CN107099051A - A kind of processing method of waste resin catalytic pyrolysis oxidation - Google Patents
A kind of processing method of waste resin catalytic pyrolysis oxidation Download PDFInfo
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- CN107099051A CN107099051A CN201710391106.2A CN201710391106A CN107099051A CN 107099051 A CN107099051 A CN 107099051A CN 201710391106 A CN201710391106 A CN 201710391106A CN 107099051 A CN107099051 A CN 107099051A
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- China
- Prior art keywords
- resin
- catalyst
- waste resin
- waste
- catalytic pyrolysis
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- 239000011347 resin Substances 0.000 title claims abstract description 125
- 229920005989 resin Polymers 0.000 title claims abstract description 125
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 51
- 230000003647 oxidation Effects 0.000 title claims abstract description 40
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 24
- 238000003672 processing method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 139
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910001868 water Inorganic materials 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000012530 fluid Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 15
- 238000005336 cracking Methods 0.000 claims abstract description 6
- 230000008878 coupling Effects 0.000 claims abstract description 5
- 238000010168 coupling process Methods 0.000 claims abstract description 5
- 238000005859 coupling reaction Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 238000005096 rolling process Methods 0.000 claims description 23
- 239000003456 ion exchange resin Substances 0.000 claims description 12
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 12
- 238000001694 spray drying Methods 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- -1 phenolic aldehyde Chemical class 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 2
- 235000011941 Tilia x europaea Nutrition 0.000 claims 2
- 239000004571 lime Substances 0.000 claims 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 229920005990 polystyrene resin Polymers 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 2
- 210000003296 saliva Anatomy 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 34
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 26
- 239000002131 composite material Substances 0.000 description 22
- 238000001035 drying Methods 0.000 description 22
- 239000007921 spray Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 229910002651 NO3 Inorganic materials 0.000 description 16
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 238000007493 shaping process Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000004231 fluid catalytic cracking Methods 0.000 description 11
- 238000011068 loading method Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 6
- CYWFSMVOKXDHCX-UHFFFAOYSA-N C(=C)C1=C(C=CC=C1)C=C.ClC=CC1=CC=CC=C1 Chemical compound C(=C)C1=C(C=CC=C1)C=C.ClC=CC1=CC=CC=C1 CYWFSMVOKXDHCX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229960004424 carbon dioxide Drugs 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 2
- 229910019020 PtO2 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical group O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 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
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of processing method of waste resin catalytic pyrolysis oxidation, in the system that fluid bed is connected with fixed bed reactors, the purified treatment of waste resin is realized using the method for waste resin cracking and oxidation coupling.In 0.1~0.25MPa absolute pressures, reaction temperature is 250~450 DEG C, and waste resin feed rate is 0.05~0.5kg/ (kgCat, fluid bedH), the feed rate of water is 5~15 times of spent resin feed rate, and air mass flow is 720~2500L/ (kgCat, fluid bedH), in fixed bed reactors reaction temperature under 200~400 DEG C of reaction condition, the saliva that goes out after catalytic purification reaches country《Integrated wastewater discharge standard》VOCs contents in (GB8978~96) first discharge standard, incoagulability tail gas reach emission request.The catalyst of the present invention can realize the degradable of spent resin at a lower temperature.Present invention process is simple, mild condition, it is easy to accomplish.
Description
Technical field
The present invention relates to a kind of processing method of waste resin catalytic pyrolysis oxidation, category trade waste treatment technology neck
Domain.
Background technology
With the development and the progress of technology of society, ion exchange resin is in water process, food industry and pharmaceutical industry etc.
Field is widely used, but has large quantities of discarded ion exchange resin to produce every year thereupon.Discarded ion exchange
Resin belongs to solid hazardous waste, and country has strict regulation to its disposal options.Once it is mishandling to its, be to environment
When and it is potentially hazardous very big, severe contamination may be caused to the soil, water source, air on disposal ground.Domestic current solid danger
Dangerous offal treatment ability wretched insufficiency, and processing cost is high.Part producer is caused not appoint discarded ion exchange resin
Where is managed, and is directly discarded in soot, endangers environment.
At present, waste resin oxidation Decomposition technique has dry oxidation (burning), hydrogen peroxide wet oxidation, microbiological oxidation
The methods such as edman degradation Edman, plasma oxidation.
The A of CN 102230628 are burned after discarded ion exchange resin is mixed with raw coal.Discarded ion exchange resin incorporation
Ratio in raw coal is controlled within 10%, boiler powder and powder feeding temperature no more than 200 DEG C, burner hearth central temperature 1100~
More than 1200 DEG C, ion exchange resin is discarded before incorporation raw coal combustion, should be air-dried more than first quarter moon, anionic ion-exchange resins
Should also be by regenerating transformed for OH-Type.The A of CN 105546552, will by adjusting excess air coefficient using adiabatic furnace wall structure
Flue-gas temperature is adjusted to 1100~1200 DEG C, efficient removal bioxin, while using SNCR (SNCR) denitration
Technique, ammoniacal liquor is injected directly into flue gas, and ammoniacal liquor is heated to produce a large amount of ammonia reducing agents, and nitrogen oxides (NOx) is reduced into nitrogen
Gas and water, denitration efficiency are higher.Burning method generally comprises waste pre-treatment, burning and the part of gas cleaning three, each several part technique
Parameter request is high, and pretreating process is complicated, and cost is high, and fire box temperature is more than 1100~1200 DEG C, and power consumption is big.
Anion exchange resin and a certain amount of Fe that the A of patent CN 103366850 will be swelled after acidifying2+And Ce3+Put simultaneously
Stirred in reactor, reaction temperature is 80~99 DEG C, while H2O2Reactor, course of reaction relaying are added dropwise to given pace
It is continuous that Fe is added dropwise2+And Ce3+Solution, by reacting the oxidative free radical (such as OH) produced by anion exchange resin oxidation point
Solution.It is up to 99% that this method resin decomposition rate, which reaches as high as 100%, TOC clearances,.But this method need to use it is substantial amounts of
Organic acid solvent and hydrogen peroxide, the waste water that reaction is generated are high saliferous without machine residue, it is necessary to which further purification could qualified discharge.
The A of patent CN 105861320 employ microbial degradation method.But the method can only be to the structure of ion exchange resin
Destroyed, it is impossible to which resin is degraded into inorganic molecules.
The A of patent CN 102723117 use plasma oxidation technical finesse waste resin, first by waste resin at 1300 DEG C
At a temperature of heated, after in waste resin organic principle decompose generation imflammable gas after, pass through plasma high-temperature oxygen
Change is handled, and ignition temperature needs to reach 1100~1200 DEG C.The method needs at high temperature to pre-process waste resin, energy consumption compared with
It is high.
The content of the invention
The present invention relates to a kind of processing method of waste resin catalytic pyrolysis, and in particular to following steps：
A kind of processing method of waste resin catalytic pyrolysis oxidation, it is characterised in that：This method comprises the following steps：
(1) waste resin after crushing is added water carry out decentralized processing, obtains the waste resin suspension with mobility；
(2) the waste resin suspension and air of step (1) are added in fluidized-bed reactor simultaneously, in catalyst
Under effect, waste resin carries out catalytic pyrolysis oxidation reaction, obtains the gas after pyrolysis oxidization；
(3) gas after step (2) pyrolysis oxidization is delivered into the fixed bed reactors connected with fluidized-bed reactor
Middle carry out catalyst combustion reaction, makes the organic molecule content in gas be reduced to 40mg/m3Below；
(4) gas of step (3) fixed bed reactors outlet is cooled down after heat exchanger reclaims heat by condenser
It is used for the scattered of waste resin to condensate liquid, tail gas is directly emptied after alkali liquor absorption.
In technical solution of the present invention：Described waste resin refers to that can not regenerate the ion without metallic element used hands over
Resin is changed, preferably described waste resin is phenylethylene resin series, acrylic resin, phenolic aldehyde system resin, epoxy system resin, second
One or more in annulated pyridine system resin and ureaformaldehyde system resin.
In technical solution of the present invention：Waste resin particle diameter after crushing is less than or equal to 40 microns；In waste resin suspension
The quality of water and waste resin is 5~15：1.
In technical solution of the present invention：In step (2) fluidized-bed reactor, in the presence of oxygen atmosphere and catalyst, discard
The coupling of cracking and oxidation occurs for resin, and dioxy is oxidized to while resin is cracked into low molecule amount organic molecule
Change the inorganic molecules such as carbon, water vapour.
In technical solution of the present invention：Organic molecule in step (3) is the organic molecule that molecular weight is 16~300.
In technical solution of the present invention：The catalytic pyrolysis oxidation reaction condition of waste resin in step (2) fluidized-bed reactor
It is that absolute pressure is 0.1~0.25MPa, reaction temperature is 250~450 DEG C.
In technical solution of the present invention：The feed rate of step (2) waste resin is 0.05~0.5kg/ (kgcatFluid bed·
H), air mass flow is 720~2500L/ (kgcatFluid bed·h)。
In technical solution of the present invention：200~400 DEG C of reaction temperature in fixed bed reactors.
In technical solution of the present invention：COD in step (4) condensate liquid is less than or equal to 80mg/L, and tail gas passes through alkali liquor absorption
Afterwards, the content of the volatile organic compound in emptying gas is less than or equal to 40mg/m3。
In technical solution of the present invention：The catalyst of step (2) and step (3) is specially O composite metallic oxide catalyst,
The active component of catalyst is one or both of copper, iron, cobalt, nickel, ruthenium, cerium, lanthanum, platinum, titanium, palladium, yttrium, manganese, active component
Oxide form in the catalyst is present.The loadings of catalyst reactor press air total air speed in a fluidized bed reactor
For 400~2400L/ (kgCat, fluid bedH) count.Activearm in step (2) and step (3) preferred steps (2) and step (3) carrier
Sub-oxide load capacity is 10~20%.
In technical solution of the present invention：Step (2) catalytic pyrolysis oxidation reaction is that waste resin is organic small by catalytic pyrolysis
The inorganic molecules such as carbon dioxide, water vapour are catalytically oxidized to after molecule again, the heat discharged is aoxidized and is carried for resin cracking
While energy supply amount, make the water vapor in suspension and take away unnecessary heat, to maintain heat balance in fluidized-bed reactor.
In technical solution of the present invention：The calorific value of described waste resin reaches 2000~45000kJ/kg, anti-in fluid bed
Answer in device, in the presence of oxygen atmosphere and catalyst, the coupling of cracking and oxidation occurs for waste resin, is cracked into resin
The inorganic molecules such as carbon dioxide, water vapour are oxidized to while low molecule amount organic molecule；When resin cracks what is formed
Low molecule amount organic molecule is in oxidation, and the heat discharged provides energy for the cracking of resin again, and unnecessary heat is also needed
Remove reactor.Therefore, waste resin is carried out decentralized processing by proposition of the present invention with water, on the one hand can increase waste resin
Mobility, convenient charging, on the other hand because the latent heat of vaporization of water is about 2260kJ/kg, therefore will using the vaporization of water
The unnecessary heat produced during spent resin catalysis oxidation removes reactor, the temperature in reactor is maintained suitable scope
It is interior, to reach the purpose of reactor stable operation.Heretofore described organic molecule, it is 16~300 to refer to molecular weight
Organic molecule.
For containing only carbon, hydrogen, oxygen element resin, the inorganic molecules formed after pyrolysis oxidization be carbon dioxide and
Water；And for containing chlorine element, nitrogen or element sulphur resin, except forming inorganic molecules two after pyrolysis oxidization
Beyond carbonoxide and water, hydrogen chloride, chlorine, nitrogen oxides or sulfur dioxide inorganic molecules, these inorganic molecules are also formed
Need to use alkali liquor absorption.After alkali liquor absorption, hydrogen chloride, chlorine, nitrogen oxides and sulfur dioxide in vent gas
Content is no more than 50mg/m3, waste gas emission standard is reached, can directly be discharged without further processing, a step can be achieved with
The deep purifying of waste resin, can greatly reduce equipment investment at a lower temperature, reduce fuel consumption, cost-effective.
In technical solution of the present invention：The carrier of fluid bed used catalyst is molecular sieve, such as ZSM-5, MCM-41, Y molecule
Any of sieve, ReY molecular sieves；Carrier used in fixed-bed catalytic combustion catalyst is Al2O3、SiO2, in atlapulgite
It is any.Fluid bed is 1~20% with load capacity of the active component oxide on carrier in fixed bed catalyst.
In technical solution of the present invention：The particle diameter of fluid bed used catalyst is 60~200 μm, the particle diameter of fixed bed catalyst
For 2~4mm.
The technique effect of the present invention is as follows：
The present invention is directed to the discarded ion exchange resin produced in industrial production, is connected in fluid bed with fixed bed reactors
System in, the purified treatment that waste resin is realized with the method for oxidation coupling is cracked using waste resin, can be real at low temperature
Now to discarding the processing of ion exchange resin, while the heat discharged when organic matter is purified using the vaporization of water removes reaction
Device, realizes efficient, low cost, the processing waste resin of low energy consumption.
Brief description of the drawings
Fig. 1 is the process chart for the processing method that waste resin catalytic pyrolysis of the present invention is aoxidized.
Embodiment
Below in conjunction with the accompanying drawings, the present invention is described in further detail.
As illustrated, the technological process of processing is：Spent resin suspension is added at the top of fluidized-bed reactor, while in fluidisation
Bed reactor bottom is passed through air, and in a fluidized bed reactor in the presence of catalyst, most of organic matter is by catalytic pyrolysis oxygen
Carbon dioxide and water vapour are melted into, also has the micro small molecule not being cleaned organic in the gas in fluidized-bed reactor exit
Thing, burning is further catalyzed into the fixed bed reactors connected with fluidized-bed reactor.By fluidized-bed reactor and fixation
The joint catalytic purification of bed reactor, the gas in fixed bed reactors exit exchanges heat by heat exchanger to be cooled down in obtained liquid
COD be no more than 80mgO2/ L, in the preparation for being circularly used for waste resin suspension, tail gas is after alkali liquor absorption, air-discharging
The content of VOCs (volatile organic compound) in body is no more than 40mg/m3, hydrogen chloride, chlorine, sulfur dioxide and nitrogen oxides
Content be no more than 50mg/m3, can directly empty.
Fluid catalytic cracking oxidation catalyst used in the present invention is made using spray drying process, preparation method：Will
The presoma (nitrate) of active component is soluble in water, and support powder is impregnated after 12h in the above-mentioned aqueous solution, adds carrier matter
The binding agent of amount 10% stirs, the spray shaping in spray dryer, and in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxygen
Compound catalyst, catalyst particle size be 60~200 μm, load capacity of the catalyst activity component oxide on carrier be 1~
20%.
Fixed bed catalyst employed in present example is supported complex oxide catalyst, during catalyst preparation
Prepared using mixed rolling method, preparation method：The presoma (nitrate) of active component is soluble in water, after carrier mixing and rolling uniformly,
The extrusion molding in banded extruder, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~
4mm, load capacity of the catalyst activity component oxide on carrier is 1~20%.
With reference to embodiment, the present invention is described in further detail.
Embodiment 1：
By embodiment 1, reaction is carried out using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.1MPa,
Fluid catalyst is CeO2/ Y, CeO2Load capacity be 15%, fixed bed catalyst is TiO2/Al2O3, TiO2Load capacity be
20%, fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 400gCe (NO3)3·
6H2O is dissolved in 300mL water, and 900gY powder is impregnated after 12h in the above-mentioned aqueous solution, and it is 30% to add 333g mass fractions
Ludox stirs, the spray shaping in spray dryer, and in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalytic
Agent, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：860g tetrabutyl titanates are dissolved in 300mL water, with 1000gAl2O3After mixing and rolling uniformly, in extrusion
Extrusion molding in machine, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~4mm.
Spent resin is chlorostyrene-divinylbenzene strong acidic ion resin, and purification temperature is 410 DEG C, and air enters
Stream speed is set as 43.46L/h, and spent resin feed rate is 0.0025kg/h, and the solid mass ratio of water is 5, fixed bed hot(test)-spot temperature
For 374 DEG C.Under the reaction system, spent resin thermal discharge is 62.5kJ/h, while it is 40.635kJ/h that water vapor, which absorbs heat,
It is 21.87kJ/h that atmosphere temperature rising, which absorbs heat, and final system reaches thermal balance.Fixed bed exports COD：16mg/L, vent gas
Middle VOCs contents：19mg/m3, the content of hydrogen chloride：33mg/m3, the content of chlorine：18mg/m3, the content of sulfur dioxide：
37mg/m3。
Embodiment 2：
By embodiment 2, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.18MPa
OK, fluid catalyst is CuO-La2O3/ Y, CuO load capacity are 15%, La2O3Load capacity be 5%, fixed bed catalyst
For TiO2/SiO2, TiO2Load capacity be 20%, fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 360gCu (NO3)2With
180gLa(NO3)3·6H2O is dissolved in 300mL water, and 900gY powder is impregnated after 12h in the above-mentioned aqueous solution, adds 333g matter
Amount fraction is stirred for 30% Ludox, the spray shaping in spray dryer, and in 120 DEG C of drying, 550 DEG C of roasting 3h are obtained
Composite oxide catalysts, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：860g tetrabutyl titanates are dissolved in 300mL water, with 1000gSiO2After mixing and rolling uniformly, in extrusion
Extrusion molding in machine, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~4mm.
Spent resin is styrene strong acidic ion resin, and purification temperature is 340 DEG C, and air feed flow rate set is
80.17L/h, spent resin feed rate is 0.004kg/h, and the solid mass ratio of water is 7, and fixed bed hot(test)-spot temperature is 374.3 DEG C.At this
Under reaction system, spent resin thermal discharge is 120.0kJ/h, while it is 86.906kJ/h that water vapor, which absorbs heat, atmosphere temperature rising is inhaled
Receipts heat is 33.09kJ/h, and final system reaches thermal balance.Fixed bed exports COD：VOCs contents in 28mg/L, vent gas：
26mg/m3, the content of sulfur dioxide：43mg/m3。
Embodiment 3：
By embodiment 3, reaction is carried out using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.2MPa,
Fluid catalyst is Fe2O3-Co2O3/ ReY, Fe2O3Load capacity be 15%, Co2O3Load capacity be 5%, fixed-bed catalytic
Agent is MnO2/Al2O3, MnO2Load capacity be 15%, fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 760gFe (NO3)3·
9H2O and 176gCo (NO3)2·6H2O is dissolved in 300mL water, and 900gReY powder is impregnated after 12h in the above-mentioned aqueous solution, plus
Enter the Ludox that 333g mass fractions are 30% to stir, the spray shaping in spray dryer, in 120 DEG C of drying, 550 DEG C
Roasting 3h obtains composite oxide catalysts, and catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：By the Mn (NO that 403mL mass fractions are 50%3)3Solution and 1000gAl2O3After mixing and rolling uniformly,
Extrusion molding in banded extruder, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~
4mm。
Spent resin is chlorostyrene-divinylbenzene strong acidic ion resin, and purification temperature is 360 DEG C, and air enters
Stream speed is set as 76.81L/h, and spent resin feed rate is 0.0055kg/h, and the solid mass ratio of water is 6, fixed bed hot(test)-spot temperature
For 375.1 DEG C.Under the reaction system, spent resin thermal discharge is 137.5kJ/h, while water vapor absorption heat is
103.811kJ/h, it is 33.69kJ/h that atmosphere temperature rising, which absorbs heat, and final system reaches thermal balance.Fixed bed exports COD：
VOCs contents in 16mg/L, vent gas：19mg/m3, the content of hydrogen chloride：35mg/m3, the content of chlorine：13mg/m3, dioxy
Change the content of sulphur：29mg/m3。
Embodiment 4：
By embodiment 4, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.16MPa
OK, fluid catalyst is RuO2-NiO2/ MCM-41, RuO2Load capacity be 1%, NiO2Load capacity be 10%, fixed bed
Catalyst is PtO2/SiO2, PtO2Load capacity be 2%, fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 16gRuCl3·3H2O and
389g Ni(NO3)2·6H2O is dissolved in 300mL water, and 900g MCM-41 powder is impregnated after 12h in the above-mentioned aqueous solution, is added
333g mass fractions stir for 30% Ludox, the spray shaping in spray dryer, in 120 DEG C of drying, 550 DEG C of roastings
Burn 3h and obtain composite oxide catalysts, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：By 48gPtCl4It is dissolved in 200mL water, with 1000gAl2O3After mixing and rolling uniformly, squeezed in banded extruder
Go out shaping, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~4mm.
Spent resin is styrene-divinylbenzene acidulous cation resin, and purification temperature is 370 DEG C, air feed flow velocity
It is set as 47.23L/h, spent resin feed rate is 0.008kg/h, and the solid mass ratio of water is 8, and fixed bed hot(test)-spot temperature is 380.5
℃.Under the reaction system, spent resin thermal discharge is 224.0kJ/h, while it is 202.675kJ/h that water vapor, which absorbs heat, it is empty
It is 21.32kJ/h that gas lift temperature, which absorbs heat, and final system reaches thermal balance.Fixed bed exports COD：In 62mg/L, vent gas
VOCs contents：36mg/m3。
Embodiment 5：
By embodiment 5, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.13MPa
OK, fluid catalyst is PdO/Y, and PdO load capacity is 5%, and fixed bed catalyst is MnO2-TiO2/Al2O3, MnO2It is negative
Carrying capacity is 10%, TiO2Load capacity be 10%, fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 75gPdCl2It is dissolved in
In 200mL water, 900gY powder is impregnated after 12h in the above-mentioned aqueous solution, 333g mass fractions is added and is stirred for 30% Ludox
Mix uniform, the spray shaping in spray dryer, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, are catalyzed
Agent particle diameter is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：427g tetrabutyl titanates are dissolved in the Mn (NO that 268mL mass fractions are 50%3)3In solution, then with
1000gAl2O3After mixing and rolling uniformly, the extrusion molding in banded extruder, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxides and urged
Agent, catalyst particle size is 2~4mm.
Spent resin is chlorostyrene-divinylbenzene acidulous cation resin, and purification temperature is 380 DEG C, and air enters
Stream speed is set as 49.19L/h, and spent resin feed rate is 0.0225kg/h, and the solid mass ratio of water is 14, fixed bed hot(test)-spot temperature
For 393.6 DEG C.Under the reaction system, spent resin thermal discharge is 1012.5kJ/h, while water vapor absorption heat is
990.927kJ/h, it is 21.57kJ/h that atmosphere temperature rising, which absorbs heat, and final system reaches thermal balance.Fixed bed exports COD：
VOCs contents in 56mg/L, vent gas：34mg/m3, the content of hydrogen chloride：29mg/m3, the content of chlorine：15mg/m3。
Embodiment 6：
By embodiment 6, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.16MPa
OK, fluid catalyst is Co2O3-CeO2/ Y, Co2O3Load capacity be 5%, CeO2Load capacity be 10%, fixed-bed catalytic
Agent is MnO2/Al2O3, MnO2Load capacity be 10%, fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 88gCo (NO3)2·
6H2O and 253gCe (NO3)3·6H2O is dissolved in 300mL water, and 900gY powder is impregnated after 12h in the above-mentioned aqueous solution, is added
333g mass fractions stir for 30% Ludox, the spray shaping in spray dryer, in 120 DEG C of drying, 550 DEG C of roastings
Burn 3h and obtain composite oxide catalysts, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：By the Mn (NO that 268mL mass fractions are 50%3)3Solution and 1000gAl2O3After mixing and rolling uniformly,
Extrusion molding in banded extruder, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~
4mm。
Spent resin is styrene strongly basic anionic resin, and purification temperature is 360 DEG C, and air feed flow rate set is
105.10L/h, spent resin feed rate is 0.0125kg/h, and the solid mass ratio of water is 9, and fixed bed hot(test)-spot temperature is 382.3 DEG C.
Under the reaction system, spent resin thermal discharge is 400.0kJ/h, while it is 353.903kJ/h, atmosphere temperature rising that water vapor, which absorbs heat,
Absorption heat is 46.10kJ/h, and final system reaches thermal balance.Fixed bed exports COD：VOCs contains in 63mg/L, vent gas
Amount：38mg/m3, the content of nitrogen oxides：41mg/m3。
Embodiment 7：
By embodiment 7, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.14MPa
OK, fluid catalyst is CeO2-Y2O3/ Y molecular sieve, CeO2Load capacity be 15%, Y2O3Load capacity be 5%, fixed bed
Catalyst is Co2O3/Al2O3, Co2O3Load capacity be 20%.Fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 380gCe (NO3)3·
6H2O and 170gY (NO3)3·6H2O is dissolved in 300mL water, and 900gY powder is impregnated after 12h in the above-mentioned aqueous solution, is added
333g mass fractions stir for 30% Ludox, the spray shaping in spray dryer, in 120 DEG C of drying, 550 DEG C of roastings
Burn 3h and obtain composite oxide catalysts, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：By 702gCe (NO3)2·6H2O is dissolved in 300mL water, with 1000gAl2O3After mixing and rolling uniformly, squeezing
Extrusion molding in bar machine, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~4mm.
Spent resin is acrylic acid strongly basic anionic resin, and purification temperature is 360 DEG C, and air feed flow rate set is
50.98L/h, spent resin feed rate is 0.0145kg/h, and the solid mass ratio of water is 10, and fixed bed hot(test)-spot temperature is 377 DEG C.At this
Under reaction system, spent resin thermal discharge is 478.5kJ/h, while it is 456.141kJ/h that water vapor, which absorbs heat, atmosphere temperature rising is inhaled
Receipts heat is 22.36kJ/h, and final system reaches thermal balance.Fixed bed exports COD：VOCs contents in 72mg/L, vent gas：
40mg/m3, the content of nitrogen oxides：27mg/m3。
Embodiment 8：
By embodiment 8, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.16MPa
OK, fluid catalyst is CeO2/ ZSM-5, CeO2Load capacity be 15%, fixed bed catalyst is CuO/Al2O3, CuO's is negative
Carrying capacity is 20%, and fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 380gCe (NO3)3·
6H2O is dissolved in 300mL water, and 900gZSM-5 powder is impregnated after 12h in the above-mentioned aqueous solution, is added 333g mass fractions and is
30% Ludox stirs, the spray shaping in spray dryer, and in 120 DEG C of drying, 550 DEG C of roasting 3h obtain combined oxidation
Thing catalyst, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：By 468.9gCu (NO3)2It is dissolved in 300mL water, with 1000gAl2O3After mixing and rolling uniformly, in extrusion
Extrusion molding in machine, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~4mm.
Spent resin is chlorostyrene-divinylbenzene strongly basic anionic resin, and purification temperature is 370 DEG C, and air enters
Stream speed is set as 122.68L/h, and spent resin feed rate is 0.0175kg/h, and the solid mass ratio of water is 11, fixed bed focus temperature
Spend for 361 DEG C.Under the reaction system, spent resin thermal discharge is 665.0kJ/h, while water vapor absorption heat is
609.609kJ/h, it is 55.39kJ/h that atmosphere temperature rising, which absorbs heat, and final system reaches thermal balance.Fixed bed exports COD：
VOCs contents in 32mg/L, vent gas：26mg/m3, the content of hydrogen chloride：31mg/m3, the content of chlorine：18mg/m3, nitrogen oxygen
The content of compound：33mg/m3。
Embodiment 9：
By embodiment 9, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.11MPa
OK, fluid catalyst is MnO2/ ReY, MnO2Load capacity be 10%, fixed bed catalyst is TiO2/Al2O3, TiO2It is negative
Carrying capacity is 5%, and fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：It is by 268mL mass fractions
50% Mn (NO3)3Solution is impregnated after 12h with 900gReY powder in the above-mentioned aqueous solution, and it is 30% to add 333g mass fractions
Ludox stir, the spray shaping in spray dryer, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxides and urged
Agent, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：214g tetrabutyl titanates are dissolved in 300mL water, with 1000gAl2O3After mixing and rolling uniformly, in extrusion
Extrusion molding in machine, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~4mm.
Spent resin is styrene weak anion resin, and purification temperature is 400 DEG C, and air feed flow rate set is
37.21L/h, spent resin feed rate is 0.019kg/h, and the solid mass ratio of water is 13, and fixed bed hot(test)-spot temperature is 384 DEG C.At this
Under reaction system, spent resin thermal discharge is 816kJ/h, while it is 797.761kJ/h that water vapor, which absorbs heat, atmosphere temperature rising absorbs
Heat is 18.24kJ/h, and final system reaches thermal balance.Fixed bed exports COD：VOCs contents in 10mg/L, vent gas：
13mg/m3, the content of nitrogen oxides：36mg/m3。
Embodiment 10：
By embodiment 10, reaction is entered using the combined purifying device of fluid bed-fixed bed series connection under pressure 0.13MPa
OK, fluid catalyst is CeO2/ Y molecular sieve, CeO2Load capacity be 15%, fixed bed catalyst is TiO2/SiO2, TiO2's
Load capacity is 10%.Fluid bed and fixed bed catalyst loadings are 0.05kg.
Fluid catalytic cracking oxidation catalyst is made using spray drying process, preparation method：By 380gCe (NO3)3·
6H2O is dissolved in 300mL water, and 900gY powder is impregnated after 12h in the above-mentioned aqueous solution, and it is 30% to add 333g mass fractions
Ludox stirs, the spray shaping in spray dryer, and in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalytic
Agent, catalyst particle size is 60~200 μm.
Fixed bed catalyst employed in example is supported complex oxide catalyst, using mixed during catalyst preparation
Prepared by rolling method, preparation method：427g tetrabutyl titanates are dissolved in 300mL water, with 1000g SiO2After mixing and rolling uniformly, in extrusion
Extrusion molding in machine, in 120 DEG C of drying, 550 DEG C of roasting 3h obtain composite oxide catalysts, and catalyst particle size is 2~4mm.
Spent resin is acrylic acid weak anion resin, and purification temperature is 390 DEG C, and air feed flow rate set is
64.18L/h, spent resin feed rate is 0.0205kg/h, and the solid mass ratio of water is 12, and fixed bed hot(test)-spot temperature is 363 DEG C.At this
Under reaction system, spent resin thermal discharge is 820.0kJ/h, while it is 789.365kJ/h that water vapor, which absorbs heat, atmosphere temperature rising is inhaled
Receipts heat is 30.64kJ/h, and final system reaches thermal balance.Fixed bed exports COD：VOCs contents in 67mg/L, vent gas：
32mg/m3, the content of nitrogen oxides：26mg/m3。
Claims (10)
1. a kind of processing method of waste resin catalytic pyrolysis oxidation, it is characterised in that：This method comprises the following steps：
(1) waste resin after crushing is added water carry out decentralized processing, obtains the waste resin suspension with mobility；
(2) the waste resin suspension and air of step (1) are added in fluidized-bed reactor simultaneously, in the effect of catalyst
Under, waste resin carries out catalytic pyrolysis oxidation reaction, obtains the gas after pyrolysis oxidization；
(3) gas after step (2) pyrolysis oxidization is delivered into enter in the fixed bed reactors connected with fluidized-bed reactor
Row catalyst combustion reaction, makes the organic molecule content in gas be reduced to 40mg/m3Below；
(4) gas of step (3) fixed bed reactors outlet obtains cold after heat exchanger reclaims heat by condenser cooling
Lime set is used for the scattered of waste resin, and tail gas is directly emptied after alkali liquor absorption.
2. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：Described is discarded
Resin refers to regenerate the ion exchange resin without metallic element used, and preferably described waste resin is polystyrene
Resin, acrylic resin, phenolic aldehyde system resin, epoxy system resin, vinylpyridine system resin and one kind in ureaformaldehyde system resin or
It is a variety of.
3. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：It is useless after crushing
Resin particle diameter is abandoned less than or equal to 40 microns；The quality of waste resin suspension reclaimed water and waste resin is 5~15：1.
4. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：Step (2) flows
In fluidized bed reactor, in the presence of oxygen atmosphere and catalyst, the coupling of cracking and oxidation occurs for waste resin, in resin
The inorganic molecules such as carbon dioxide, water vapour are oxidized to while being cracked into low molecule amount organic molecule.
5. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：In step (3)
Organic molecule be molecular weight be 16~300 organic molecule.
6. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：Step (2) flows
The catalytic pyrolysis oxidation reaction condition of waste resin is that absolute pressure is 0.1~0.25MPa in fluidized bed reactor, and reaction temperature is
250~450 DEG C.
7. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：In step (2)
The feed rate of waste resin is 0.05~0.5kg/ (kgcatFluid bedH), air mass flow is 720~2500L/
(kgcatFluid bed·h)。
8. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：Fixed bed reaction
200~400 DEG C of reaction temperature in device.
9. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：Step (4) is cold
COD in lime set is less than or equal to 80mg/L, and tail gas is after alkali liquor absorption, the content of the volatile organic compound in emptying gas
Less than or equal to 40mg/m3。
10. the processing method of waste resin catalytic pyrolysis oxidation according to claim 1, it is characterised in that：Step (2) and
The active component of step (3) catalyst is one or both of copper, iron, cobalt, nickel, ruthenium, cerium, lanthanum, platinum, titanium, palladium, yttrium, manganese, and
The oxide form of active component in the catalyst is present；The carrier of fluid bed used catalyst is molecular sieve in step (2), excellent
Elect any of ZSM-5, MCM-41, Y molecular sieve, ReY molecular sieves as, catalyst is made using spray drying process, and catalysis
Agent particle diameter is 60~200 μm,；Carrier in step (3) used in fixed-bed catalytic combustion catalyst is Al2O3、SiO2, activity it is white
Any of soil, catalyst is prepared using mixed rolling method, and catalyst particle size is 2~4mm,；Preferred steps (2) and step (3) are carried
The oxide carried amount of active component is 10~20% on body.
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