technology of preparing provided by CN107722396A, the tensile strength of rubber increases
About 22%~30%.The selected rubber trade mark is N330.
Embodiment 5
The performance test of lignin metal salt:
In order to test the performance of lignin metal salt obtained by the present invention, control experiment is designed.Method for preparing rubber: NR
(natural rubber) 40g, SBR (butadiene-styrene rubber) 25g, BR (butadiene rubber) 30g, reclaimed rubber 70g, ZnO5g, SA 2g, CZ 3g prevent
Old agent A 2g, paraffin 1g, pine tar 1g, N330 or compounded mix 45g, clay 25g, S2.2g.It is above mass parts.By NR,
SBR, BR, reclaimed rubber are kneaded uniformly on a mill, obtain rubber master batch.Other cooperation machines are added after open mill is cooling to be kneaded
To rubber compound.Rubber compound is molded the test piece that 2mm thickness is made in vulcanization, vulcanization time t90 on compression molding instrument, and pressure is
10MPa.By 1-4 of the embodiment of the present invention preparation respectively obtain the wooden plain sheet of nanometer, sub-micron, cobalt, nickel, zinc salt respectively with carbon black
After ratio (the being 500g) mixing of mass ratio 1:1, it is applied to rubber as reinforcing agent, the rubber being prepared is drawn
Stretch experiment.Tensile property test is tested based on GB/T 1040-2006.Carbon black is not added, lignin is not added and lignin gold
Belong to the blank of salt as 1 group of control；The simple lignin of carbon black is not added as 2 groups of control；With patent CN107722396A institute
After the obtained lignin of method and carbon black are stated with the ratio mixing of mass ratio 1:1, it is applied to rubber system for during as reinforcing agent,
As compareing 3 groups.The Tensile Test Results of rubber are shown in Table 1 when not filled/addition different fillers.
Embodiment 6
The lignin suspension for taking 3L paper industry to generate, is pre-processed first, and more tiny fibre is contained in suspension
Dimension, size is small, structural form, and chemical property is inhomogenous, is retained using the polypropylene fibre filter cloth of 300 mesh to its fiber fines,
Obtain lignin black liquor.Black liquor is subjected to ultrasonic treatment 15min, ultrasonic power 30KHz, it is anti-that black liquor is then transferred to glass
It answers in kettle, is mixed and dispersed with bilayer stirring, lower layer's stirring is three blade push type agitating paddles, and upper layer is stainless steel periphery
The diameter of dentation dispersion impeller, lower layer's agitating paddle and upper layer dispersion impeller is suitable, and accounts for about the 0.6~0.7 of glass reactor internal diameter, turns
Speed is adjusted to 800rpm, ferric chloride solution (mass fraction of iron chloride is 5%) is then added then, wood contained by addition system
The ethylene glycol of quality gross mass 0.5% is warming up to 50 DEG C, continues to stir 2h.Heat preservation terminates, and is slowly dropped to room temperature, will react it
Lignin metal salt solid-liquid mixing system afterwards is separated by solid-liquid separation at 8000rpm using ultracentrifuge, and the time is
20min, precipitating are washed with methanol/water solution (methanol v: water v=6:4), then that precipitating merging vacuum oven is dry,
Condition is 60 DEG C, 8h, obtains lignin molysite crude product.Lignin molysite crude product is subjected to pulverization process, the grinding used
Instrument is spherical grinder, and milling time 2h, revolving speed 600rpm, grinding obtains sub-micron after completing or nanometer is wooden
Plain sheet salt particle, by scanning electron microscope it is found that nano lignin molysite partial size is about in 20~110nm and with Malvern grain
It spends instrument and carries out size distribution detection, find its d10=25nm, d50=65nm, d90=105nm.
Polyvinyl chloride (PVC) formula: lignin/lignin metal salt and PVC are added according to 30%, 60% mass fraction
Enter miniature high-speed mixer, calcium zinc stabilizer CZ866, the phthalic acid two for then successively adding PVC mass fraction 3% are different pungent
Ester (DOP) 5%, polyethylene (PE) wax 1%, calcium stearate 0.5%, super mixer mix.By above-mentioned sample mixing in 180 DEG C of double rollers
5min, slice are kneaded in kneading machine.After cooling, it cuts into pieces, after stacking with three sheet frame moulds on 200 DEG C of vulcanizing press
Hot pressing 5min, pressure 20MPa then under uniform pressure, are cold-pressed 5min, are pressed into the sheet material that thickness is respectively 2mm and 4mm, so
Cut into dumbbell shape and v-notch impact batten respectively afterwards.Then mechanical property is carried out on CMT-7503 type universal testing machine
Experiment, rate of extension 5mm/min determine power and decay to 80%；Bending rate is 2mm/min, determines power and decays to 10%.Cantilever beam punching
Test is hit to carry out on Zwick Roller5133.300 type shock machine.The sky of lignin and lignin metal salt is not added
It is white as control 4 groups, using add lignin as control 5 groups, it is not filled/addition different fillers when PVC Mechanics Performance Testing
Experimental result is shown in Table 2.Tensile property and bending property test are based respectively on GB/T 1447-2005, GB/T1449-2005 progress
Test, impact property are tested according to GB/T 1043-92.The result shows that the nano lignin molysite is compared with lignin,
Tensile strength, the bending strength of PVC has increased separately about 18%~25% and 14%~22%, and impact strength increases 28%~
36%.
Embodiment 7
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 400 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 20min, ultrasonic power 35KHz, it then will be after filtering ultrasound
Black liquor moves into 5L glass reactor, is mixed and is dispersed using Double-layer stirring paddle, and lower layer's stirring is that four blade push types stir
Mix paddle, upper layer is stainless steel double-sided tooth dispersion impeller, and revolving speed is adjusted to 900rpm, be then pumped into dropwise cobalt chloride solution (cobalt chloride
5%) mass fraction is.Then, the glycerine of lignin gross mass 0.4% contained by addition system, is warming up to 55 DEG C, continues to stir
2h.Heat preservation terminates, and is slowly dropped to room temperature, and by the lignin metal salt solid-liquid mixing system after reaction, lower tank uses centrifuge
Be separated by solid-liquid separation at 12000rpm, time 15min, precipitating use ethyl alcohol v: the ethanol/water mixed solvent of water v=8:2 into
Row washing, then that precipitating merging vacuum oven is dry, condition is 65 DEG C, 6h, obtains lignin cobalt salt crude product.It will be wooden
Plain cobalt salt crude product carries out pulverization process, and the grinding instrument used is spherical grinder, milling time 3h, and revolving speed is
500rpm, grinding obtains sub-micron or nano lignin cobalt salt particle after completing, by scanning electron microscope it is found that sub-micro
Rice lignin cobalt salt partial size carries out size distribution detection with Malvern ParticleSizer about in 200~550nm, finds its d10=
205nm, d50=365nm, d90=545nm.
Polyvinyl chloride (PVC) formula: lignin or lignin metal salt and PVC are divided according to 30%, 60% quality
Miniature high-speed mixer is added in number, then successively adds calcium zinc stabilizer CZ866, the phthalic acid two of PVC mass fraction 3%
Different monooctyl ester (DOP) 5%, 1% part of polyethylene (PE) wax, calcium stearate 0.5%, super mixer mix.By above-mentioned sample mixing 180
5min, slice are kneaded in DEG C double roll mill.After cooling, it cuts into pieces, the plate sulphur after stacking with three sheet frame moulds at 200 DEG C
Hot pressing 5min on change machine, pressure 20MPa then under uniform pressure, are cold-pressed 5min, are pressed into the piece that thickness is respectively 2mm and 4mm
Then material cuts into dumbbell shape and v-notch impact batten respectively.Then mechanics is carried out on CMT-7503 type universal testing machine
Performance test, rate of extension 5mm/min determine power and decay to 80%；Bending rate is 2mm/min, determines power and decays to 10%.Cantilever
Beam impact test carries out on Zwick Roller5133.300 type shock machine.Lignin and lignin metal salt is not added
Blank as control 4 groups, using add lignin as control 5 groups, it is not filled/addition different fillers when PVC mechanical property
Test experiments the results are shown in Table 2.Tensile property and bending property test are based respectively on GB/T 1447-2005, GB/T 1449-2005
It is tested, impact property is tested according to GB/T 1043-92.The result shows that the sub-micron lignin cobalt salt and lignin
It compares, tensile strength, the bending strength of PVC has increased separately about 12%~20% and 10%~18%, and impact strength increases
26%~35%.
Embodiment 8
The lignin suspension for taking 3L paper industry to generate, cuts its fiber fines using the polypropylene fibre filter cloth of 300 mesh
It stays, obtains lignin black liquor.Black liquor is subjected to ultrasonic treatment 15min, ultrasonic power 40KHz, it then will be after filtering ultrasound
Black liquor moves into 5L glass reactor, is mixed and is dispersed using Double-layer stirring paddle, and lower layer's stirring is that four blade push types stir
Mix paddle, upper layer is stainless steel double-sided tooth dispersion impeller, and revolving speed is adjusted to 1000rpm, be then pumped into dropwise nickel chloride solution (nickel chloride
5%) mass fraction is.Then, the polyethylene glycol of lignin gross mass 0.4% contained by addition system, is warming up to 50 DEG C, continues to stir
Mix 2h.Heat preservation terminates, and is slowly dropped to room temperature, and by the lignin metal salt solid-liquid mixing system after reaction, lower tank uses centrifugation
Machine is separated by solid-liquid separation at 11000rpm, time 20min, precipitating ethyl alcohol v: the ethanol/water mixed solvent of water v=7:3
It is washed, then that precipitating merging vacuum oven is dry, condition is 60 DEG C, 7h, obtains lignin nickel salt crude product.It will be wooden
Quality nickel salt crude product carries out pulverization process, and the grinding instrument used is spherical grinder, and milling time 3h, revolving speed is
500rpm, grinding obtains sub-micron or nano lignin nickel salt particle after completing, by scanning electron microscope it is found that sub-micro
Rice lignin nickel salt partial size carries out size distribution detection with Malvern ParticleSizer about in 150~520nm, finds its d10=
155nm, d50=320nm, d90=510nm.
Polyvinyl chloride (PVC) formula: lignin or lignin metal salt and PVC are divided according to 30%, 60% quality
Miniature high-speed mixer is added in number, then successively adds calcium zinc stabilizer CZ866, the phthalic acid two of PVC mass fraction 3%
Different monooctyl ester (DOP) 5%, 1% part of polyethylene (PE) wax, calcium stearate 0.5%, super mixer mix.By above-mentioned sample mixing 180
5min, slice are kneaded in DEG C double roll mill.After cooling, it cuts into pieces, the plate sulphur after stacking with three sheet frame moulds at 200 DEG C
Hot pressing 5min on change machine, pressure 20MPa then under uniform pressure, are cold-pressed 5min, are pressed into the piece that thickness is respectively 2mm and 4mm
Then material cuts into dumbbell shape and v-notch impact batten respectively.Then mechanics is carried out on CMT-7503 type universal testing machine
Performance test, rate of extension 5mm/min determine power and decay to 80%；Bending rate is 2mm/min, determines power and decays to 10%.Cantilever
Beam impact test carries out on Zwick Roller5133.300 type shock machine.Lignin and lignin metal salt is not added
Blank as control 4 groups, using add lignin as control 5 groups, it is not filled/addition different fillers when PVC mechanical property
Test experiments the results are shown in Table 2.Tensile property and bending property test are based respectively on GB/T 1447-2005, GB/T 1449-2005
It is tested, impact property is tested according to GB/T 1043-92.The result shows that the sub-micron lignin nickel salt and lignin
It compares, tensile strength, the bending strength of PVC has increased separately about 15%~23% and 12%~20%, and impact strength increases
28%~36%.
Table 1
Table 2
By table 1,2 as it can be seen that sub-micron or nano lignin iron that the present invention is prepared, cobalt, nickel, zinc salt are as benefit
Strong agent is applied to rubber, in PVC composite material, shows excellent performance.It is special in view of the material of lignin metal salt itself
It is anisotropic, functional and with the compatibility of other macromolecule mediums, intercommunity, be applied to rubber using lignin metal salt as reinforcing agent
In glue, wood plastic composite, it is expected to obviously improve rubber, the mechanical property of Wood model compound products, thermal stability and barrier property
Energy.
The present invention provides the thinking and method of a kind of lignin metal salt and the preparation method and application thereof, specific implementation should
There are many method and approach of technical solution, the above is only a preferred embodiment of the present invention, it is noted that for this technology
For the those of ordinary skill in field, various improvements and modifications may be made without departing from the principle of the present invention, this
A little improvements and modifications also should be regarded as protection scope of the present invention.Existing skill can be used in each component part being not known in the present embodiment
Art is realized.
Claims (10)
1. the preparation method of lignin metal salt, which comprises the steps of:
(1) lignin suspension is separated by solid-liquid separation, obtains lignin black liquor；
(2) in the lignin black liquor obtained to step (1), metal salt and dispersing agent is added, is sufficiently stirred, obtains solid-liquid mixture
System；
(3) solid-liquid mixing system that step (2) obtains is separated by solid-liquid separation, obtained solid is washed, dry, crushing obtains Asia
Micron or nano lignin metal salt.
2. the preparation method of lignin metal salt according to claim 1, which is characterized in that described wooden in step (1)
Plain suspension is paper industry or the lignin suspension that biorefinery generates, and pH value is 11~13, and main component includes wooden
Element, cellulose, hemicellulose, polysaccharide and ash content, wherein content of lignin is 10~300g/L；
The solid-liquid separating method is filtering or centrifugation, and filtering is outstanding to lignin using 300 mesh and the above nylon-type filter cloth, filter bag
Supernatant liquid is filtered.
3. the preparation method of lignin metal salt according to claim 1, which is characterized in that in step (2), the gold
Belonging to salt includes iron, cobalt, nickel, zinc, manganese, copper, the sulfate of calcium, chlorate, one in nitrate and metal oxide, hydroxide
Kind or a variety of combinations；Amount of metal salts is 0.1~50% of lignin gross mass in lignin black liquor.
4. the preparation method of lignin metal salt according to claim 1, which is characterized in that in step (2), point
Powder is ethylene glycol, polyethylene glycol, glycerine, polyvinyl alcohol, sodium pyrophosphate, calgon, any in Sodium Polyacrylate
It is a kind of；Dispersant dosage is 0.1~5% of lignin gross mass in lignin black liquor.
5. the preparation method of lignin metal salt according to claim 4, which is characterized in that in step (2), the metal
Salt is added in the form of metal salt solid, aqueous metal salt or metal salt dispersion liquid；Aqueous metal salt or metal salt
The concentration of dispersion liquid is 2~40wt%, and the solvent of metal salt dispersion liquid is methanol, ethyl alcohol, any one or more in acetone
Mixing.
6. the preparation method of lignin metal salt according to claim 1, which is characterized in that described wooden in step (2)
Plain black liquor is first ultrasonically treated 3~30min at 20~50KHz, and metal salt and dispersing agent, stirring are then added under stirring
Using double-layered stirrer, bottom is propeller agitator, and upper layer is dentation dispersion impeller, and mixing speed is 200~2000rpm.
7. the preparation method of lignin metal salt according to claim 1, which is characterized in that in step (2), metal is added
After salt and dispersing agent, system is warming up at 40~60 DEG C and continues 2~3h of stirring.
8. the preparation method of lignin metal salt according to claim 1, which is characterized in that in step (3), the washing
Use one of water, methanol, ethyl alcohol, acetone or a variety of mixed solvents；It is described dry using vacuum drying mode, drying temperature
Be 40~80 DEG C, drying time be 2~for 24 hours；The crushing is first crushed using pulverizer, is then ground using ball mill
Mill.
9. the lignin metal salt that any one of claim 1~8 preparation method is prepared.
10. lignin metal salt as claimed in claim 9 is added to rubber, the application in wood plastic composite as reinforcing agent.
Priority Applications (1)
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| CN116214655A (en) * | 2023-03-06 | 2023-06-06 | 南京林业大学 | Wood-based hydrogel and preparation method thereof |
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| CN112920424A (en) * | 2021-04-08 | 2021-06-08 | 长沙理工大学 | Polypropylene composition based on esterified lignin metal salt nucleating agent |
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| CN113817237A (en) * | 2021-11-02 | 2021-12-21 | 赛轮集团股份有限公司 | Hydroxymethylated lignin modified cobalt neodecanoate/natural rubber coprecipitation rubber, and preparation method and application thereof |
| CN113817237B (en) * | 2021-11-02 | 2023-08-11 | 赛轮集团股份有限公司 | Co-precipitated rubber of hydroxymethylated lignin modified cobalt neodecanoate/natural rubber, preparation method and application |
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