CN115368618B - Method for preparing light phenolic resin heat-insulating material from biomass - Google Patents
Method for preparing light phenolic resin heat-insulating material from biomass Download PDFInfo
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- CN115368618B CN115368618B CN202211068501.4A CN202211068501A CN115368618B CN 115368618 B CN115368618 B CN 115368618B CN 202211068501 A CN202211068501 A CN 202211068501A CN 115368618 B CN115368618 B CN 115368618B
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- solution
- lignin
- phenolic resin
- phenol
- biomass
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 49
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 49
- 239000002028 Biomass Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000011810 insulating material Substances 0.000 title claims abstract description 27
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229920005610 lignin Polymers 0.000 claims abstract description 86
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000003513 alkali Substances 0.000 claims abstract description 51
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002893 slag Substances 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 238000005187 foaming Methods 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 11
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims abstract description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 claims abstract description 10
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 79
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000000413 hydrolysate Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 15
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 230000003472 neutralizing effect Effects 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000002296 pyrolytic carbon Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 210000003298 dental enamel Anatomy 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 3
- 229920002675 Polyoxyl Polymers 0.000 claims description 3
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000007667 floating Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002344 surface layer Substances 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 239000010451 perlite Substances 0.000 claims description 2
- 235000019362 perlite Nutrition 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 abstract description 7
- 239000001913 cellulose Substances 0.000 abstract description 5
- 229920002678 cellulose Polymers 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002153 silicon-carbon composite material Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000012704 multi-component copolymerization Methods 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 235000011187 glycerol Nutrition 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- KLIDCXVFHGNTTM-UHFFFAOYSA-N 2,6-dimethoxyphenol Chemical compound COC1=CC=CC(OC)=C1O KLIDCXVFHGNTTM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of furfural
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/009—Use of pretreated compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
A method for preparing a light phenolic resin heat-insulating material from biomass belongs to the field of biomass energy chemical industry, and comprises the steps of hydrolyzing and dehydrating hemicellulose to produce furfural; preparing phenolic resin by using alkali-soluble catalytic degradation of phenolized lignin and furfuraldehyde and formaldehyde multi-component copolymerization, preparing porous carbon by carbonizing alkali-soluble slag, and preparing hollow silicon carbon composite particles on the surface of the silica closed porous carbon; and compounding and curing auxiliary agents such as phenolic resin, hollow carbon, foaming agent and the like to prepare the phenolic resin foaming heat-insulating material. According to the invention, the lignin is catalytically degraded into lignin phenol micromolecules by adopting the synergistic catalysis of alkali and sodium thiosulfate, and phenol is partially or completely substituted for phenol to synthesize phenolic resin; synthesizing phenolic resin by using self-produced furfural to partially or completely replace formaldehyde; the heat-insulating material prepared by utilizing the surface-closed porous material and the self-produced phenolic resin through composite foaming has the industrialized advantages of light weight and low cost; and hemicellulose, lignin and cellulose in biomass are fully utilized in the whole process, so that comprehensive utilization is realized.
Description
Technical Field
The invention belongs to the field of biomass energy chemical industry, and particularly relates to a method for preparing a light phenolic resin heat-insulating material from biomass.
Background
With the increasing awareness of greenhouse gas emission and shortage of fossil resources, the search for the substitution of renewable resources for fossil resources for the production of polymeric materials is a growing trend.
Polymer foams play an important role in everyday life, and common polymer foams include polystyrene, polyurethane, polyisocyanurate and phenolic foams. However, they have a high flammability and toxic gas emissions during combustion, which negatively affects these foams. In addition, the need to increase energy efficiency in construction has prompted the construction industry to increasingly specify insulation materials with excellent insulation properties. Although each type of foam has its advantages and disadvantages, phenolic foam is widely used as a thermal insulation material in the construction industry due to its extremely low thermal conductivity, low flammability, low density, high rigidity, good chemical and heat resistance. However, the main problems with phenolic foam are its relatively low mechanical strength and high brittleness compared to other commercial foams. To ameliorate these weaknesses, phenolic foam has been reinforced with natural and synthetic fibers, nanoparticles and inert fillers. Despite certain technological advances, the selection of renewable materials that are cost effective and environmentally friendly is a necessary trend. Lignin is the second most common natural polymer next to cellulose, accounting for 25% of the weight and 40% of the energy content of lignocellulosic biomass. Lignin is produced annually in amounts approaching 5000-7000 ten thousand tons worldwide, but only 2-5% is used as a precursor for chemical and material production, and a large amount of lignin is still burned as a low heating value fuel. Moreover, the high value utilization of lignin is critical to the economic viability of comprehensive utilization of biomass. However, the complex three-dimensional polymeric structure of lignin is formed by the condensation of phenylpropane units, of which parahydroxyphenol (H), guaiacol (G) and syringol (S) are the main precursors. Most biorefinery schemes focus on the use of readily convertible fractions, while lignin is still relatively underutilized in its potential due to its complex structure and stable linkages. Although the structural similarity of lignin to phenol makes it suitable as a substitute for phenolic foam. Due to the lower reactivity of lignin, the proportion of substituted phenol in the foam is lower, and the high lignin content adversely affects the mechanical properties of the foam. In addition, the high molecular weight of lignin causes the resin to gel during foam formation. In order to address these problems, numerous attempts have been made over the past decades to replace petroleum-based phenols with cost-effective biomass phenols extracted from biomass. However, there are still huge obstacles in commercialization, mainly for the following reasons:
(1) Lignin has a complex structure and cannot be degraded into a product of uniform molecular formula even though a large amount of researches adopt a degradation fractionation method.
(2) Even through degradation, the heterogeneous structure and the more and more reactive functional groups reduce reactivity, resulting in a product with poorer properties than petroleum-based products. Lignin-based phenolic foams still generally have lower properties than petroleum-based phenolic foams.
(3) The degradation product has complex components, no definite application target product and huge obstacle for large-scale application.
There is therefore a need in the art for a new solution to these problems.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a lightweight phenolic resin thermal insulation material from biomass, the method comprising: hydrolyzing and dehydrating hemicellulose to produce furfural; preparing phenolic resin by using alkali-soluble catalytic degradation of phenolized lignin and furfuraldehyde and formaldehyde multi-component copolymerization, preparing porous carbon by carbonizing alkali-soluble slag, and preparing hollow silicon carbon composite particles on the surface of the silica closed porous carbon; and compounding and curing auxiliary agents such as phenolic resin, hollow carbon, foaming agent and the like to prepare the phenolic resin foaming heat-insulating material.
In order to achieve the above purpose, the invention adopts the following technical scheme: the method for preparing the light phenolic resin heat-insulating material by using the biomass is characterized by comprising the following steps of:
step one, according to the solid-to-liquid ratio of the dry basis of the siliceous biomass to the sulfuric acid solution of 1kg: (5-10) adding the silicon-containing biomass with the crushed average particle diameter of 10-20 mm into an enamel reaction kettle, spraying and adding sulfuric acid solution with the concentration of 1-3 wt% from above, heating and refluxing for 2-4 hours, extruding and filtering, separating hydrolysate, soaking and washing obtained hydrolysate residues with equal volume of deionized water, extruding for two times to obtain washing residues, and returning the washing water containing dilute sugar acid to an acid preparation process for recycling; concentrating the hydrolysate to obtain xylose solution with the concentration of 10-15 wt% and sending the xylose solution to a furfural workshop to prepare furfural;
step two, according to the solid-to-liquid ratio of the dry washing slag to the sodium hydroxide solution of 1kg: (5-10) L, adding a sodium hydroxide solution with the concentration of 3-8wt% into the washing slag obtained in the step one, uniformly mixing, heating and refluxing for reaction for 2-4 h, cooling, filtering and separating alkali slag to obtain an alkali lignin solution containing sodium silicate, and drying the obtained alkali slag in a rotary furnace; neutralizing the obtained alkali lignin solution containing sodium silicate with sulfuric acid solution with the concentration of 10-15 wt% until the pH value is 10-11 to form alkali lignin solution containing silicic acid aggregate;
step three, placing the dried alkali-soluble slag prepared in the step two into a tube furnace, heating to 500-800 ℃ for treatment for 1h at a heating rate of 10 ℃/min under the protection of nitrogen, cooling to room temperature to obtain porous pyrolytic carbon, and crushing to 10-100 meshes to form porous pyrolytic carbon powder;
step four, adding the porous pyrolytic carbon powder obtained in the step three into the alkali lignin solution containing silicic acid aggregate, which is prepared in the step two and is neutralized to pH=10-11, stirring, adsorbing and coating for 10-20 min, neutralizing with acid to pH=8-8.5, stirring for 30-40 min, filtering and separating the alkali lignin solution, drying a filter cake to prepare porous carbon with silica coated on the surface, and scattering for later use;
regulating the sodium hydroxide content of the alkali lignin solution prepared in the step four to be 3wt%, adding a catalyst sodium thiosulfate accounting for 0.5-3 wt% of the system, adding the catalyst sodium thiosulfate into a hydrothermal reaction kettle, heating to 150-220 ℃, reacting for 10-40 min, cooling and discharging to obtain a degraded alkali lignin phenol solution;
step six, adding the alkali lignin phenol degradation solution, phenol and sodium hydroxide obtained in the step five into a reaction device, heating to 80-100 ℃, and refluxing for 0.5-2 h to obtain a phenolized prepolymerized alkali lignin phenol solution;
the mass of lignin in the alkali lignin degrading phenol solution accounts for 50-100 wt% of the total mass of lignin and phenol, and the mass of sodium hydroxide accounts for 5wt% of the total mass of lignin and phenol; wherein the mass of lignin in the solution of degrading alkali lignin phenol accounts for 100% of the total mass of lignin and phenol, and is lignin phenol completely substituted phenol;
step seven, adding furfural, formaldehyde or mixed solution of furfural and formaldehyde produced in the step one into the phenolized prepolymerized alkali lignin phenol solution obtained in the step six in batches according to the mass ratio, adjusting the system temperature to 60-70 ℃ in the first batch, carrying out addition reaction for 0.5-1.5 h, then heating to 75-90 ℃, adding the rest 20% mixed solution, carrying out constant-temperature reaction for 1-2.5 h, and reducing the temperature to 50-70 ℃; neutralizing with acetic acid to pH=5.5-6.5, and distilling under reduced pressure until the solid content of the solution reaches 70-80 wt%;
the mass ratio of the alkali lignin phenol to the aldehyde is 1:1-2; the mass ratio of the furfural to the formaldehyde in the mixed solution is as follows: 0:100-100: 0;
step eight, mixing 100 parts of phenolic resin prepared in the step seven, 2 parts of surfactant, 5 parts of foaming agent and 1 part of stabilizer glycerol, stirring uniformly, adding 30-60 parts of porous material, 8 parts of curing agent, stirring rapidly for 10-30 min, adding into a mould, foaming for 5min at 30-50 ℃, heating to 75-85 ℃, and curing for 30-35 min to obtain the biomass-based phenolic resin composite foaming heat-insulating material.
Further, the siliceous biomass in the first step comprises one or a combination of several of rice hulls, rice straw, wheat hulls, wheat straw, and bamboo branches.
Further, the extrusion filtering method in the first step is as follows: the bottom of the enamel reaction kettle is provided with a filter screen, compressed air or high-pressure steam is introduced above the materials, the hydrolysate is discharged out of the reaction kettle under the action of pressure, and deionized water with the same volume as the hydrolysate slag is added for soaking, extrusion and dehydration for two times.
Further, the method for preparing furfural by sending the hydrolysate separated in the step one to a furfural workshop comprises the following steps:
adding 2mol/L sulfuric acid as a catalyst solution into a reactor, introducing nitrogen at 150-200 ℃ into the bottom of the reactor, heating by a nitrogen heater until the catalyst solution flows back, adding promoter sodium chloride to saturation, stirring to form a rotating liquid surface with a fixed concentration of catalyst and promoter, concentrating the hydrolysate to obtain a xylose solution with concentration of 10-15 wt%, spraying the xylose solution into the reactor at the speed of 150-300 mL/min, performing xylose dehydration reaction on the liquid surface layer to generate furfural steam, and condensing by a condenser to obtain the furfural solution.
Further, the surfactant in the step eight is one or a mixture of more of Tween T-80, SPAN-80 and polyoxyl castor oil.
Further, the foaming agent in the step eight is one or a mixture of more than one of n-pentane, n-hexane, methylene dichloride, carbonate, bicarbonate and azo compounds.
Further, the curing agent in the step eight is one or a mixture of more of toluene sulfonic acid, phenol sulfonic acid and phosphoric acid.
Further, the porous material in the step eight comprises one or a mixture of coal glass floating beads, diatomite, perlite and the porous carbon coated with silicon dioxide prepared in the step four.
Further, in the third step, the dry alkali solution slag is replaced by other light porous biomass, and the other light porous biomass comprises one or a mixture of more of xylose slag, furfural slag, papermaking black liquor lignin and ethanol lignin.
Through the design scheme, the invention has the following beneficial effects:
(1) The alkali lignin solution containing sodium silicate is neutralized to pH=10-11 by acid, and the size of silicate aggregate formed by sodium silicate can be regulated and controlled by pH according to the diameter of the porous carbon hole, so that the silicate aggregate is coated on the surface of the porous carbon to form hollow porous carbon with a closed surface. The silica is used as a sealing agent for preparing the hollow porous carbon, and is used as a flame retardant for increasing the flame retardant property of the resin foam.
(2) The invention provides a high-efficiency modification method for catalyzing lignin depolymerization, demethylation and phenolization at a medium temperature, wherein a reaction mixture is directly used for preparing phenolic resin without further separation and purification.
(3) According to the invention, the lignin is catalytically degraded into lignin phenol micromolecules by adopting the synergistic catalysis of alkali and sodium thiosulfate, and phenol is partially or completely substituted for phenol to synthesize phenolic resin; synthesizing phenolic resin by using self-produced furfural to partially or completely replace formaldehyde; and preparing the heat-insulating material by utilizing the surface-closed porous material and phenolic resin composite foaming.
(4) The invention adopts acid-soluble hemicellulose and other acid-soluble substances, alkali-soluble lignin and silicon dioxide to prepare a three-dimensional space reticular void structure mainly formed by cellulose and part of undegraded lignin, volatile matters escape after carbonization, a large number of micropores are formed to prepare light porous carbon, porous carbon powder is coated on the sealing surface by sheet silicic acid to prepare closed-pore light porous carbon, and the closed-pore light porous carbon is compounded with phenolic resin to foam to prepare a light heat-insulating material, so that the load of a building main body or the load of an application main body is greatly reduced.
(5) According to the invention, the hemicellulose in biomass is utilized to produce furfural, lignin is utilized to produce lignin phenol, and cellulose is utilized to produce porous carbon, so that comprehensive utilization is realized.
(6) The invention fully utilizes biomass carbon, realizes negative carbon dioxide emission, replaces phenol and formaldehyde to synthesize phenolic resin, and reduces carbon dioxide emission.
Detailed Description
The invention utilizes hemicellulose to hydrolyze and dehydrate to produce furfural; preparing phenolic resin by alkali-soluble catalytic degradation of phenolized lignin and multi-element copolymerization of the phenolized lignin, furfural and formaldehyde; carbonizing alkali slag to prepare porous carbon, and sealing the porous surface with silicon dioxide to prepare hollow silicon carbon composite particles; and compounding and curing auxiliary agents such as phenolic resin, hollow carbon, foaming agent and the like to prepare the phenolic resin foaming heat-insulating material. According to the invention, the lignin is catalytically degraded into lignin phenol micromolecules by adopting the synergistic catalysis of alkali and sodium thiosulfate, and phenol is partially or completely substituted for phenol to synthesize phenolic resin; synthesizing phenolic resin by using self-produced furfural to partially or completely replace formaldehyde; the heat-insulating material prepared by utilizing the surface-closed porous material and the self-produced phenolic resin through composite foaming has the industrialized advantages of light weight and low cost; and hemicellulose, lignin and cellulose in biomass are fully utilized in the whole process, so that comprehensive utilization is realized.
The invention will be further described in connection with preferred embodiments for the sake of clarity, it being understood by those skilled in the art that the following detailed description is intended to be illustrative, but not limiting, of the scope of the invention. Well-known methods and procedures have not been described in detail so as not to obscure the present invention.
Example 1
Preparing porous carbon with surface coated with silicon dioxide, which comprises the following steps:
step one, according to the solid-to-liquid ratio of the straw dry basis to the sulfuric acid solution of 1kg:5L, adding the crushed straws with the average particle size of 10mm into an enamel reaction kettle, spraying and adding sulfuric acid solution with the concentration of 2wt% from the upper part, heating and refluxing for reaction for 180min, extruding and filtering, separating hydrolysate, soaking and washing the obtained hydrolysate with deionized water with the same volume, extruding for 2 times to obtain washing residues, and returning the washing water containing dilute sugar acid generated in the washing process to an acid preparation process for recycling; concentrating the hydrolysate to obtain xylose solution with concentration of 10-15 wt% and sending the xylose solution to a furfural workshop to prepare furfural;
step two, according to the solid-to-liquid ratio of the dry washing slag to the sodium hydroxide solution of 1kg:8L, adding a sodium hydroxide solution with the concentration of 5wt% into the washing slag obtained in the first step, heating and refluxing for reaction for 240min, cooling, filtering and separating alkali solution slag to obtain an alkali lignin solution containing sodium silicate; neutralizing the obtained alkali lignin solution containing sodium silicate with sulfuric acid solution with the concentration of 10wt% until the pH=10 to form alkali lignin solution containing silicic acid aggregate, and drying the obtained alkali solution slag in a rotary furnace;
step three, placing the dried alkali-soluble slag prepared in the step two into a tube furnace, heating to 600 ℃ for treatment for 1h at a heating rate of 10 ℃/min under the protection of nitrogen, cooling to obtain porous pyrolytic carbon, and crushing to 10-100 meshes to form porous pyrolytic carbon powder;
and step four, adding the porous pyrolytic carbon powder obtained in the step three into the alkali lignin solution which is prepared in the step two and is neutralized to pH=10 and contains silicic acid aggregates, stirring and adsorbing for 10min, neutralizing with acid to pH=8, stirring for 30min, filtering and separating the alkali lignin solution, drying a filter cake to prepare the porous carbon with the surface coated with silicon dioxide, and scattering for later use.
Example 2
The stirring adsorption time in the fourth step of example 1 was changed to 20 minutes, and the other conditions were the same as in example 1 to prepare a porous carbon having a silica coated surface.
Example 3
In step four, the porous carbon surface-coated with silica was prepared by neutralizing with an acid to ph=8.5 under the same conditions as in example 1.
Example 4
Adding 2mol/L sulfuric acid as a catalyst solution into a reactor, introducing nitrogen at 150-200 ℃ into the bottom of the reactor, heating by a nitrogen heater until the catalyst solution flows back, adding promoter sodium chloride to saturation, stirring to form a rotating liquid surface with a fixed concentration of catalyst and promoter, spraying the concentrated hydrolysate in the step one in the embodiment 1 into the reactor at the speed of 300mL/min, performing xylose dehydration reaction on the liquid surface layer to generate furfural steam, condensing by a condenser to obtain furfural solution, and introducing the furfural solution into the embodiment 5 to prepare phenolic resin.
Example 5
(1) Adjusting the sodium hydroxide content of the alkali lignin solution prepared in the step four in the example 1 to 3 weight percent by using 10 weight percent sodium hydroxide, adding a catalyst sodium thiosulfate, wherein the adding amount of the catalyst sodium thiosulfate is 0.5 weight percent of the system, adding the catalyst sodium thiosulfate into a hydrothermal reaction kettle, heating to 180 ℃, reacting for 90min, cooling and discharging to obtain a degraded alkali lignin phenol solution;
(2) adding the alkali lignin phenol degradation solution and phenol obtained in the step (1) into a reaction device, heating to 90 ℃, and refluxing for 1h to obtain a phenolized prepolymerized alkali lignin phenol solution;
the mass of lignin in the alkali lignin degradation phenol solution accounts for 80wt% of the total mass of lignin and phenol;
(3) adding the mixed solution of furfural and formaldehyde produced in the example 2 into the phenolized prepolymerized alkali lignin phenol solution obtained in the step (2) in batches according to the mass ratio, adjusting the temperature of a system to 70 ℃ in the first batch, carrying out addition reaction for 60min, then heating to 90 ℃, adding the rest 20% mixed solution, carrying out constant-temperature reaction for 90min, and reducing the temperature to 50-70 ℃; neutralizing with acetic acid to pH=6.5, and distilling under reduced pressure until the solid content of the solution reaches 75wt%;
the mass ratio of the alkali lignin phenol to the mixed aldehyde is 1:2; the mass ratio of furfural to formaldehyde in the mixed solution is 1:1, the mixed aldehyde is the mixture of furfural and formaldehyde.
Example 6
Mixing 100 parts of phenolic resin prepared in the step (3) in the embodiment 3, 2 parts of SPAN-80 surfactant, 5 parts of foaming agent n-pentane and 1 part of stabilizer glycerin, uniformly stirring, adding 50 parts of silica coated porous material, 8 parts of curing agent toluene sulfonic acid, rapidly stirring for 10min, adding into a mold, foaming for 5min at the temperature of 45 ℃, heating to 80 ℃, and curing for 30min to obtain the biomass-based phenolic resin composite foaming heat-insulating material.
Example 7
Mixing 100 parts of phenolic resin prepared in the step (3) in the embodiment 3, 2 parts of polyoxyl castor oil surfactant, 5 parts of foaming agent sodium bicarbonate and 1 part of stabilizer glycerol, uniformly stirring, adding 50 parts of silica coated porous material, 8 parts of curing agent phenolsulfonic acid, rapidly stirring for 10min, adding into a mold, foaming for 5min at the temperature of 45 ℃, heating to 80 ℃, and curing for 30min to obtain the biomass-based phenolic resin composite foaming heat-insulating material.
Example 8
Mixing 100 parts of phenolic resin prepared in the step (3) in the embodiment 3, 2 parts of Tween T-80 surfactant, 3 parts of foaming agent n-pentane+2 parts of n-hexane and 1 part of stabilizer glycerol, uniformly stirring, adding 30 parts of coal glass floating beads, 4 parts of curing agent phenolsulfonic acid+4 parts of phosphoric acid, rapidly stirring for 10min, adding into a mold, foaming for 5min at 45 ℃, heating to 80 ℃, and curing for 30min to obtain the biomass-based phenolic resin composite foaming heat-insulating material.
The method for preparing the light phenolic resin heat-insulating material from the siliceous biomass has the advantages of simple process, low cost, small volume density and high compression strength, and can obtain the phenolic resin heat-insulating material with the oxygen index of more than 32%, the compression strength of more than 100kPa and the volume density of less than 40kg/m 3 And phenolic foam materials with heat conductivity lower than 0.038W/(m.K) and high added value, and the phenolic foam materials are compounded with the standard specified by national standard GB/T20974-2007.
Table 1 performance index of example preparation of biomass-based phenolic resin composite foamed insulation material
Claims (8)
1. The method for preparing the light phenolic resin heat-insulating material by using the biomass is characterized by comprising the following steps of:
step one, according to the solid-to-liquid ratio of the dry basis of the siliceous biomass to the sulfuric acid solution of 1kg: (5-10) adding the silicon-containing biomass with the crushed average particle diameter of 10-20 mm into an enamel reaction kettle, spraying and adding sulfuric acid solution with the concentration of 1-3 wt% from above, heating and refluxing for 2-4 hours, extruding and filtering, separating hydrolysate, soaking and washing obtained hydrolysate residues with equal volume of deionized water, extruding for two times to obtain washing residues, and returning the washing water containing dilute sugar acid to an acid preparation process for recycling; concentrating the hydrolysate to obtain xylose solution with the concentration of 10-15 wt% and sending the xylose solution to a furfural workshop to prepare furfural;
step two, according to the solid-to-liquid ratio of the dry washing slag to the sodium hydroxide solution of 1kg: (5-10) L, adding a sodium hydroxide solution with the concentration of 3-8wt% into the washing slag obtained in the step one, uniformly mixing, heating and refluxing for reaction for 2-4 h, cooling, filtering and separating alkali slag to obtain an alkali lignin solution containing sodium silicate, and drying the obtained alkali slag in a rotary furnace; neutralizing the obtained alkali lignin solution containing sodium silicate with sulfuric acid solution with the concentration of 10-15 wt% until the pH value is 10-11 to form alkali lignin solution containing silicic acid aggregate;
step three, placing the dried alkali-soluble slag prepared in the step two into a tube furnace, heating to 500-800 ℃ for treatment for 1h at a heating rate of 10 ℃/min under the protection of nitrogen, cooling to room temperature to obtain porous pyrolytic carbon, and crushing to 10-100 meshes to form porous pyrolytic carbon powder;
step four, adding the porous pyrolytic carbon powder obtained in the step three into the alkali lignin solution containing silicic acid aggregate, which is prepared in the step two and is neutralized to pH=10-11, stirring, adsorbing and coating for 10-20 min, neutralizing with acid to pH=8-8.5, stirring for 30-40 min, filtering and separating the alkali lignin solution, drying a filter cake to prepare porous carbon with silica coated on the surface, and scattering for later use;
regulating the sodium hydroxide content of the alkali lignin solution prepared in the step four to be 3wt%, adding a catalyst sodium thiosulfate accounting for 0.5-3 wt% of the system, adding the catalyst sodium thiosulfate into a hydrothermal reaction kettle, heating to 150-220 ℃, reacting for 10-40 min, cooling and discharging to obtain a degraded alkali lignin phenol solution;
step six, adding the alkali lignin phenol degradation solution, phenol and sodium hydroxide obtained in the step five into a reaction device, heating to 80-100 ℃, and refluxing for 0.5-2 h to obtain a phenolized prepolymerized alkali lignin phenol solution;
the mass of lignin in the alkali lignin degrading phenol solution accounts for 50-100 wt% of the total mass of lignin and phenol, and the mass of sodium hydroxide accounts for 5wt% of the total mass of lignin and phenol; wherein the mass of lignin in the solution of degrading alkali lignin phenol accounts for 100% of the total mass of lignin and phenol, and is lignin phenol completely substituted phenol;
step seven, adding furfural, formaldehyde or mixed solution of furfural and formaldehyde produced in the step one into the phenolized prepolymerized alkali lignin phenol solution obtained in the step six in batches according to the mass ratio, adjusting the system temperature to 60-70 ℃ in the first batch, carrying out addition reaction for 0.5-1.5 h, then heating to 75-90 ℃, adding the rest 20% mixed solution, carrying out constant-temperature reaction for 1-2.5 h, and reducing the temperature to 50-70 ℃; neutralizing with acetic acid to pH=5.5-6.5, and distilling under reduced pressure until the solid content of the solution reaches 70-80 wt%;
the mass ratio of the alkali lignin phenol to the aldehyde is 1:1-2; the mass ratio of the furfural to the formaldehyde in the mixed solution is as follows: 0:100-100: 0;
step eight, mixing 100 parts of phenolic resin prepared in the step seven, 2 parts of surfactant, 5 parts of foaming agent and 1 part of stabilizer glycerol, uniformly stirring, then adding 30-60 parts of porous material, 8 parts of curing agent, rapidly stirring for 10-30 min, adding into a mould, foaming for 5min at 30-50 ℃, heating to 75-85 ℃, and curing for 30-35 min to obtain the biomass-based phenolic resin composite foaming heat-insulating material;
the porous material in the step eight comprises one or a mixture of coal glass floating beads, diatomite, perlite and the porous carbon coated with silicon dioxide prepared in the step four.
2. The method for preparing the light phenolic resin heat-insulating material from the biomass according to claim 1, wherein the method comprises the following steps: the siliceous biomass in the first step comprises one or a combination of more of rice hulls, rice straws, wheat hulls, wheat straws and bamboo branches.
3. The method for preparing the light phenolic resin heat-insulating material from the biomass according to claim 1, wherein the method comprises the following steps: the extrusion filtering method in the first step comprises the following steps: the bottom of the enamel reaction kettle is provided with a filter screen, compressed air or high-pressure steam is introduced above the materials, the hydrolysate is discharged out of the reaction kettle under the action of pressure, and deionized water with the same volume as the hydrolysate slag is added for soaking, extrusion and dehydration for two times.
4. The method for preparing the light phenolic resin heat-insulating material from the biomass according to claim 1, wherein the method comprises the following steps: the method for preparing furfural from the hydrolysate separated in the step one by sending the hydrolysate to a furfural workshop comprises the following steps:
adding 2mol/L sulfuric acid as a catalyst solution into a reactor, introducing nitrogen at 150-200 ℃ into the bottom of the reactor, heating by a nitrogen heater until the catalyst solution flows back, adding promoter sodium chloride to saturation, stirring to form a rotating liquid surface with a fixed concentration of catalyst and promoter, concentrating the hydrolysate to obtain a xylose solution with concentration of 10-15 wt%, spraying the xylose solution into the reactor at the speed of 150-300 mL/min, performing xylose dehydration reaction on the liquid surface layer to generate furfural steam, and condensing by a condenser to obtain the furfural solution.
5. The method for preparing the light phenolic resin heat-insulating material from the biomass according to claim 1, wherein the method comprises the following steps: the surfactant in the eighth step is one or a mixture of more of Tween T-80, SPAN-80 and polyoxyl castor oil.
6. The method for preparing the light phenolic resin heat-insulating material from the biomass according to claim 1, wherein the method comprises the following steps: in the eighth step, the foaming agent is one or a mixture of more than one of n-pentane, n-hexane, methylene dichloride, carbonate, bicarbonate and azo compounds.
7. The method for preparing the light phenolic resin heat-insulating material from the biomass according to claim 1, wherein the method comprises the following steps: and in the eighth step, the curing agent is one or a mixture of more of toluene sulfonic acid, phenol sulfonic acid and phosphoric acid.
8. The method for preparing the light phenolic resin heat-insulating material from the biomass according to claim 1, wherein the method comprises the following steps: in the third step, the dry alkali solution slag is replaced by other light porous biomass, and the other light porous biomass comprises one or a mixture of more of xylose slag, furfural slag, papermaking black liquor lignin and ethanol lignin.
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