CN106635110A - Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues - Google Patents
Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues Download PDFInfo
- Publication number
- CN106635110A CN106635110A CN201610958690.0A CN201610958690A CN106635110A CN 106635110 A CN106635110 A CN 106635110A CN 201610958690 A CN201610958690 A CN 201610958690A CN 106635110 A CN106635110 A CN 106635110A
- Authority
- CN
- China
- Prior art keywords
- thermal cracking
- agriculture
- phenols
- waste material
- organic waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 36
- 150000002989 phenols Chemical class 0.000 title claims abstract description 25
- 239000012263 liquid product Substances 0.000 title claims abstract description 10
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 title abstract description 7
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006555 catalytic reaction Methods 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 40
- 239000010815 organic waste Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 13
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000010504 bond cleavage reaction Methods 0.000 claims description 12
- 230000007017 scission Effects 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229920005610 lignin Polymers 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 150000002366 halogen compounds Chemical class 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 239000002023 wood Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021431 alpha silicon carbide Inorganic materials 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- NNYBQONXHNTVIJ-UHFFFAOYSA-N etodolac Chemical compound C1COC(CC)(CC(O)=O)C2=C1C(C=CC=C1CC)=C1N2 NNYBQONXHNTVIJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003306 harvesting Methods 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229940063718 lodine Drugs 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 claims description 4
- 229910001630 radium chloride Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 3
- CEBDXRXVGUQZJK-UHFFFAOYSA-N 2-methyl-1-benzofuran-7-carboxylic acid Chemical compound C1=CC(C(O)=O)=C2OC(C)=CC2=C1 CEBDXRXVGUQZJK-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- RNIPBGMVTAUWNH-UHFFFAOYSA-N [F].[I] Chemical compound [F].[I] RNIPBGMVTAUWNH-UHFFFAOYSA-N 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229940107816 ammonium iodide Drugs 0.000 claims description 3
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 3
- MZJUGRUTVANEDW-UHFFFAOYSA-N bromine fluoride Chemical compound BrF MZJUGRUTVANEDW-UHFFFAOYSA-N 0.000 claims description 3
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- KNSWNNXPAWSACI-UHFFFAOYSA-N chlorine pentafluoride Chemical compound FCl(F)(F)(F)F KNSWNNXPAWSACI-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- XRURPHMPXJDCOO-UHFFFAOYSA-N iodine heptafluoride Chemical compound FI(F)(F)(F)(F)(F)F XRURPHMPXJDCOO-UHFFFAOYSA-N 0.000 claims description 3
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 claims description 3
- -1 IBr Chemical compound 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 2
- 229910015900 BF3 Inorganic materials 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000002916 wood waste Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 8
- 239000002028 Biomass Substances 0.000 abstract description 6
- 239000007790 solid phase Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 241000218652 Larix Species 0.000 description 2
- 235000005590 Larix decidua Nutrition 0.000 description 2
- 244000204900 Talipariti tiliaceum Species 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- FQFKTKUFHWNTBN-UHFFFAOYSA-N trifluoro-$l^{3}-bromane Chemical compound FBr(F)F FQFKTKUFHWNTBN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- CQKBIUZEUFGQMZ-UHFFFAOYSA-N [Ru].[Au] Chemical compound [Ru].[Au] CQKBIUZEUFGQMZ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003416 augmentation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a method for preparing a liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues and belongs to the technical field of biomass energy. The method is a new method for obtaining the liquid product containing rich phenols and alcohols by organically combining microwave absorbent silicon carbide with a catalytic active metal component and through primary solid-phase microwave catalytic thermal cracking and secondary gas-phase cracking reaction, and resourceful conversion and high-value utilization of the forestry and agricultural residues are promoted.
Description
Technical field
The invention belongs to biomass energy technology field, and in particular to prepared by a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking
Method rich in phenols, alcohol-based liquid product.
Background technology
Agriculture and forestry organic waste material is a kind of important biomass resource, mainly remaining including agricultural crop straw, rice husk, the harvesting of wood
Thing, wood machining residues etc., it is one of study hotspot of field of renewable energy that its energy conversion is utilized.Thermal cracking liquefaction skill
Agriculture and forestry organic waste material can be converted into pyrolysis oil, pyrolytic carbon and pyrolysis gas by art, be important turn of agriculture and forestry organic waste material recycling
Change means.However, traditional thermal-cracking method is due to mainly adopting quartz sand or Ceramic Balls etc. to transfer heat to indirectly for bed
Agriculture and forestry organic waste material particle, causes to exist that heat transfer is uneven, exotherm is serious, thermal cracking liquid yield is low, active principle
The problems such as not being enriched with.And microwave thermal cracking is used as a kind of brand-new mode of heating, due to the unique heat and mass rule of the method
With more preferable heating uniformity so that it also begins to be paid close attention in thermal cracking field.
Patent (CN100999676A, CN100999677A) individually discloses biomass microwave catalytic pyrolysis and prepares rich in third
The method of keto-alcohol bio oil and the method rich in furol biological oil, mainly with carborundum as microwave absorption medium, respectively with carbon
Sour sodium and ferric sulfate are catalyst, are obtained through microwave catalysis thermal cracking.Patent (CN104357071A) discloses a kind of utilization
The method of microwave catalysis pyrolysis biomass orientation production biomass carbon, bio-oil and biogas, main method is by biology
Matter adds catalyst and is well mixed Jing after removal of impurities, broken, drying, then carries out microwave-heating and obtains gaseous product and solid product
Thing, catalyst used is the metal oxide oxidation catalysts such as metal-based catalysts or aluminum oxide, calcium oxide such as sodium carbonate, potassium carbonate
Agent.Patent (CN105295970A) discloses a kind of method of rice straw microwave cracking gas-carbon cogeneration, mainly by rice straw material Jing
Cross after process without catalyst or addition Na2CO3、ZnCl2, a kind of catalyst in CaO, carry out in a nitrogen atmosphere micro-
Ripple is cracked.In sum, in microwave thermal cracking processes, microwave absorption and catalyst are for final product yield and quality
Affect extremely crucial.
Carborundum is a kind of conventional cheap microwave absorption, with anti-oxidant, resistance to elevated temperatures it is good the characteristics of, be a kind of
The suction ripple material of nonreactive activity phase, with catalyst complex can effectively utilizes microwave energy improving catalytic efficiency.Therefore, how
Effective combination of microwave absorption carborundum and catalyst is realized, will for the catalysis orientation conversion of agriculture and forestry organic waste material resource thermal cracking
Have great importance.
The content of the invention
It is an object of the invention to provide prepared by a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking be rich in phenols, alcohol-based liquid
The method of product, to overcome the defect of prior art, the present invention is by by microwave absorption carborundum and catalytically-active metals group
The combination for dividing, and react through a solid phase microwave catalysis thermal cracking and secondary vapor-phase thermal cracking, obtain and be rich in phenols, alcohols
The new method of product liquid, may advantageously facilitate the resourcable transformation and high-value-use of agriculture and forestry organic waste material.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of agriculture and forestry organic waste material microwave catalysis thermal cracking is prepared and is rich in phenols, the method for alcohol-based liquid product, including following
Step：
(1) it is silicon-carbide particle and halogen or halogen compounds or interhalogen compounds is anti-at a temperature of 1000～1800 DEG C
Answer 0.5～3 hour, obtain modified carborundum；Wherein, described silicon-carbide particle is mutually changed with halogen or halogen compounds or halogen
The mol ratio of thing is 1：(0.2～5)；
(2) nitrate of 1 weight portion is dissolved in the absolute ethyl alcohol of 5 weight portions, adds after dissolving in step (1) and obtain
Then the modified carborundum of 1～5 weight portion for arriving, sealing and standing after stirring is evaporated absolute ethyl alcohol using water-bath, then will be steamed
Solid after dry is calcined in air atmosphere, obtains metal oxide supported type catalyst；
(3) chlorate of 1 weight portion is dissolved in the absolute ethyl alcohol of 5 weight portions, adds after dissolving in step (1) and obtain
Then the modified carborundum of 1～5 weight portion for arriving, sealing and standing after stirring is evaporated absolute ethyl alcohol using water-bath, then will be steamed
Solid after dry is calcined in air atmosphere, and the solid after calcining is reduced in the mixed gas of hydrogen and nitrogen, after reduction
To metal simple-substance loaded catalyst；
(4) by the metal oxide supported type of 2～10 weight portions in 10 weight portion agriculture and forestry organic waste material particles and step (2)
Catalyst mixes, and in microwave action heat cracking reaction is issued, and generates the thermal cracking steam for carrying lignin oligomer；
(5) metal simple-substance for carrying 1～5 weight portion of the thermal cracking steam of lignin oligomer in step (3) is born
Supported catalyst carries out secondary gas phase microwave catalysis reaction, and quadric catalysis cracked vapors are generated after reaction；
(6) quadric catalysis cracked vapors are condensed under 0～5 DEG C of condensation temperature, collect condensed fluid, as rich in phenols,
Alcohol-based liquid product.
Further, the silicon-carbide particle described in step (1) be industrial carborundum, nanometer silicon carbide, alpha-silicon carbide or
Silicon B-carbide, particle size range is 10 μm～500 μm.
Further, the halogen described in step (1) is one or more mixing in fluorine, chlorine, bromine, iodine, described halogen
Plain compound is the one kind in hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, institute
The interhalogen compounds stated be fluorine iodine, bromine fluoride, chlorine fluoride, lodine chloride, bromine chloride, IBr, iodine triflouride, bromine trifluoride,
One kind in chlorine trifluoride, iodine pentafluoride, BPF, chlorine pentafluoride, iodine heptafluoride.
Further, mixing time is 30～60 minutes in step (2) and step (3), and the sealing and standing time is 12
～24 hours, bath temperature was 50～70 DEG C.
Further, step (2) and the temperature of the middle calcining of step (3) are 600～800 DEG C, and the time is 3～6 hours.
Further, the nitrate described in step (2) is the one kind in nickel nitrate, ferric nitrate, calcium nitrate, copper nitrate.
Further, the chlorate described in step (3) is the one kind in palladium bichloride, ruthenic chloride, radium chloride, cobalt chloride.
Further, hydrogen and nitrogen mixed gas flow are 100～500mL/min, hydrogen and nitrogen in step (3)
Product is than being 1:2, reduction temperature is 200～400 DEG C, and the recovery time is 1～3 hour.
Further, microwave frequency is 2.45GHz in step (4) and step (5), and microwave power is 0.01～
1600W, the reaction time is 5～20 minutes；In step (4) heat scission reaction atmosphere be nitrogen, nitrogen flow be 50～
200mL/min。
Further, the agriculture and forestry organic waste material described in step (4) adds for agricultural crop straw, harvesting of wood residue or timber
Work residue, particle diameter be 0.1mm～2.0mm, moisture content≤12%.
Compared with prior art, the present invention has following beneficial technique effect：
Agriculture and forestry organic waste material microwave catalysis thermal cracking proposed by the present invention is prepared and is rich in phenols, the method for alcohol-based liquid product,
Be favorably improved the value of agriculture and forestry organic waste material, turn waste into wealth, and be obtain from agriculture and forestry organic waste material renewable phenols and
Alcohols high value chemical products or chemical intermediate provide new approach, and concrete advantage is as follows：
(1) traditional industry carborundum is due to specific surface area very little, and is unsuitable for the carrier as catalyst, and the present invention is logical
Surface high-temp carbonization treatment is crossed, the element silicon of silicon carbide is removed, the flourishing carbon-coating material of hole is left, is become good
Catalyst carrier, has been effectively maintained carborundum as the function of microwave absorption again.
(2) present invention carries out traditional microwave absorption after surface carbonation modification, is prepared for fitting by infusion process
For the metal load type catalyst of agriculture and forestry organic waste material thermal cracking.On the one hand the catalyst still possesses the function of microwave absorption,
Can augmentation of heat transfer, promote the fast charring of agriculture and forestry organic waste material, the agriculture and forestry organic waste material after charing itself is also with very strong suction ripple
Ability, so as to thermal cracking efficiency is greatly improved；On the other hand, the catalytic active component of the catalyst surface load can have
Effect promotes the controllable orientation conversion of three big component fibre elements, hemicellulose and lignin in agriculture and forestry organic waste material.
(3) present invention is prepared for respectively metal oxide supported type catalyst and metal simple-substance loaded catalyst, passes through
The mode of two-stage catalytic obtains the high value product liquid rich in phenols, alcohols；First paragraph is urged for metal oxide supported type
Agent directly mixes with solid-state agriculture and forestry organic waste material, and this catalysis can realize the cellulose and half for being easy to be pyrolyzed in agriculture and forestry organic waste material
Effective catalysis of cellulose generates the product based on alcohols, and metal oxide is difficult coking as active component；Second segment
For metal simple-substance loaded catalyst catalytic pyrolysis steam, it is mainly used in the lignin oligomer to carrying in thermal cracking steam
(pyrolysis lignin) carries out quadric catalysis conversion, so that it is converted into valuable micromolecule phenolic；Therefore, this two class
Catalyst and two-part reaction each have unique catalysis.
Description of the drawings
Fig. 1 is the FB(flow block) of the present invention.
Specific embodiment
Embodiments of the present invention are described in further detail below in conjunction with the accompanying drawings：
Referring to Fig. 1, agriculture and forestry organic waste material microwave catalysis thermal cracking proposed by the present invention is prepared and is rich in phenols, alcohol-based liquid product
Method, comprise the steps：
(1) silicon-carbide particle reacts with halogen or halogen compounds or interhalogen compounds under 1000～1800 DEG C of high temperature
0.5～3 hour, obtain modified carborundum；Wherein, described carborundum and halogen or halogen compounds or interhalogen compounds rub
You are than being 1：(0.2～5)；The carborundum that described silicon-carbide particle is obtained for various forms, including industrial carborundum, nano-sized carbon
SiClx, alpha-silicon carbide, silicon B-carbide etc., particle size range is 10 μm～500 μm；Described halogen is in fluorine, chlorine, bromine, iodine
Plant or various mixing, described halogen compounds is hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, ammonium fluoride, ammonium chloride, bromination
One kind in ammonium, ammonium iodide, described interhalogen compounds is fluorine iodine, bromine fluoride, chlorine fluoride, lodine chloride, bromine chloride, bromination
One kind in iodine, iodine triflouride, bromine trifluoride, chlorine trifluoride, iodine pentafluoride, BPF, chlorine pentafluoride, iodine heptafluoride.
(2) nitrate of 1 weight portion is dissolved in the absolute ethyl alcohol of 5 weight portions, adds after dissolving in step (1) and obtain
The modified carborundum of (1～5) weight portion for arriving, is stirred continuously 30～60 minutes, sealing and standing 12～24 hours, at 50～70 DEG C
Absolute ethyl alcohol is evaporated in water-bath, then by the solid after being evaporated in air atmosphere, 600～800 DEG C calcine 3～6 hours, obtain
To metal oxide supported type catalyst；Wherein, described nitrate is in nickel nitrate, ferric nitrate, calcium nitrate, copper nitrate
Kind.
(3) chlorate of 1 weight portion is dissolved in the absolute ethyl alcohol of 5 weight portions, adds after dissolving in step (1) and obtain
The modified carborundum of (1～5) weight portion for arriving, is stirred continuously 30～60 minutes, sealing and standing 12～24 hours, at 50～70 DEG C
Absolute ethyl alcohol is evaporated in water-bath, then by the solid after being evaporated in air atmosphere, 600～800 DEG C calcine 3～6 hours, forge
Solid after burning is reduced in the mixed gas of hydrogen and nitrogen, and reduction temperature is 200～400 DEG C, and the recovery time is 1～3 little
When, metal simple-substance loaded catalyst is obtained after reduction；Wherein, described chlorate is palladium bichloride, ruthenic chloride, radium chloride, chlorine
Change the one kind in cobalt, described hydrogen and nitrogen mixed gas flow is 100～500mL/min, and hydrogen and nitrogen volume ratio are
1:2。
(4) by the metal oxide supported of (2～10) weight portion in 10 weight portion agriculture and forestry organic waste material particles and step (2)
Type catalyst mixes, and in microwave action heat cracking reaction is issued, and microwave frequency is 2.45GHz, and microwave power is 0.01～
1600W continuously adjustabes, the reaction time is 5～20 minutes, and heat scission reaction atmosphere is nitrogen, and nitrogen flow is 50～200mL/
min；Heat scission reaction generates the thermal cracking steam for carrying lignin oligomer；Wherein, described agriculture and forestry organic waste material is crops
Stalk, harvesting of wood residue, wood machining residues etc., particle diameter be 0.1mm～2.0mm, moisture content≤12%.
(5) metal simple-substance of (1～5) weight portion of the thermal cracking steam of lignin oligomer in step (3) is carried
Loaded catalyst carries out secondary gas phase microwave catalysis reaction, and the conditional synchronization of microwave catalysis reaction is rapid (4), and two are generated after reaction
Secondary catalytic cracking steam.
(6) quadric catalysis cracked vapors rapid condensation under 0～5 DEG C of condensation temperature, collects condensed fluid, as rich in phenol
Class, alcohol-based liquid product.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
With particle diameter as 0.1mm～the larch sawdust (moisture content is 10%) of the 0.45mm, work that particle diameter is 10 μm～100 μm
The implementation process that the present invention is introduced as a example by industry carborundum is as follows：
1 mole of industrial silicon-carbide particle and 5 moles of chlorine are reacted 2 hours at 1000 DEG C, modified carbonization is obtained
Silicon.The nickel nitrate of 10g is dissolved in the absolute ethyl alcohol of 50g, the modified carborundum of 10g is subsequently adding, is stirred continuously 30 minutes, it is close
After envelope stands 12 hours, be evaporated in 50 DEG C of water-baths, then by the solid after being evaporated in air atmosphere, 600 DEG C of calcinings it is 6 little
When, obtain nickel oxide loaded type catalyst.The palladium bichloride of 10g is dissolved in the absolute ethyl alcohol of 50g, 10g is subsequently adding and is modified
Carborundum, is stirred continuously 30 minutes, and sealing and standing was evaporated absolute ethyl alcohol in 50 DEG C of water-baths after 12 hours, then will be evaporated
Solid afterwards in air atmosphere, 600 DEG C calcine 6 hours, the solid after calcining volume ratio be 1:2nd, flow is 100mL/min
Hydrogen and nitrogen mixed gas in reduce, reduction temperature be 400 DEG C, the recovery time be 1 hour, palladium metal is obtained after reduction
Loaded catalyst.10g larches sawdust is mixed with the nickel oxide loaded type catalyst of 2g, in microwave action heat cracking is issued
Reaction, microwave frequency is 2.45GHz, and microwave power is 800W, and the reaction time is 5 minutes, and heat scission reaction atmosphere is nitrogen, nitrogen
Throughput is 50mL/min；Heat scission reaction generates one-level thermal cracking steam, then through the palladium metal loaded catalyst of 1g
Secondary gas phase microwave catalysis reaction is carried out, quadric catalysis cracked vapors are generated, the rapid condensation under 5 DEG C of condensation temperatures is collected cold
Lime set body, condensed fluid constituent analysis is shown in Table 1.
Embodiment 2
With particle diameter as 0.45mm～maize straw (moisture content is 8%) of the 0.9mm, nanometer that particle diameter is 100 μm～200 μm
The implementation process that the present invention is introduced as a example by carborundum is as follows：
1 mole of nanometer silicon carbide and 0.2 mole of hydrogen fluoride are reacted 1.5 hours at 1200 DEG C, carbon modified is obtained
SiClx.The ferric nitrate of 10g is dissolved in the absolute ethyl alcohol of 50g, the modified carborundum of 12g is subsequently adding, is stirred continuously 45 minutes,
After sealing and standing 20 hours, be evaporated in 55 DEG C of water-baths, then by the solid after being evaporated in air atmosphere, 650 DEG C of calcinings it is 4 little
When, obtain iron oxide loaded catalyst.The ruthenic chloride of 10g is dissolved in the absolute ethyl alcohol of 50g, 12g is subsequently adding and is modified
Carborundum, is stirred continuously 40 minutes, and sealing and standing was evaporated absolute ethyl alcohol in 70 DEG C of water-baths after 15 hours, then will be evaporated
Solid afterwards in air atmosphere, 800 DEG C calcine 4 hours, the solid after calcining volume ratio be 1:2nd, flow is 300mL/min
Hydrogen and nitrogen mixed gas in reduce, reduction temperature be 350 DEG C, the recovery time be 1.5 hours, obtain after reduction ruthenium gold
Category loaded catalyst.10g corn stalk raw materials are mixed with 5g iron oxide loaded catalysts, in microwave action heat is issued
Cracking reaction, microwave frequency is 2.45GHz, and microwave power is 600W, and the reaction time is 10 minutes, and heat scission reaction atmosphere is nitrogen
Gas, nitrogen flow is 100mL/min；Heat scission reaction generates one-level thermal cracking steam, then through the ruthenium metal load type of 3g
Catalyst carries out secondary gas phase microwave catalysis and reacts, generation quadric catalysis cracked vapors, the rapid condensation under 2 DEG C of condensation temperatures,
Condensed fluid is collected, condensed fluid constituent analysis is shown in Table 1.
Embodiment 3
With particle diameter as 0.9mm～wheat stalk (moisture content is 6%) of 1.2mm, α-carbon that particle diameter is 250 μm～350 μm
The implementation process that the present invention is introduced as a example by SiClx is as follows：
1 mole of alpha-silicon carbide and 3 moles of ammonium bromide are reacted 0.5 hour at 1800 DEG C, modified carborundum is obtained.
The calcium nitrate of 10g is dissolved in the absolute ethyl alcohol of 50g, the modified carborundum of 50g is subsequently adding, is stirred continuously 60 minutes, sealed
After standing 24 hours, be evaporated in 70 DEG C of water-baths, then by the solid after being evaporated in air atmosphere, 800 DEG C of calcinings it is 3.5 little
When, obtain calcium oxide loaded catalyst.The radium chloride of 10g is dissolved in the absolute ethyl alcohol of 50g, 50g is subsequently adding and is modified
Carborundum, is stirred continuously 60 minutes, and sealing and standing was evaporated absolute ethyl alcohol in 70 DEG C of water-baths after 24 hours, then will be evaporated
Solid afterwards in air atmosphere, 800 DEG C calcine 4 hours, the solid after calcining volume ratio be 1:2nd, flow is 500mL/min
Hydrogen and nitrogen mixed gas in reduce, reduction temperature be 200 DEG C, the recovery time be 3 hours, rhodium metal is obtained after reduction
Loaded catalyst.10g wheat stalks raw material is mixed with 10g calcium oxide loaded catalysts, in microwave action heat is issued
Cracking reaction, microwave frequency is 2.45GHz, and microwave power is 1600W, and the reaction time is 15 minutes, and heat scission reaction atmosphere is
Nitrogen, nitrogen flow is 200mL/min；Heat scission reaction generates one-level thermal cracking steam, and then the rhodium metal through 5g is loaded
Type catalyst carries out secondary gas phase microwave catalysis reaction, generates quadric catalysis cracked vapors, the fast quickly cooling under 0 DEG C of condensation temperature
It is solidifying, condensed fluid is collected, condensed fluid constituent analysis is shown in Table 1.
Embodiment 4
With particle diameter as 1.2mm～the cotton wood particle (moisture content is 4%) of 2.0mm, particle diameter be 350 μm～500 μm
The implementation process that the present invention is introduced as a example by silicon B-carbide is as follows：
1 mole of silicon B-carbide and 4 moles of lodine chloride are reacted 3 hours at 1600 DEG C, modified carborundum is obtained.Will
The copper nitrate of 10g is dissolved in the absolute ethyl alcohol of 50g, is subsequently adding the modified carborundum of 15g, is stirred continuously 50 minutes, is sealed quiet
After putting 16 hours, be evaporated in 65 DEG C of water-baths, then by the solid after being evaporated in air atmosphere, 700 DEG C calcine 3 hours, obtain
To cupric oxide loaded catalyst.The cobalt chloride of 10g is dissolved in the absolute ethyl alcohol of 50g, the modified carbonizations of 15g are subsequently adding
Silicon, is stirred continuously 50 minutes, and sealing and standing was evaporated absolute ethyl alcohol in 65 DEG C of water-baths after 16 hours, after being then evaporated
Solid in air atmosphere, 700 DEG C calcine 3 hours, the solid after calcining volume ratio be 1:2nd, flow is the hydrogen of 400mL/min
Reduce in the mixed gas of gas and nitrogen, reduction temperature is 280 DEG C, and the recovery time is 2 hours, and cobalt Metal Supported is obtained after reduction
Type catalyst.10g cotton woods particulate material is mixed with 6g cupric oxide loaded catalysts, heat is issued in microwave action and is split
Solution reaction, microwave frequency is 2.45GHz, and microwave power is 1400W, and the reaction time is 20 minutes, and heat scission reaction atmosphere is nitrogen
Gas, nitrogen flow is 150mL/min；Heat scission reaction generates one-level thermal cracking steam, then through the cobalt metal load type of 2g
Catalyst carries out secondary gas phase microwave catalysis and reacts, generation quadric catalysis cracked vapors, the rapid condensation under 3 DEG C of condensation temperatures,
Condensed fluid is collected, condensed fluid constituent analysis is shown in Table 1.
The product liquid chemical composition analysis of table 1
Claims (10)
1. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking is prepared and is rich in phenols, the method for alcohol-based liquid product, it is characterised in that
Comprise the following steps：
(1) silicon-carbide particle is reacted with halogen or halogen compounds or interhalogen compounds at a temperature of 1000～1800 DEG C
0.5～3 hour, obtain modified carborundum；Wherein, described silicon-carbide particle and halogen or halogen compounds or interhalogen compounds
Mol ratio be 1：(0.2～5)；
(2) nitrate of 1 weight portion is dissolved in the absolute ethyl alcohol of 5 weight portions, adds what is obtained in step (1) after dissolving
Then the modified carborundum of 1～5 weight portion, sealing and standing after stirring is evaporated absolute ethyl alcohol using water-bath, after being then evaporated
Solid calcine in air atmosphere, obtain metal oxide supported type catalyst；
(3) chlorate of 1 weight portion is dissolved in the absolute ethyl alcohol of 5 weight portions, adds what is obtained in step (1) after dissolving
Then the modified carborundum of 1～5 weight portion, sealing and standing after stirring is evaporated absolute ethyl alcohol using water-bath, after being then evaporated
Solid calcine in air atmosphere, the solid after calcining is reduced in the mixed gas of hydrogen and nitrogen, and gold is obtained after reduction
Category simple substance loaded catalyst；
(4) by the metal oxide supported type catalysis of 2～10 weight portions in 10 weight portion agriculture and forestry organic waste material particles and step (2)
Agent mixes, and in microwave action heat cracking reaction is issued, and generates the thermal cracking steam for carrying lignin oligomer；
(5) the metal simple-substance support type of 1～5 weight portion of the thermal cracking steam of lignin oligomer in step (3) is carried
Catalyst carries out secondary gas phase microwave catalysis reaction, and quadric catalysis cracked vapors are generated after reaction；
(6) quadric catalysis cracked vapors are condensed under 0～5 DEG C of condensation temperature, condensed fluid are collected, as rich in phenols, alcohols
Product liquid.
2. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that the silicon-carbide particle described in step (1) is industrial carborundum, nanometer silicon carbide, alpha-silicon carbide
Or silicon B-carbide, particle size range is 10 μm～500 μm.
3. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that the halogen described in step (1) is one or more mixing in fluorine, chlorine, bromine, iodine, described
Halogen compounds is the one kind in hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide,
Described interhalogen compounds is fluorine iodine, bromine fluoride, chlorine fluoride, lodine chloride, bromine chloride, IBr, iodine triflouride, borontrifluoride
One kind in bromine, chlorine trifluoride, iodine pentafluoride, BPF, chlorine pentafluoride, iodine heptafluoride.
4. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that mixing time is 30～60 minutes in step (2) and step (3), and the sealing and standing time is
12～24 hours, bath temperature was 50～70 DEG C.
5. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that the temperature of calcining is 600～800 DEG C in step (2) and step (3), and it is little that the time is 3～6
When.
6. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that the nitrate described in step (2) is in nickel nitrate, ferric nitrate, calcium nitrate, copper nitrate
Kind.
7. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that the chlorate described in step (3) is in palladium bichloride, ruthenic chloride, radium chloride, cobalt chloride
Kind.
8. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that hydrogen and nitrogen mixed gas flow are 100～500mL/min, hydrogen and nitrogen in step (3)
Air volume ratio is 1:2, reduction temperature is 200～400 DEG C, and the recovery time is 1～3 hour.
9. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that microwave frequency is 2.45GHz in step (4) and step (5), microwave power is 0.01～
1600W, the reaction time is 5～20 minutes；In step (4) heat scission reaction atmosphere be nitrogen, nitrogen flow be 50～
200mL/min。
10. a kind of agriculture and forestry organic waste material microwave catalysis thermal cracking according to claim 1 is prepared and produced rich in phenols, alcohol-based liquid
The method of thing, it is characterised in that the agriculture and forestry organic waste material described in step (4) is agricultural crop straw, harvesting of wood residue or wood
Material industrial wood waste, particle diameter be 0.1mm～2.0mm, moisture content≤12%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999676A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis |
| WO2010033512A1 (en) * | 2008-09-16 | 2010-03-25 | Regents Of The University Of Minnesota | Improved process for preparing bio-oils from biomass |
| CN104258866A (en) * | 2014-10-13 | 2015-01-07 | 河北科技大学 | Preparation method and application of microwave catalyst |
| CN105038837A (en) * | 2015-07-24 | 2015-11-11 | 南昌大学 | Method for preparing hydrocarbon fuel through rapeseed oil residues |
-
2016
- 2016-10-27 CN CN201610958690.0A patent/CN106635110B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999676A (en) * | 2006-12-31 | 2007-07-18 | 安徽理工大学 | Process of preparing rich acetone alcohol biological oil by biomass microwave catalytic pyrolysis |
| WO2010033512A1 (en) * | 2008-09-16 | 2010-03-25 | Regents Of The University Of Minnesota | Improved process for preparing bio-oils from biomass |
| CN104258866A (en) * | 2014-10-13 | 2015-01-07 | 河北科技大学 | Preparation method and application of microwave catalyst |
| CN105038837A (en) * | 2015-07-24 | 2015-11-11 | 南昌大学 | Method for preparing hydrocarbon fuel through rapeseed oil residues |
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|---|---|---|---|---|
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| CN112604702A (en) * | 2020-12-10 | 2021-04-06 | 南昌大学 | Preparation method and application of microwave-driven catalyst |
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| CN113457576A (en) * | 2021-06-07 | 2021-10-01 | 东南大学 | Waste plastic melting continuous feeding coupling microwave pyrolysis system and method |
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