CN116254128B - Method for producing petrochemical products by utilizing waste plastics - Google Patents
Method for producing petrochemical products by utilizing waste plastics Download PDFInfo
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- CN116254128B CN116254128B CN202310115046.7A CN202310115046A CN116254128B CN 116254128 B CN116254128 B CN 116254128B CN 202310115046 A CN202310115046 A CN 202310115046A CN 116254128 B CN116254128 B CN 116254128B
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- 239000004033 plastic Substances 0.000 title claims abstract description 111
- 229920003023 plastic Polymers 0.000 title claims abstract description 111
- 239000002699 waste material Substances 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 67
- 238000000197 pyrolysis Methods 0.000 claims abstract description 41
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims description 126
- 239000003795 chemical substances by application Substances 0.000 claims description 82
- 239000003921 oil Substances 0.000 claims description 54
- 239000003223 protective agent Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 37
- 238000004523 catalytic cracking Methods 0.000 claims description 36
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 26
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 26
- 239000012752 auxiliary agent Substances 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 23
- 239000002808 molecular sieve Substances 0.000 claims description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 230000000382 dechlorinating effect Effects 0.000 claims description 20
- 239000012535 impurity Substances 0.000 claims description 20
- 238000005336 cracking Methods 0.000 claims description 18
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006298 dechlorination reaction Methods 0.000 claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000012634 fragment Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 230000001877 deodorizing effect Effects 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- -1 VIB metal oxide Chemical group 0.000 claims description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000000969 carrier Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 19
- 239000000295 fuel oil Substances 0.000 abstract description 14
- 239000010813 municipal solid waste Substances 0.000 abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002910 solid waste Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 37
- 238000005516 engineering process Methods 0.000 description 15
- 239000003502 gasoline Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000012263 liquid product Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000010812 mixed waste Substances 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- 239000004597 plastic additive Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002023 wood Substances 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
-
- 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
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/10—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with stationary catalyst bed
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- 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
- C10G2300/1003—Waste materials
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
-
- 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)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention belongs to the field of environmental protection, and particularly relates to a method for producing petrochemical products by utilizing waste plastics. The method comprises the following steps: waste plastics sequentially undergo anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis and product separation to obtain different types of petrochemical products. The method provided by the invention can convert the solid waste plastics separated from garbage into products such as low-carbon olefin, aromatic hydrocarbon, fuel oil and the like by utilizing a series of process flows of anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis, product separation and the like, and realizes the high-value utilization of the waste plastics while eliminating white pollution.
Description
Technical Field
The invention belongs to the field of environmental protection, and particularly relates to a method for producing petrochemical products by utilizing waste plastics.
Background
The economic development is rapid, and the urbanization process is continuously accelerated. But in the process of town, some non-negligible problems are exposed. For example, the proportion of waste plastics in urban solid waste is about 13wt.%, and the trend of the annual growth is that the white pollution brings great harm to land and marine ecology environment, and the health of human beings is potentially threatened. Although the practice of garbage classification and the like can limit the harm of waste plastics to a certain extent, some garbage waste plastics cannot be properly treated due to insufficient terminal treatment capacity. Therefore, how to utilize the waste plastics in the urban garbage in a high-value manner becomes a problem to be solved urgently at present.
The waste plastics are treated by landfill, incineration, regeneration and utilization, oiling and other methods. Landfill is a more common method for treating solid wastes, but the method is gradually eliminated because waste plastics cause soil hardening and waste of land resources; the incineration can convert waste plastics into heat energy for heat supply, power generation and the like, is a relatively efficient treatment method, but dioxin generated in the incineration process can cause secondary pollution to the environment, releases a large amount of CO 2 and is not suitable for the 'carbon reduction' target in the current society; the recycling is to granulate and melt the waste plastics after cleaning treatment, but the quality of the regenerated composite recycled plastics is generally poor and the economical efficiency is lower; the waste plastics are converted into fuel oil or chemicals through pyrolysis or catalytic pyrolysis, so that the current problem of energy shortage in the society can be relieved, the carbon emission can be obviously reduced, the economic benefit is higher, and the method is the best choice for the reduction and recycling of urban garbage waste plastics.
The existing patents related to the waste plastic oiling technology are mainly focused on a certain technology, such as gasoline, diesel oil and the like produced by catalytic pyrolysis, and the existing patents relate to a complete technology system for high-value utilization of waste plastics. Although the core of the high-valued utilization of the waste plastic oil is catalytic cracking, a plurality of difficulties exist before and after the catalytic cracking process. For example, unlike clean plastics, waste plastics obtained by sorting and recycling garbage are stained with dirt such as sewage, soil, oil stain and the like on the surface, and the generated oil obtained by direct pyrolysis is poor in quality; the waste plastics have different shapes and low bulk density, if a solid feeding mode is adopted, the cracking device is difficult to operate continuously, and the treatment efficiency of the device is low; due to the influence of plastic additives and the properties of the plastic additives, the pyrolysis oil inevitably contains some impurities, and especially when the waste plastic contains polyvinyl chloride (PVC), the chlorine content of the pyrolysis oil is seriously out of standard, so that the pyrolysis oil is poor in quality and difficult to directly use; the existing waste plastic pyrolysis technology is mostly focused on producing fuel oil such as gasoline, diesel oil and the like with lower added value, and a novel technology needs to be developed to carry out deep processing on the pyrolysis oil so as to improve the yield of high-added value chemicals such as low-carbon olefins, aromatic hydrocarbons and the like.
In view of the foregoing, there is a need to develop a complete solution suitable for high-value utilization of waste plastics, so as to properly solve the problems encountered in the catalytic cracking process of waste plastics, and further improve the high-value utilization level of urban garbage waste plastics.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for producing petrochemical products by using waste plastics, which can efficiently convert waste plastics into petrochemical products such as low-carbon olefins, aromatic hydrocarbons, fuel oil and the like, and convert waste plastics from "white pollution" into available potential energy and resources.
The invention provides a method for producing petrochemical products by utilizing waste plastics, which comprises the following steps:
Waste plastics sequentially undergo anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis and product separation to obtain different types of petrochemical products;
The components of the liquefaction solvent used for the multistage liquefaction comprise alkane and aromatic hydrocarbon; the alkane is one or more of cyclohexane, normal hexane, normal heptane and octane, the aromatic hydrocarbon is one or more of benzene, toluene, xylene and ethylbenzene, and the alkane accounts for 40-90 wt% of the total mass of the alkane and the aromatic hydrocarbon;
The catalytic cracking is performed in a fixed fluidized bed; the catalyst used for catalytic cracking comprises a catalyst carrier, an adhesive and an active component; the catalyst carrier is one or more of alumina, silica, kaolin and halloysite, the adhesive is one or more of silica sol, alumina sol, silica alumina sol and silica alumina gel, the active component is ZSM-5 molecular sieve and/or Y-type molecular sieve, the catalyst carrier accounts for 40-60 wt% of the total mass of the catalyst carrier, the adhesive and the active component, and the active component accounts for 10-40 wt% of the total mass of the catalyst carrier, the adhesive and the active component;
the equipment used for hydrofining comprises a hydrogenation pretreatment reactor and a hydrofining main reactor which are arranged in series; the hydrogenation pretreatment reactor is filled with a dechlorinating agent, a demetallizing agent and a protecting agent; the dechlorination agent comprises a hydrodechlorination catalyst and an alkaline earth metal dechlorination agent; the hydrodechlorination catalyst comprises a hydrodechlorination catalyst carrier, an active component A, an active component B and an auxiliary agent, wherein the active component A is a VIII metal oxide, the active component B is a VIB metal oxide, the auxiliary agent is one or more of a Ca oxide, a Cu oxide, a Ti oxide, a Zr oxide, a B oxide and a P oxide, the hydrodechlorination catalyst carrier is modified alumina, the active component A accounts for 1-5wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, the active component B accounts for 10-15wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, and the auxiliary agent accounts for 1-5wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent; the hydrofining main reactor is filled with hydrofining catalyst.
Preferably, the specific process of the anhydrous clean pretreatment comprises the following steps:
Sequentially carrying out shredding, winnowing impurity removal, drying and gas-solid separation on the waste plastics to obtain treated waste plastic fragments.
Preferably, the specific process of the anhydrous clean pretreatment further comprises the following steps:
and dedusting and deodorizing the gas separated in the gas-solid separation process.
Preferably, the specific process of multistage liquefaction comprises:
Delivering the waste plastics subjected to anhydrous clean pretreatment into a first-stage liquefaction kettle, adding a liquefaction solvent into the first-stage liquefaction kettle, and delivering the obtained mixture into a second-stage liquefaction kettle after the waste plastics and the liquefaction solvent are fully stirred and mixed; continuously stirring the mixture in a secondary liquefaction kettle under the anaerobic condition, filtering to remove solid impurities, and feeding the obtained liquefied liquid into a tertiary liquefaction kettle; the liquefied liquid stays in the three-stage liquefying kettle for a certain time and is then conveyed to a catalytic cracking process.
Preferably, the stirring rates of the primary liquefaction kettle, the secondary liquefaction kettle and the tertiary liquefaction kettle are independently selected to be 20-50 rpm; the temperatures of the primary liquefaction kettle, the secondary liquefaction kettle and the tertiary liquefaction kettle are independently selected to be 170-210 ℃; the residence time of the liquefied liquid in the three-stage liquefying kettle is 80-160 min.
Preferably, the catalytic cracking temperature is 400-600 ℃; the catalyst-oil ratio of the catalytic cracking is 3-6.
Preferably, the alkaline earth metal dechlorinating agent comprises a pseudo-boehmite carrier and an alkaline earth metal active component; the alkaline earth metal active components comprise calcium oxide and magnesium oxide, wherein the calcium oxide accounts for 30-50wt% of the total mass of the pseudo-boehmite carrier and the alkaline earth metal active components, and the magnesium oxide accounts for 15-25wt% of the total mass of the pseudo-boehmite carrier and the alkaline earth metal active components;
The components of the demetallizing agent comprise demetallizing agent carriers and demetallizing agent active components; the demetallizing agent carrier is an alumina carrier, the demetallizing agent active components are NiO and MoO 3, the NiO accounts for 1-5wt% of the total mass of the demetallizing agent carrier and the demetallizing agent active components, and the MoO 3 accounts for 5-15wt% of the total mass of the demetallizing agent carrier and the demetallizing agent active components;
the components of the protective agent comprise a protective agent carrier and a protective agent active component; the protective agent carrier is an alumina carrier, the protective agent active components comprise NiO and MoO 3, the NiO accounts for 1-5wt% of the total mass of the protective agent carrier and the protective agent active components, and the MoO 3 accounts for 5-15wt% of the total mass of the protective agent carrier and the protective agent active components;
the hydrofining catalyst comprises hydrofining catalyst carriers and hydrofining catalyst active components; the hydrofining catalyst carrier is an alumina carrier, the active components of the hydrofining catalyst are NiO and MoO 3, the NiO accounts for 2-10wt% of the total mass of the hydrofining catalyst carrier and the active components of the hydrofining catalyst, and the MoO 3 accounts for 20-30wt% of the total mass of the hydrofining catalyst carrier and the active components of the hydrofining catalyst.
Preferably, the hydrofining temperature is 300-400 ℃; the hydrogen partial pressure of the hydrofining is 3-7 MPa; the volume ratio of the hydrofined hydrogen oil is (400-600) 1; the volume airspeed of the hydrofining is 1-2 h -1.
Preferably, the components of the catalyst used for the secondary cracking comprise Al 2O3、Na2O、Fe2O3 and ZRP molecular sieves; the Al 2O3 accounts for 40-50wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve, the Na 2 O accounts for 0.01-0.1wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve, and the Fe 2O3 accounts for 0.2-0.35wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve.
Preferably, the temperature of the secondary cracking is 610-630 ℃; the reaction pressure of the secondary cracking is 0.05-0.2 MPa; the ratio of the agent to the oil of the secondary cracking is 10-30; the water-oil ratio of the secondary pyrolysis is 0.05-0.5; the volume airspeed of the secondary pyrolysis is 0.5-5 h -1; the residence time of the secondary cracking is 0.5-3 s.
Compared with the prior art, the invention provides a method for producing petrochemical products by utilizing waste plastics, which comprises the following steps: waste plastics sequentially undergo anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis and product separation to obtain different types of petrochemical products; the components of the liquefaction solvent used for the multistage liquefaction comprise alkane and aromatic hydrocarbon; the alkane is one or more of cyclohexane, normal hexane, normal heptane and octane, the aromatic hydrocarbon is one or more of benzene, toluene, xylene and ethylbenzene, and the alkane accounts for 40-90 wt% of the total mass of the alkane and the aromatic hydrocarbon; the catalytic cracking is performed in a fixed fluidized bed; the catalyst used for catalytic cracking comprises a catalyst carrier, an adhesive and an active component; the catalyst carrier is one or more of alumina, silica, kaolin and halloysite, the adhesive is one or more of silica sol, alumina sol, silica alumina sol and silica alumina gel, the active component is ZSM-5 molecular sieve and/or Y-type molecular sieve, the catalyst carrier accounts for 40-60 wt% of the total mass of the catalyst carrier, the adhesive and the active component, and the active component accounts for 10-40 wt% of the total mass of the catalyst carrier, the adhesive and the active component; the equipment used for hydrofining comprises a hydrogenation pretreatment reactor and a hydrofining main reactor which are arranged in series; the hydrogenation pretreatment reactor is filled with a dechlorinating agent, a demetallizing agent and a protecting agent; the dechlorination agent comprises a hydrodechlorination catalyst and an alkaline earth metal dechlorination agent; the hydrodechlorination catalyst comprises a hydrodechlorination catalyst carrier, an active component A, an active component B and an auxiliary agent, wherein the active component A is a VIII metal oxide, the active component B is a VIB metal oxide, the auxiliary agent is one or more of a Ca oxide, a Cu oxide, a Ti oxide, a Zr oxide, a B oxide and a P oxide, the hydrodechlorination catalyst carrier is modified alumina, the active component A accounts for 1-5wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, the active component B accounts for 10-15wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, and the auxiliary agent accounts for 1-5wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent; the hydrofining main reactor is filled with hydrofining catalyst. The method provided by the invention can convert the solid waste plastics separated from garbage into products such as low-carbon olefin, aromatic hydrocarbon, fuel oil and the like by utilizing a series of process flows of anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis, product separation and the like, and realizes the high-value utilization of the waste plastics while eliminating white pollution.
More specifically, the technical scheme provided by the invention has the following technical advantages:
(1) The waste plastics recovered from the garbage are pretreated by utilizing an anhydrous clean pretreatment technology, so that the waste of water resources by the traditional water washing clean method is avoided, and the impurity removal rate can reach more than 93 percent;
(2) The multi-stage liquefaction treatment is carried out before the catalytic pyrolysis, so that the downstream pyrolysis device can be guaranteed to be fed continuously in a liquid state, and the treatment efficiency and the operation period of the catalytic pyrolysis device are improved;
(3) The specific liquefaction solvent is adopted to carry out multistage dissolution and liquefaction on the waste plastics, so that the liquefaction temperature of different types of waste plastics can be effectively reduced, the liquefaction time is shortened, and the highest waste plastics liquefaction rate can reach more than 98%;
(4) The fixed fluidized bed device is used for carrying out catalytic pyrolysis on the waste plastic liquefied liquid, and the distribution of pyrolysis products can be effectively improved by matching with a specific catalytic pyrolysis catalyst, and the conversion rate of the waste plastic liquefied liquid is improved, so that the total conversion rate of the waste plastic liquefied liquid can reach more than 95wt percent;
(5) The equipment used in hydrofining consists of a hydrogenation pretreatment reactor and a hydrofining main reactor which are connected in series, wherein chloride and metal element impurities in waste plastic pyrolysis oil are removed in the hydrogenation pretreatment reactor firstly, and then impurities such as sulfur, nitrogen and oxides are removed in the hydrofining main reactor, so that the requirement of deep refining of the oil product is finally met;
(6) The catalytic cracking technology in the oil refining industry is used for carrying out secondary cracking on the waste plastic pyrolysis oil obtained by hydrofining, and high-added-value chemicals such as low-carbon olefin, aromatic hydrocarbon and the like are produced by optimizing the reaction conditions.
(7) And by means of the separation technology in the oil refining industry, high-value chemicals such as low-carbon olefin, aromatic hydrocarbon and the like and fuel oil such as gasoline, diesel oil, heavy oil and the like are obtained, and finally, the high-value utilization of urban garbage waste plastics is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a process flow diagram of a petrochemical production process using waste plastics provided in an embodiment of the present invention;
FIG. 2 is a schematic flow chart of the anhydrous clean pretreatment of waste plastics provided by the embodiment of the invention;
fig. 3 is a schematic structural view of a small-sized fixed fluidized bed reactor provided in an embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for producing petrochemical products by utilizing waste plastics, which comprises the following steps:
Waste plastics sequentially undergo anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis and product separation to obtain different types of petrochemical products.
In the method provided by the invention, the waste plastics are preferably town refuse waste plastics, including but not limited to one or more of household refuse waste plastics, paper mill waste plastics and waste recycling company waste plastics.
In the method provided by the invention, the specific process of the anhydrous clean pretreatment preferably comprises the following steps: sequentially carrying out shredding, winnowing, impurity removal, drying and gas-solid separation on the waste plastics to obtain treated waste plastic fragments; wherein the size of the shreds is preferably 3-8 cm, more preferably 5cm. In the present invention, the specific process of the anhydrous clean pretreatment preferably further comprises: dedusting and deodorizing the gas separated in the gas-solid separation process; wherein, the equipment used for dedusting and deodorizing preferably comprises a cloth bag dust remover, an air cooling condenser and a UV photolytic deodorizing device which are arranged in series.
In the method provided by the invention, the components of the liquefaction solvent used for the multistage liquefaction preferably comprise alkane and aromatic hydrocarbons; the alkane is preferably one or more of cyclohexane, n-hexane, n-heptane and octane, the aromatic hydrocarbon is preferably one or more of benzene, toluene, xylene and ethylbenzene, and the alkane preferably accounts for 40-90 wt%, preferably 50-85 wt%, and in particular may be 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or 90wt% of the total mass of the alkane and the aromatic hydrocarbon.
In the method provided by the invention, the specific process of multistage liquefaction preferably comprises the following steps: delivering the waste plastics subjected to anhydrous clean pretreatment into a first-stage liquefaction kettle, adding a liquefaction solvent into the first-stage liquefaction kettle, and delivering the obtained mixture into a second-stage liquefaction kettle after the waste plastics and the liquefaction solvent are fully stirred and mixed; continuously stirring the mixture in a secondary liquefaction kettle under the anaerobic condition, filtering to remove solid impurities, and feeding the obtained liquefied liquid into a tertiary liquefaction kettle; the liquefied liquid stays in the three-stage liquefying kettle for a certain time and is then conveyed to a catalytic cracking process. Wherein the stirring rate of the primary liquefaction kettle, the secondary liquefaction kettle and the tertiary liquefaction kettle is independently preferably 20-50 rpm, and specifically can be 20rpm, 25rpm, 30rpm, 35rpm, 40rpm, 45rpm or 50rpm, and most preferably is 30rpm; the temperatures of the primary liquefaction kettle, the secondary liquefaction kettle and the tertiary liquefaction kettle are independently preferably 170-210 ℃, specifically 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃ or 210 ℃ and most preferably 190 ℃; the heating rate to reach the temperature is preferably 10-30 ℃/min, and can be specifically 10 ℃/min, 15 ℃/min, 20 ℃/min, 25 ℃/min or 30 ℃/min, and most preferably 20 ℃/min; the residence time of the liquefied liquid in the three-stage liquefying kettle is preferably 80-160 min, specifically can be 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min, and is most preferably 120min.
In the process provided by the present invention, the catalytic cracking is preferably carried out in a fixed fluidized bed.
In the method provided by the invention, the components of the catalyst used for catalytic cracking preferably comprise a catalyst carrier, a binder and an active component; wherein the catalyst carrier is preferably one or more of alumina, silica, kaolin and halloysite, more preferably alumina and kaolin, and the mass ratio of the alumina to the kaolin is preferably 3 (1-3), more preferably 3:2; the catalyst carrier preferably accounts for 40-60 wt%, specifically 40wt%, 45wt%, 50wt%, 55wt% or 60wt%, most preferably 50wt% of the total mass of the catalyst carrier, the binder and the active components; the adhesive is preferably one or more of silica sol, alumina sol, silica-alumina sol and silica-alumina gel; the binder preferably accounts for 2-10wt%, specifically 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%, most preferably 10wt% of the total mass of the catalyst carrier, the binder and the active component; the active component is a molecular sieve, preferably a ZSM-5 molecular sieve and/or a Y-type molecular sieve; the active component preferably comprises 10 to 40wt% of the combined mass of the catalyst support, binder and active component, and may be in particular 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%, most preferably 40wt%.
In the method provided by the invention, the temperature of the catalytic cracking is preferably 400-600 ℃, specifically 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, and most preferably 500 ℃; the catalyst to oil ratio of the catalytic cracking is preferably 3 to 6, and may be specifically 3, 3.5, 4, 4.5, 5 or 6, and most preferably 4.
In the method provided by the invention, the equipment used for hydrofining preferably comprises a hydrotreating pretreatment reactor and a hydrofining main reactor which are arranged in series; wherein, the hydrogenation pretreatment reactor is filled with a dechlorinating agent, a demetallizing agent and a protecting agent; the hydrofining main reactor is filled with hydrofining catalyst.
In the method provided by the invention, the dechlorination agent comprises a hydrodechlorination catalyst and an alkaline earth metal dechlorination agent in a hydrogenation pretreatment reactor; wherein, the components of the hydrodechlorination catalyst preferably comprise a hydrodechlorination catalyst carrier, an active component A, an active component B and an auxiliary agent; the active component A is preferably a group VIII metal oxide, more preferably nickel oxide; the active component A preferably accounts for 1 to 5 weight percent of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, and can be 1 weight percent, 2 weight percent, 3 weight percent, 4 weight percent or 5 weight percent, and most preferably 3 weight percent; the active component B is preferably a group VIB metal oxide, more preferably molybdenum oxide; the active component B preferably accounts for 10 to 15 weight percent of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, and can be particularly 10 weight percent, 11 weight percent, 12 weight percent, 13 weight percent, 14 weight percent or 15 weight percent, and most preferably 15 weight percent; the auxiliary agent is one or more of Ca oxide, cu oxide, ti oxide, zr oxide, B oxide and P oxide, and more preferably phosphorus oxide; the auxiliary agent preferably accounts for 1 to 5 weight percent of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, and can be 1 weight percent, 2 weight percent, 3 weight percent, 4 weight percent or 5 weight percent, and most preferably is 2 weight percent; the hydrodechlorination catalyst support is preferably a modified alumina, more preferably pseudo-boehmite.
In the method provided by the invention, in the dechlorinating agent, the alkaline earth metal dechlorinating agent preferably comprises a pseudo-boehmite carrier and an alkaline earth metal active component; the alkaline earth metal active component is preferably calcium oxide and magnesium oxide; the calcium oxide preferably accounts for 30-50 wt% of the total mass of the pseudo-boehmite carrier and the alkaline earth active component, and specifically can be 30wt%, 35wt%, 40wt%, 45wt% or 50wt%, and most preferably 40wt%; the magnesium oxide preferably comprises 15 to 25wt%, in particular 15wt%, 17wt%, 20wt%, 23wt% or 25wt%, most preferably 20wt%, of the combined mass of the pseudo-boehmite carrier and alkaline earth active component.
In the method provided by the invention, in the dechlorination agent, the mass ratio of the hydrodechlorination catalyst to the alkaline earth metal dechlorination agent is preferably 1 (1-5), specifically can be 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, and is most preferably 1:3.
In the method provided by the invention, the components of the demetallizing agent in the hydrogenation pretreatment reactor preferably comprise a demetallizing agent carrier and a demetallizing agent active component; the demetallizing agent carrier is preferably an alumina carrier; the active component of the demetallizing agent is preferably NiO and/or MoO 3; the NiO preferably accounts for 1-5 wt% of the total mass of the demetallizing agent carrier and the demetallizing agent active component, and specifically can be 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt%, and most preferably is 3wt%; the MoO 3 preferably accounts for 5 to 15wt%, specifically 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%, most preferably 12wt%, of the total mass of the demetallizing agent carrier and the demetallizing agent active component.
In the method provided by the invention, the components of the protective agent preferably comprise a protective agent carrier and a protective agent active component in the hydrogenation pretreatment reactor; the protective agent carrier is preferably an alumina carrier; the active component of the protective agent is preferably NiO and/or MoO 3; the NiO preferably accounts for 1 to 5 weight percent of the total mass of the protective agent carrier and the protective agent active component, and can be specifically 1 weight percent, 1.5 weight percent, 2 weight percent, 2.5 weight percent, 3 weight percent, 3.5 weight percent, 4 weight percent, 4.5 weight percent or 5 weight percent, and most preferably is 2.5 weight percent; the MoO 3 preferably accounts for 5 to 15wt%, specifically 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%, most preferably 10wt%, of the total mass of the protectant carrier and the protectant active component.
In the method provided by the invention, the protective agent preferably accounts for 5-15 wt% of the total mass of the dechlorinating agent, the demetallizing agent and the protective agent in the hydrogenation pretreatment reactor, and specifically can be 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, and most preferably 8wt%; the demetallizing agent preferably accounts for 10-20 wt% of the total mass of the dechlorinating agent, the demetallizing agent and the protecting agent, and specifically can be 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt% or 20wt%, and most preferably is 12wt%; the rest is dechlorinating agent.
In the method provided by the invention, in the hydrogenation pretreatment reactor, the protective agent, the demetallizing agent, the hydrodechlorination catalyst and the alkaline earth metal dechlorinating agent are preferably filled in layers in the reactor from top to bottom; the total packing density of the protective agent, demetallizing agent, hydrodechlorination catalyst and alkaline earth metal dechlorinating agent in the hydrotreatment reactor is preferably 0.6-1 g/cm 3, in particular 0.6g/cm3、0.65g/cm3、0.7g/cm3、0.75g/cm3、0.8g/cm3、0.83g/cm3、0.85g/cm3、0.9g/cm3、0.95g/cm3 or 1g/cm 3, most preferably 0.83g/cm 3.
In the method provided by the invention, the components of the hydrofining catalyst preferably comprise a hydrofining catalyst carrier and hydrofining catalyst active components in a hydrofining main reactor; the hydrofining catalyst carrier is preferably an alumina carrier; the active component of the hydrofining catalyst is preferably NiO and/or MoO 3; the NiO preferably accounts for 2-10wt% of the total mass of the hydrofining catalyst carrier and the hydrofining catalyst active component, and specifically can be 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%, and most preferably is 5wt%; the MoO 3 preferably accounts for 20-30 wt%, specifically 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt%, 26wt%, 27wt%, 28wt%, 29wt% or 30wt%, most preferably 26wt%, of the total mass of the hydrofining catalyst carrier and the hydrofining catalyst active component.
In the method provided by the invention, the loading bulk density of the hydrofining catalyst in the hydrofining main reactor is preferably 0.6-1 g/cm 3, particularly 0.6g/cm3、0.65g/cm3、0.7g/cm3、0.75g/cm3、0.8g/cm3、0.83g/cm3、0.85g/cm3、0.9g/cm3、0.95g/cm3 or 1g/cm 3, and most preferably 0.83g/cm 3; the ratio of the loading volume of the hydrofining catalyst in the hydrofining main reactor to the total loading volume of the protecting agent, the demetallizing agent, the hydrodechlorination catalyst and the alkaline earth metal dechlorinating agent in the hydrotreating reactor is preferably (2-10): 30, specifically may be 2:30, 3:30, 4:30, 5:30, 6:30, 7:30, 8:30, 9:30 or 10:30, and most preferably is 6:30.
In the method provided by the invention, the hydrofining temperature is preferably 300-400 ℃, specifically 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃ or 400 ℃, most preferably 350 ℃; the hydrogen partial pressure of the hydrofining is preferably 3-7 MPa, and can be specifically 3MPa, 4MPa, 5MPa, 6MPa or 7MPa, and most preferably 5MPa; the volume ratio of the hydrofined hydrogen oil is preferably (400-600) 1, specifically can be 400:1, 420:1, 450:1, 470:1, 500:1, 520:1, 550:1, 570:1 or 600:1, and is most preferably 500:1; the volume space velocity of the hydrofinishing is preferably 1 to 2h -1, in particular 1h-1、1.1h-1、1.2h-1、1.3h-1、1.4h-1、1.5h-1、1.6h-1、1.7h-1、1.8h-1、1.9h-1 or 2h -1, most preferably 1.5h -1.
In the method provided by the invention, the components of the catalyst used for the secondary cracking preferably comprise Al 2O3、Na2O、Fe2O3 and ZRP molecular sieves; the Al 2O3 preferably accounts for 40-50 wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve, and specifically can be 40wt%, 41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 46.3wt%, 47wt%, 48wt%, 49wt% or 50wt%, and most preferably 46.3wt%; the Na 2 O preferably accounts for 0.01 to 0.1wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve, and specifically can be 0.01wt%, 0.02wt%, 0.03wt%, 0.04wt%, 0.05wt%, 0.06wt%, 0.07wt%, 0.08wt%, 0.09wt% or 0.1wt%, and most preferably 0.04wt%; the Fe 2O3 preferably accounts for 0.2 to 0.35wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and ZRP molecular sieve, and particularly can be 0.2wt％、0.21wt％、0.22wt％、0.23wt％、0.24wt％、0.25wt％、0.26wt％、0.27wt％、0.28wt％、0.29wt％、0.3wt％、0.31wt％、0.32wt％、0.33wt％、0.34wt％ or 0.35wt%, and most preferably is 0.27wt%.
In the method provided by the invention, the temperature of the secondary pyrolysis is preferably 610-630 ℃, and can be 610 ℃, 612 ℃, 615 ℃, 617 ℃, 620 ℃, 623 ℃, 625 ℃, 627 ℃ or 630 ℃ and most preferably 620 ℃; the reaction pressure of the secondary cracking is preferably 0.05-0.2 MPa, particularly 0.05MPa、0.06MPa、0.07MPa、0.08MPa、0.09MPa、0.1MPa、0.11MPa、0.12MPa、0.13MPa、0.14MPa、0.15MPa、0.16MPa、0.17MPa、0.18MPa、0.19MPa or 0.2MPa, and most preferably 0.1MPa; the ratio of the agent to the oil of the secondary cracking is preferably 10 to 30, and can be 10, 12, 15, 18, 20, 23, 25, 28 or 30, and most preferably 20; the water-oil ratio of the secondary pyrolysis is preferably 0.05 to 0.5, and specifically may be 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, and most preferably 0.3; the volume space velocity of the secondary pyrolysis is preferably 0.5-5 h -1, in particular 0.5h-1、1h-1、1.5h-1、2h-1、2.5h-1、3h-1、3.5h-1、4h-1、4.5h-1 or 5h -1, most preferably 2h -1; the residence time of the secondary cleavage is preferably from 0.5 to 3s, in particular may be 0.5s, 0.7s, 1s, 1.2s, 1.5s, 1.7s, 2s, 2.3s, 2.5s, 2.7s or 3s, most preferably 1.5s.
In the method provided by the invention, the product separation mode comprises one or more of gas-liquid separation, aromatic hydrocarbon extraction and fraction cutting; the petrochemical products obtained by separation include, but are not limited to, high value-added chemicals such as low-carbon olefins and aromatic hydrocarbons, and fuel oils such as gasoline, diesel oil and heavy oil, wherein the heavy oil can be recycled as a liquefied solvent.
The method provided by the invention can convert the solid waste plastics separated from garbage into products such as low-carbon olefin, aromatic hydrocarbon, fuel oil and the like by utilizing a series of process flows of anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis, product separation and the like, and realizes the high-value utilization of the waste plastics while eliminating white pollution.
For the sake of clarity, the following examples will be described in detail with reference to fig. 1 to 3.
Example 1
Example 1 is intended to illustrate the technique of anhydrous clean pretreatment of waste plastics:
Unlike the conventional water washing and cleaning method for wasting water resource, the method adopts the anhydrous cleaning technology to pretreat the waste plastic, and the treatment process flow is shown in figure 2, and the specific process comprises the following steps: firstly, shredding 100kg of recovered waste plastics into fragments of about 5cm by using a shredder, and conveying the plastic fragments into a winnowing and impurity removing system by using a screw conveyor; simultaneously blowing hot air into the winnowing and impurity removing system, separating residues such as waste steel wires, wood blocks, aluminum sheets, stones and the like in the winnowing and impurity removing device through a rotary valve below the winnowing and impurity removing system, and enabling waste plastic fragments to enter a dryer, drying by the hot air and then entering a gas-solid separator; the plastic fragments after shredding, winnowing, impurity removal and gas-solid separation are vertically lifted by adopting air flow and conveyed to a distributing valve, and then the waste plastic fragments are conveyed to a primary liquefying kettle by a screw propeller; the gas separated by gas-solid separation is introduced into a dust-removing and deodorizing system through an induced draft fan, and is exhausted through an exhaust pipe after being treated, and the dust-removing and deodorizing system consists of a bag-type dust remover, an air-cooling condenser and a UV photolysis deodorizing device.
The drying efficiency of the waste plastics can reach more than 94 percent and the impurity removal rate can reach more than 93 percent after the anhydrous clean pretreatment.
Example 2
Example 2 is intended to illustrate a multistage liquefaction technique of waste plastics:
The waste plastics subjected to anhydrous clean pretreatment is sent into a first-stage liquefaction kettle by a screw propeller, a special liquefaction solvent (80 wt% of cyclohexane and 20wt% of toluene) is added into the first-stage liquefaction kettle, and the waste plastics fragments and the liquefaction solvent are fully stirred and mixed and then enter a second-stage liquefaction kettle; stirring under the anaerobic condition, filtering to remove solid impurities, and feeding the solid impurities into a three-stage liquefaction kettle; after the liquefied liquid stays in the three-stage liquefying kettle for a period of time, the liquefied liquid is conveyed to a waste plastic liquefied liquid catalytic cracking system by a raw material pump.
The multi-stage liquefaction technology is adopted to carry out liquefaction tests on mixed waste plastics from different sources respectively, the test feeding amount is 20kg, the heating rate in the liquefaction process is 20 ℃/min, the stirring rate is 30rpm, and the liquefaction condition of the waste plastics in the test process is observed; the test results show that under the same liquefaction condition, the dissolution time of waste plastics from different sources is not much different, and the liquefaction rate is more than 98.0%. The specific test results are shown in table 1:
TABLE 1 multistage liquefaction Effect of Mixed waste plastics from different sources
Based on the results of the liquefaction test in table 1, the residence time of the liquefied liquid in the three-stage liquefaction tank is preferably set to 2 hours, taking into consideration the liquefaction dissolution condition of the plastic chips and the liquefaction treatment efficiency in combination.
Example 3
Example 3 is intended to illustrate the catalytic cracking technique of waste plastic liquefies:
the technology refers to the catalytic cracking technology in the oil refining industry, and in a self-designed fixed fluidized bed reactor, the self-developed catalytic cracking catalyst is used for carrying out high-efficiency catalytic conversion on waste plastic liquefied liquid to obtain gas and liquid products; the catalyst developed independently can improve the distribution of cracked products and the conversion rate of waste plastic liquefied liquid.
The structure of the fixed fluidized bed reactor used in this implementation is shown in fig. 3, and the apparatus is divided into four parts: the device comprises a feeding system (oil inlet and water inlet), a heating system (preheating and reaction), a product separation and collection system and a temperature control system; the raw materials required by the reaction are stored in an incubator, the constant temperature is set according to the properties of the raw materials in an experiment to improve the fluidity of the raw materials, and then the raw materials are pumped into a reactor by a piston pump; pumping distilled water into a preheating furnace by a horizontal pump to be heated and vaporized into water vapor, and then mixing the water vapor with the preheated oil sample and then entering a reactor; the lowest part of the reactor is an oil agent contact zone, the middle part is an inverted cone-shaped main reaction zone, the upper section is a cylindrical dilute phase zone, and reaction products and the catalyst are separated in the zone through an outlet filter; the product is condensed into a gas product and a liquid product through a first stage, the liquid product enters a separating funnel, and the gas product is collected through a drainage method after the second stage condensation.
The catalytic cracking catalyst used in the implementation consists of a catalyst carrier, an adhesive and active components, wherein the catalyst carrier is alumina and kaolin which respectively account for 30wt% and 20wt% of the total mass of the catalyst; the adhesive is aluminum sol, and accounts for 10wt% of the total mass of the catalyst; the active component is ZSM-5 molecular sieve, accounting for 40wt% of the total mass of the catalyst.
Under the reaction conditions that the reaction temperature is 500 ℃, the preheating box temperature is 80 ℃, the catalyst loading amount is 190g and the catalyst-to-oil ratio is 4, the commercial catalyst (reference agent) and the independently developed catalyst are adopted to carry out catalytic cracking test on waste plastic liquefied liquid, and the cracking product distribution of different types of catalysts is shown in table 2:
TABLE 2 distribution of waste Plastic liquefied cracking products for different types of catalysts
From the data in Table 2, it can be seen that the catalyst developed independently can increase the liquid product yield, reduce the coke yield and the material loss during the cracking reaction, and the conversion rate of the waste plastic liquefied liquid is as high as 95wt% or more, compared with the reference agent.
Example 4
Example 4 is intended to illustrate the hydrofining technique of waste plastic pyrolysis to produce oil:
the invention relates to a waste plastic pyrolysis oil hydrofining reaction system which is formed by connecting a hydrogenation pretreatment reactor and a hydrofining main reactor in series, wherein organic chloride and metal element impurities in pyrolysis oil are removed by the hydrogenation pretreatment reactor, and pretreated oil enters the hydrofining main reactor to deeply remove sulfur, nitrogen and oxide in the oil, so that product oil with qualified quality is finally obtained.
In the embodiment, the protecting agent, the demetallizing agent and the dechlorinating agent are filled in the hydrogenation pretreatment reactor in a layered manner, wherein the protecting agent and the demetallizing agent can remove metal impurities in the pyrolysis oil, the dechlorinating agent has excellent reaction selectivity, the removal rate of organic chloride is up to more than 99%, the removal rate of sulfur and nitride is lower, the toxicity of the chloride to the hydrofining catalyst can be effectively slowed down, and meanwhile, the shutdown of the reaction device due to the ammonium salt crystallization blocking is avoided.
In the embodiment, the protective agent is a commercial hydrogenation protective agent, and specifically comprises active components of NiO, moO 3 and carrier alumina, wherein the content of NiO is 2.5wt%, the content of MoO 3 is 10wt%, and the balance is the alumina carrier; the protective agent has high dirt interception capability.
In the embodiment, the demetallizing agent is a commercial hydrodemetallization agent, and specifically comprises active components of NiO, moO 3 and carrier alumina, wherein the content of NiO is 3wt%, the content of MoO 3 is 12wt%, and the balance is an alumina carrier; the demetallizing agent has a macroporous structure, and has strong asphaltene conversion capability, strong demetallizing capability and certain carbon residue conversion capability.
In the embodiment, the dechlorinating agent consists of a hydrodechlorination catalyst and an alkaline earth metal dechlorinating agent, the hydrodechlorination catalyst can convert organic chloride which is difficult to remove into HCl gas which is easy to remove, and then the organic chloride is timely removed by the alkaline earth metal dechlorinating agent, so that the concentration of HCl in a reaction system can be reduced, the toxicity of HCl to the catalyst is slowed down, and the corrosion to a reaction device is avoided; the hydrodechlorination catalyst consists of a carrier, an active component A, an active component B and an auxiliary agent, wherein the carrier is pseudo-boehmite (accounting for 80wt% of the total mass of the catalyst), the active component A is nickel oxide (accounting for 3wt% of the total mass of the catalyst), the active component B is molybdenum oxide (accounting for 15wt% of the total mass of the catalyst), and the auxiliary agent is phosphorus oxide (accounting for 2wt% of the total mass of the catalyst); the alkaline earth metal dechlorinating agent consists of a pseudo-boehmite carrier, active components of calcium oxide and magnesium oxide, wherein the calcium oxide accounts for 40wt% and the magnesium oxide accounts for 20wt% respectively, and the rest components are the pseudo-boehmite carrier.
In this example, the specific manner of the layered packing in the hydroprocessing reactor is as follows: 2g of protective agent, 3g of demetallization agent, 5g of hydrodechlorination catalyst and 15g of alkaline earth metal dechlorination agent are sequentially filled in the reactor from top to bottom, the total filling volume of the protective agent, the demetallization agent, the hydrodechlorination catalyst and the alkaline earth metal dechlorination agent in the hydrogenation pretreatment reactor is 30mL, and the total bulk density is 0.83g/cm 3.
In the embodiment, the hydrofining catalyst filled in the hydrofining main reactor is a NiMo type commercial diesel ultra-deep hydrofining catalyst, and the specific composition of the catalyst comprises 5wt% of NiO, 26wt% of MoO 3 and the balance of alumina carrier; the loading volume was 6mL and the bulk density was 0.83g/cm 3.
The hydrogenation pretreatment-hydrofining experiment of waste plastic pyrolysis generated oil is carried out under the reaction conditions of 350 ℃ of temperature, 5MPa of hydrogen partial pressure, 500:1 of hydrogen-oil volume ratio and 1.5h -1 of main reactor volume airspeed, all indexes of the refined oil can reach relevant standards, and the properties of the oil after hydrogenation pretreatment and hydrofining are shown in table 3:
TABLE 3 Properties of oil after hydrotreatment and hydrofinishing
Example 5
Example 5 is intended to illustrate the secondary pyrolysis technique of waste plastic pyrolysis oil:
The catalytic cracking technology in the conventional oil refining industry is used for deep processing of the waste plastic pyrolysis oil subjected to hydrogenation refining, so that the waste plastic pyrolysis oil with lower added value is converted into chemicals with high added value such as low-carbon olefin, aromatic hydrocarbon and the like. Optimizing the catalytic cracking reaction condition of the refined waste plastic pyrolysis oil can improve the distribution of cracked products and produce more low-carbon olefin and high-octane gasoline rich in aromatic hydrocarbon.
The optimization of the catalytic cracking reaction condition mainly adjusts the reaction temperature, and the reaction temperature is properly increased in the reaction process to promote the reaction severity, so that the generated product is promoted to undergo secondary cracking reaction, and the yield of the low-carbon olefin can be further improved, but the dry gas and coke yield can be increased when the reaction temperature is too high.
In this example, the catalyst used was a commercial catalytic cracking catalyst, the specific chemical composition was 46.3wt.% Al 2O3, 0.04wt.% Na 2 O, 0.27wt.% Fe 2O3, and the balance being the active component ZRP molecular sieve.
In this example, the reaction temperatures 600 ℃ (before optimization) and 620 ℃ (after optimization) were selected respectively to perform catalytic cracking experiments on the refined waste plastic pyrolysis oil, the reaction pressure was 0.10Mpa (gauge pressure), the residence time was 1.5s, the catalyst-to-oil ratio was 20, the water-to-oil ratio was 0.3, and the volume space velocity was 2h -1, and the product distribution and the gasoline properties before and after optimization of the reaction conditions were as shown in table 4:
TABLE 4 distribution of products and gasoline Properties of catalytic cracking of refined waste Plastic pyrolysis oil
As can be seen from the data in table 4, under the non-optimized catalytic cracking reaction conditions, the catalytic cracking products of the refined waste plastic pyrolysis oil are mainly gasoline, and the yield of the low-carbon olefins (ethylene and propylene) is lower; under the optimized catalytic cracking reaction condition, the yield of liquid products is reduced, the yield of low-carbon olefins is greatly increased, and the conversion rate of refined waste plastic pyrolysis oil is also increased.
Although the yield of gasoline is reduced under the optimized reaction conditions, the composition of gasoline hydrocarbon is improved, and the mass fraction of aromatic hydrocarbon is nearly doubled. By matching with a continuous multistage extraction aromatic extraction technology, aromatic hydrocarbons in the gasoline fraction are extracted, and mixed aromatic hydrocarbons (aromatic hydrocarbon products with more than C9) with purity up to 99.2wt% can be obtained, and the aromatic hydrocarbon content in raffinate oil is only 0.8wt%.
Example 6
Example 6 is intended to illustrate the product isolation technique:
The obtained products are separated by reference to the technologies of gas-liquid separation, aromatic hydrocarbon extraction, fraction cutting and the like in the oil refining industry, so that high-value-added low-carbon olefin, aromatic hydrocarbon and other high-value-added chemicals and fuel oil such as gasoline, diesel oil and heavy oil are obtained, wherein the heavy oil can be recycled as a liquefied solvent component.
Example 7
The polyolefin plastic and the polystyrene plastic are produced from the obtained low-carbon olefin, aromatic hydrocarbon and other chemicals by utilizing the existing polymerization technology, so that the recycling of the inferior waste plastic can be realized, the carbon emission in the chemical recycling process of the inferior waste plastic can be effectively reduced, and the realization of a double-carbon target is assisted.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (2)
1. A method for producing petrochemical products from waste plastics, comprising the steps of:
Waste plastics sequentially undergo anhydrous clean pretreatment, multistage liquefaction, catalytic pyrolysis, hydrofining, secondary pyrolysis and product separation to obtain different types of petrochemical products;
The specific process of the anhydrous clean pretreatment comprises the following steps: sequentially carrying out shredding, winnowing, impurity removal, drying and gas-solid separation on the waste plastics to obtain treated waste plastic fragments;
The components of the liquefaction solvent used for the multistage liquefaction comprise alkane and aromatic hydrocarbon; the alkane is one or more of cyclohexane, normal hexane, normal heptane and octane, the aromatic hydrocarbon is one or more of benzene, toluene, xylene and ethylbenzene, and the alkane accounts for 40-90 wt% of the total mass of the alkane and the aromatic hydrocarbon;
The specific process of multistage liquefaction comprises the following steps: delivering the waste plastics subjected to anhydrous clean pretreatment into a first-stage liquefaction kettle, adding a liquefaction solvent into the first-stage liquefaction kettle, and delivering the obtained mixture into a second-stage liquefaction kettle after the waste plastics and the liquefaction solvent are fully stirred and mixed; continuously stirring the mixture in a secondary liquefaction kettle under the anaerobic condition, filtering to remove solid impurities, and feeding the obtained liquefied liquid into a tertiary liquefaction kettle; the liquefied liquid stays in the three-stage liquefying kettle for a certain time and then is conveyed to a catalytic cracking process; wherein the stirring rates of the primary liquefaction kettle, the secondary liquefaction kettle and the tertiary liquefaction kettle are independently selected to be 20-50 rpm; the temperatures of the primary liquefaction kettle, the secondary liquefaction kettle and the tertiary liquefaction kettle are independently selected to be 170-210 ℃; the residence time of the liquefied liquid in the three-stage liquefying kettle is 80-160 min;
The catalytic cracking is performed in a fixed fluidized bed; the catalyst used for catalytic cracking comprises a catalyst carrier, an adhesive and an active component; the catalyst carrier is one or more of alumina, silica, kaolin and halloysite, the adhesive is one or more of silica sol, alumina sol, silica alumina sol and silica alumina gel, the active component is ZSM-5 molecular sieve and/or Y-type molecular sieve, the catalyst carrier accounts for 40-60 wt% of the total mass of the catalyst carrier, the adhesive and the active component, and the active component accounts for 10-40 wt% of the total mass of the catalyst carrier, the adhesive and the active component;
The temperature of the catalytic cracking is 400-600 ℃; the catalyst-oil ratio of the catalytic cracking is 3-6;
The equipment used for hydrofining comprises a hydrogenation pretreatment reactor and a hydrofining main reactor which are arranged in series; the hydrogenation pretreatment reactor is filled with a dechlorinating agent, a demetallizing agent and a protecting agent; the hydrofining main reactor is filled with a hydrofining catalyst;
The dechlorination agent comprises a hydrodechlorination catalyst and an alkaline earth metal dechlorination agent; the hydrodechlorination catalyst comprises a hydrodechlorination catalyst carrier, an active component A, an active component B and an auxiliary agent, wherein the active component A is a VIII metal oxide, the active component B is a VIB metal oxide, the auxiliary agent is one or more of a Ca oxide, a Cu oxide, a Ti oxide, a Zr oxide, a B oxide and a P oxide, the hydrodechlorination catalyst carrier is modified alumina, the active component A accounts for 1-5wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, the active component B accounts for 10-15wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent, and the auxiliary agent accounts for 1-5wt% of the total mass of the hydrodechlorination catalyst carrier, the active component A, the active component B and the auxiliary agent; the alkaline earth metal dechlorinating agent comprises pseudo-boehmite carrier and alkaline earth metal active component; the alkaline earth metal active components comprise calcium oxide and magnesium oxide, wherein the calcium oxide accounts for 30-50wt% of the total mass of the pseudo-boehmite carrier and the alkaline earth metal active components, and the magnesium oxide accounts for 15-25wt% of the total mass of the pseudo-boehmite carrier and the alkaline earth metal active components;
The components of the demetallizing agent comprise demetallizing agent carriers and demetallizing agent active components; the demetallizing agent carrier is an alumina carrier, the demetallizing agent active components are NiO and MoO 3, the NiO accounts for 1-5wt% of the total mass of the demetallizing agent carrier and the demetallizing agent active components, and the MoO 3 accounts for 5-15wt% of the total mass of the demetallizing agent carrier and the demetallizing agent active components;
the components of the protective agent comprise a protective agent carrier and a protective agent active component; the protective agent carrier is an alumina carrier, the protective agent active components comprise NiO and MoO 3, the NiO accounts for 1-5wt% of the total mass of the protective agent carrier and the protective agent active components, and the MoO 3 accounts for 5-15wt% of the total mass of the protective agent carrier and the protective agent active components;
The hydrofining catalyst comprises hydrofining catalyst carriers and hydrofining catalyst active components; the hydrofining catalyst carrier is an alumina carrier, the active components of the hydrofining catalyst are NiO and MoO 3, the NiO accounts for 2-10wt% of the total mass of the hydrofining catalyst carrier and the active components of the hydrofining catalyst, and the MoO 3 accounts for 20-30wt% of the total mass of the hydrofining catalyst carrier and the active components of the hydrofining catalyst;
The hydrofining temperature is 300-400 ℃; the hydrogen partial pressure of the hydrofining is 3-7 MPa; the volume ratio of the hydrofined hydrogen oil is (400-600) 1; the volume airspeed of the hydrofining is 1-2h -1;
The components of the catalyst used for the secondary cracking comprise Al 2O3、Na2O、Fe2O3 and a ZRP molecular sieve; the Al 2O3 accounts for 40-50wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve, the Na 2 O accounts for 0.01-0.1wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve, and the Fe 2O3 accounts for 0.2-0.35wt% of the total mass of the Al 2O3、Na2O、Fe2O3 and the ZRP molecular sieve;
The temperature of the secondary pyrolysis is 610-630 ℃; the reaction pressure of the secondary cracking is 0.05-0.2 MPa; the ratio of the agent to the oil of the secondary cracking is 10-30; the water-oil ratio of the secondary pyrolysis is 0.05-0.5; the volume airspeed of the secondary pyrolysis is 0.5-5 h -1; the residence time of the secondary cracking is 0.5-3 s.
2. The method of claim 1, wherein the specific process of the anhydrous clean pretreatment further comprises:
and dedusting and deodorizing the gas separated in the gas-solid separation process.
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| CN115487838A (en) * | 2022-08-05 | 2022-12-20 | 中国石油化工股份有限公司 | Hydrodechlorination catalyst, catalyst system and hydrofining process method of high-chlorine-content waste plastic cracking oil |
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