CN118215723A - Refining method of waste plastic pyrolysis oil using sulfur source and molybdenum-based hydrogenation catalyst and continuous operation method thereof - Google Patents
Refining method of waste plastic pyrolysis oil using sulfur source and molybdenum-based hydrogenation catalyst and continuous operation method thereof Download PDFInfo
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- CN118215723A CN118215723A CN202280073938.9A CN202280073938A CN118215723A CN 118215723 A CN118215723 A CN 118215723A CN 202280073938 A CN202280073938 A CN 202280073938A CN 118215723 A CN118215723 A CN 118215723A
- Authority
- CN
- China
- Prior art keywords
- waste plastic
- sulfur
- pyrolysis oil
- plastic pyrolysis
- oil
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 239000011593 sulfur Substances 0.000 title claims abstract description 149
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 149
- 239000002699 waste material Substances 0.000 title claims abstract description 108
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 107
- 229920003023 plastic Polymers 0.000 title claims abstract description 101
- 239000004033 plastic Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 68
- 238000007670 refining Methods 0.000 title claims abstract description 61
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 46
- 239000011733 molybdenum Substances 0.000 title claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 42
- 239000006227 byproduct Substances 0.000 claims abstract description 35
- 239000012495 reaction gas Substances 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000000047 product Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- 239000007789 gas Substances 0.000 claims description 52
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 38
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 20
- 230000000694 effects Effects 0.000 claims description 17
- 150000002739 metals Chemical class 0.000 claims description 12
- 150000002894 organic compounds Chemical class 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 description 185
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 239000012535 impurity Substances 0.000 description 39
- 239000000460 chlorine Substances 0.000 description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 21
- 229910052801 chlorine Inorganic materials 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 150000002431 hydrogen Chemical class 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 230000009849 deactivation Effects 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000010920 waste tyre Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- QMMFVYPAHWMCMS-UHFFFAOYSA-N dimethyl monosulfide Natural products CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical group CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 3
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GUMUOYSOENKSEG-UHFFFAOYSA-N 2-methylpent-3-enenitrile Chemical compound CC=CC(C)C#N GUMUOYSOENKSEG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PLUBXMRUUVWRLT-UHFFFAOYSA-N Ethyl methanesulfonate Chemical compound CCOS(C)(=O)=O PLUBXMRUUVWRLT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- MBABOKRGFJTBAE-UHFFFAOYSA-N methyl methanesulfonate Chemical compound COS(C)(=O)=O MBABOKRGFJTBAE-UHFFFAOYSA-N 0.000 description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 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
- 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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- 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
- C10G45/04—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 characterised by the catalyst used
-
- 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
- C10G45/04—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 characterised by the catalyst used
- C10G45/06—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a refining method of waste plastic pyrolysis oil, which comprises the following steps: (S1) mixing the waste plastic pyrolysis oil with a sulfur source to prepare a mixed oil fraction; (S2) hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) in the presence of a molybdenum-based hydrogenation catalyst; and (S3) removing the hydrotreated by-product from the product of (S2) to obtain a refined oil.
Description
Technical Field
The invention relates to a refining method of waste plastic pyrolysis oil by using a sulfur source and a molybdenum-based hydrogenation catalyst and a continuous operation method thereof.
Background
Waste plastics produced from petroleum as a raw material are low in recyclability and are mostly disposed of as waste. These forms of waste are decomposed in their natural state, and as the decomposition takes a long time, soil is polluted and serious environmental pollution is caused. As a method of recycling waste plastics, the waste plastics may be pyrolyzed and converted into usable oil (usable oil), which is called waste plastics pyrolysis oil.
However, since pyrolysis oil obtained by pyrolyzing waste plastics has a high impurity content such as chlorine, nitrogen, and metals as compared with oil manufactured from crude oil by a conventional method, it may not be directly used as high value-added fuel such as gasoline and diesel, and should be subjected to refining treatment.
As a refining method for removing impurities such as chlorine, nitrogen, and metals contained in waste plastic pyrolysis oil, a hydrotreating method of reacting waste plastic pyrolysis oil with hydrogen (H 2) in the presence of a hydrotreating catalyst, a method of removing chlorine contained in waste plastic pyrolysis oil by adsorption using a chlorine adsorbent, and the like are known.
In the hydrotreating method, the waste plastic pyrolysis oil has a high content of impurities such as metals, thereby affecting the catalyst in the hydrotreating process, and thus, the catalytic activity is rapidly reduced, so that the process may not be stably performed for a long period of time.
Accordingly, there is a need for a waste plastic pyrolysis oil refining technology that improves the catalytic activity in the waste plastic pyrolysis oil hydrotreating process and allows the process to operate stably for a long period of time.
[ Related technical literature ]
[ Patent literature ]
Japanese patent publication No. 2003-034794 (2/7/2003)
Disclosure of Invention
Technical problem
It is an object of the present invention to provide a refining method of waste plastic pyrolysis oil, which can produce refined oil having remarkably low contents of impurities such as chlorine, nitrogen, oxygen, and metals.
It is another object of the present invention to provide a continuous operation method of a waste plastic pyrolysis oil refining apparatus, which maintains the activity of a molybdenum-based sulfide hydrogenation catalyst by continuously supplying sulfur from a sulfur source, thereby allowing the refining apparatus to operate for a long period of time.
Technical proposal
In one general aspect, a method for refining pyrolysis oil of waste plastics includes: (S1) mixing the waste plastic pyrolysis oil with a sulfur source to prepare a mixed oil fraction (mixed oil fraction); (S2) hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) in the presence of a molybdenum-based hydrogenation catalyst; and (S3) removing the hydrotreated by-product from the product of (S2) to obtain a refined oil.
In an exemplary embodiment of the invention, the sulfur source may include a sulfur-containing oil fraction (sulfur-containing oil fraction).
In an exemplary embodiment of the invention, the mixed oil fraction may include greater than 100ppm sulfur.
In an exemplary embodiment of the present invention, the content of the sulfur-containing oil fraction may be less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil.
In an exemplary embodiment of the present invention, the content of the sulfur-containing oil fraction may be less than 50 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil.
In one exemplary embodiment of the present invention, the sulfur source may include one or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds (sulfonate-based compounds) and sulfate-based compounds (sulfate-based compounds).
In an exemplary embodiment of the present invention, the reaction gas of (S2) may further include hydrogen sulfide gas (H 2 S).
In one exemplary embodiment of the present invention, hydrogen sulfide gas (H 2 S) may be separated from the by-product of the hydrotreatment removed in (S3) and then supplied again.
In one exemplary embodiment of the present invention, the molybdenum-based hydrogenation catalyst may be a catalyst in which a molybdenum-based metal or a metal including any one or two or more selected from nickel, cobalt and tungsten and the molybdenum-based metal are supported on a support (supported).
In one exemplary embodiment of the invention, the molybdenum-based hydrogenation catalyst may comprise a molybdenum-based sulfide hydrogenation catalyst.
In an exemplary embodiment of the present invention, (S2) may be performed at a pressure of 200 bar or less.
In one exemplary embodiment of the present invention, (S2) may be performed at a temperature of 300 ℃ or more and less than 450 ℃.
In one exemplary embodiment of the invention, (S2) may be performed at a liquid hourly space velocity (liquid hourly space velocity, LHSV) of 0.1 hours -1 to 5 hours -1.
In another general aspect, a continuous operation method of a waste plastic pyrolysis oil refining apparatus includes: (S1) mixing the waste plastic pyrolysis oil with a sulfur source to prepare a mixed oil fraction; (S2) hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) and hydrogen sulfide gas (H 2 S) in the presence of a molybdenum-based sulfide hydrogenation catalyst at a pressure of 200 bar or less; and (S3) removing the hydrotreated by-product from the product of (S2) to obtain a refined oil, wherein the hydrogen sulfide gas (H 2 S) in (S2) is separated from the hydrotreated by-product of (S3) and fed again.
In one exemplary embodiment of the invention, the activity of the molybdenum-based sulfide hydrogenation catalyst may be maintained by continuously feeding sulfur from a sulfur source.
In an exemplary embodiment of the invention, the mixed oil fraction may include greater than 100ppm sulfur. In an exemplary embodiment of the invention, the sulfur source may include a sulfur-containing oil fraction.
In an exemplary embodiment of the present invention, the content of the sulfur-containing oil fraction may be less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil.
In one exemplary embodiment of the present invention, the sulfur source may include one or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds.
Advantageous effects
The refining method of waste plastic pyrolysis oil according to the present invention can produce refined oil having remarkably low contents of impurities such as chlorine, nitrogen, oxygen, and metals.
Further, the continuous operation method of the waste plastic pyrolysis oil refining apparatus according to the present invention can maintain the activity of the molybdenum-based sulfide hydrogenation catalyst by continuously supplying sulfur from a sulfur source, thereby continuously operating the refining apparatus for a long period of time.
Drawings
The foregoing and other objects, features and advantages of the invention will be apparent from the following description of preferred embodiments, taken in conjunction with the accompanying drawings in which:
Fig. 1 shows a refining apparatus of pyrolysis oil of waste plastics according to the present invention, including: a mixer in which the waste plastic pyrolysis oil and the sulfur-containing oil fraction are introduced and mixed; a reactor in which a mixed oil fraction is introduced from the mixer, a reaction gas including hydrogen (H 2) is introduced, and hydrotreating is performed in the presence of a molybdenum-based hydrogenation catalyst; and a process for separating the by-product of the hydrotreatment from the refined oil from the reactor,
Fig. 2 shows a refining apparatus of waste plastic pyrolysis oil, which is identical to the refining apparatus of waste plastic pyrolysis oil of fig. 1, except that a sulfur-containing organic compound is introduced thereto in place of the sulfur-containing oil fraction,
Fig. 3 shows a refining apparatus of waste plastic pyrolysis oil, which is identical to the refining apparatus of waste plastic pyrolysis oil of fig. 1, except that the reaction gas further includes hydrogen sulfide gas (H 2 S),
Fig. 4 shows a refining apparatus of waste plastic pyrolysis oil, which is the same as the refining apparatus of waste plastic pyrolysis oil of fig. 3, except that a gas separation unit separating hydrogen sulfide gas (H 2 S) from byproducts and a recycling line re-supplying the separated hydrogen sulfide gas (H 2 S) to the reactor are further included.
Detailed Description
The drawings shown in the present specification are provided by way of example so that the inventive concept may be fully conveyed to those skilled in the art. Thus, the invention is not limited to the figures provided, but may be embodied in many different forms and the figures may be exaggerated in order to make the spirit of the invention clear.
Unless otherwise defined, technical and scientific terms used in the present specification have the general meaning as understood by one of ordinary skill in the art to which the present invention belongs, and descriptions of known functions and configurations that obscure the gist of the present invention will be omitted in the following description and drawings.
As used herein, the singular forms of terms may also be intended to include the plural forms unless otherwise indicated.
As used in this specification, a numerical range includes all values within that range including the lower and upper limits, forms and spans logically derived increments within the defined range, all double limit values (double limited value), and all possible combinations of upper and lower limits within the numerical range defined in different forms. Unless otherwise defined in the specification of the present invention, values that may be outside the numerical range due to experimental errors or rounding of the values are also included in the numerical range defined.
The term "comprising" as referred to in this specification is an open-ended description having the meaning equivalent to terms such as "providing," "comprising," "having," or "characterized by," and does not exclude elements, materials, or processes not further listed.
Unless otherwise defined, the unit% as used in the present specification, not specifically mentioned, refers to weight%.
Unless otherwise defined, the unit ppm not specifically mentioned as used in the present specification means mass ppm.
Unless otherwise defined, boiling point as used in this specification refers to boiling point at 1 atmosphere.
Since pyrolysis oil obtained by pyrolysis of waste plastics has a high impurity content such as chlorine, nitrogen, and metals as compared with oil manufactured from crude oil by a conventional method, it may not be directly used as high value-added fuel such as gasoline and diesel, and should be subjected to refining treatment.
As a refining method for removing impurities such as chlorine, nitrogen, and metals contained in waste plastic pyrolysis oil, a hydrotreating method of reacting waste plastic pyrolysis oil with hydrogen (H 2) in the presence of a hydrotreating catalyst, a method of removing chlorine contained in waste plastic pyrolysis oil by adsorption using a chlorine adsorbent, and the like are known.
In the hydrotreating method, the waste plastic pyrolysis oil has a high content of impurities such as metals, thereby affecting the catalyst in the hydrotreating process, and thus, the catalytic activity is rapidly reduced, so that the process may not be stably performed for a long period of time.
Accordingly, the refining method of waste plastic pyrolysis oil according to the present invention may use the manner described later, thereby producing refined oil having remarkably low contents of impurities such as chlorine, nitrogen, oxygen, and metals, and may continuously operate the refining apparatus for a long period of time by continuously supplying sulfur from a sulfur source to maintain the activity of the molybdenum-based sulfide hydrogenation catalyst.
The invention provides a refining method of waste plastic pyrolysis oil, which comprises the following steps: (S1) mixing the waste plastic pyrolysis oil with a sulfur source to prepare a mixed oil fraction; (S2) hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) in the presence of a molybdenum-based hydrogenation catalyst; and (S3) removing the hydrotreated by-product from the product of (S2) to obtain a refined oil.
Waste plastic pyrolysis oil refers to a hydrocarbon oil mixture produced by pyrolysis of waste plastic. Here, the waste plastics may include solid or liquid wastes related to the synthetic polymer compounds, such as waste synthetic resin, waste synthetic fiber, waste synthetic rubber, and waste vinyl resin (WASTE VINYL). The hydrocarbon oil mixture may include impurities such as chlorine compounds, nitrogen compounds, and metal compounds, may include impurities in the form of compounds that bond (bonded) chlorine, nitrogen, or metal in hydrocarbons in addition to hydrocarbon oils, and may include hydrocarbons in the form of olefins.
As a specific example, the waste plastic pyrolysis oil may contain 300ppm or more of nitrogen and 30ppm or more of chlorine, and may contain 20% by volume or more of olefins (1 atmosphere, 25 ℃) and 1% by volume or more of conjugated dienes (1 atmosphere, 25 ℃), but the content of impurities is only one specific example that may be included in the waste plastic pyrolysis oil, and the composition of the waste plastic pyrolysis oil is not limited thereto.
The sulfur source is a sulfur source that can continuously supply a sulfur component in the refining process.
In (S1), waste plastic pyrolysis oil and a sulfur source are mixed to prepare a mixed oil fraction, thereby suppressing deactivation of a molybdenum-based hydrogenation catalyst due to lack of a sulfur source in a refining process and operation at high temperature and maintaining catalytic activity.
In an exemplary embodiment of the invention, the sulfur source may include a sulfur-containing oil fraction. The sulfur-containing oil fraction refers to an oil fraction formed from sulfur-containing hydrocarbons obtained from crude oil as a raw material. The sulfur-containing oil fraction is not particularly limited as long as it is a sulfur-containing oil fraction, and may be, for example, light gas oil, straight run naphtha (STRAIGHT NAPHTHA), vacuum naphtha, pyrolysis naphtha, straight run kerosene, vacuum kerosene, pyrolysis kerosene, straight run diesel, vacuum diesel, pyrolysis diesel, sulfur-containing waste tire oil fraction, or the like, or any mixture thereof.
According to one specific example, the waste tire oil fraction is included as a sulfur-containing oil fraction to convert high content of sulfur contained in the waste tire into an oil fraction having hydrocarbons, and thus may be preferable as a sulfur source of the waste plastic pyrolysis oil. In addition, for reduced environmental loads due to recycling scrap tires and long-term maintenance of catalytic activity, it is advantageous to convert (divert) the scrap tire oil fraction to the sulfur source of the waste plastic pyrolysis oil.
Specifically, the sulfur-containing oil fraction may be Light Gas Oil (LGO) having a specific gravity (gravity) of 0.7 to 1. When in use, the catalyst can be uniformly mixed with waste plastic pyrolysis oil, and has high hydrotreating efficiency. Specifically, the specific gravity may be 0.75 to 0.95, and more specifically, may be 0.8 to 0.9. The sulfur-containing oil fraction may include greater than 100ppm sulfur. When the content of the sulfur component is 100ppm or less, the content of the sulfur component provided is small, so that the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may not be significant. Specifically, the content of the sulfur component may be 800ppm or more, more specifically 8000ppm or more, and 200000ppm or less, without limitation.
In an exemplary embodiment of the invention, the mixed oil fraction may include greater than 100ppm sulfur. As with the sulfur-containing oil fraction, when the content of the sulfur component is 100ppm or less, the content of the sulfur component provided is small, and thus the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may not be significant. Specifically, the content of the sulfur component may be 800ppm or more, more specifically 8000ppm or more, and 200000ppm or less, without limitation.
In an exemplary embodiment of the present invention, the content of the sulfur-containing oil fraction may be less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil. Specifically, the sulfur-containing oil fraction may be present in an amount of less than 70 parts by weight, more specifically, less than 50 parts by weight, and more than 25 parts by weight, without limitation. Since the content of the sulfur-containing oil fraction is less than 100 parts by weight, the concentration of chlorine (Cl) or nitrogen (N) contained in the waste plastic pyrolysis oil may be low to control the rate of production of ammonium salt (NH 4 Cl) and improve process stability.
In one exemplary embodiment of the present invention, the sulfur source may include one or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds. Specifically, the sulfur source may include one or a mixture of two or more selected from disulfide, dimethyl sulfide, polysulfide, dimethyl sulfoxide (DMSO), methyl mesylate, ethyl mesylate, propyl sulfonate (propylsulfonate), propenyl sulfonate, propenyl cyano ethane sulfonate, vinyl sulfate (ethylene sulfate), dicycloglyoxal sulfate (bicycloglyoxal sulfate), and methyl sulfate, which are shown as examples only, and the present invention is not limited thereto.
The content of the sulfur-containing organic compound may be 1 to 25 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil. Specifically, the content thereof may be 5 to 20 parts by weight, more specifically, 10 to 15 parts by weight. When the content thereof is less than 1 part by weight, the content of the sulfur component is small, so that the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may not be significant.
(S2) step: hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) in the presence of a molybdenum-based hydrogenation catalyst refers to a hydrogenation reaction in which hydrogen (H 2) is added to the hydrocarbon oil fraction included in the mixed oil fraction. In particular, hydrotreating may refer to conventionally known hydrotreating including hydrodesulfurization, hydrocracking, hydrodechlorination, hydrodenitrogenation, and hydrodemetallization. By hydrotreating to remove a portion of impurities including chlorine (Cl) and nitrogen (N) and olefins, other metal impurities can be removed and byproducts including these impurities are produced.
The by-products are produced by reacting chlorine (Cl), nitrogen (N), sulfur (S), or oxygen (O), which are impurities contained in the waste plastic pyrolysis oil, with hydrogen (H 2), and specifically may include hydrogen sulfide gas (H 2 S), hydrogen chloride (HCl), ammonia (NH 3), water vapor (H 2 O), and the like, and further may include unreacted hydrogen (H 2), trace methane (CH 4), ethane (C 2H5), or the like.
In one exemplary embodiment of the present invention, the molybdenum-based hydrogenation catalyst may be a catalyst in which a molybdenum-based metal or a metal including any one or two or more selected from nickel, cobalt and tungsten and the molybdenum-based metal are supported on a carrier. Molybdenum-based hydrogenation catalysts have high catalytic activity in hydrotreating and may be used alone or as a binary-based catalyst in combination with metals such as nickel, cobalt and tungsten, as desired.
As the carrier, alumina, silica-alumina, titania, molecular sieve, zirconia, aluminum phosphate, carbon, niobium oxide (niobia) or a mixture thereof may be used, but is not limited thereto.
In one exemplary embodiment of the invention, the molybdenum-based hydrogenation catalyst may comprise a molybdenum-based sulfide hydrogenation catalyst. For example, molybdenum sulfide (MoS) or molybdenum disulfide (MoS 2) may be included, but the present invention is not limited thereto, and may include known molybdenum-based sulfide hydrogenation catalysts.
In an exemplary embodiment of the present invention, the reaction gas may further include hydrogen sulfide gas (H 2 S). The hydrogen sulfide gas (H 2 S) included in the reaction gas may be used as a sulfur source and, together with the sulfur source mixed with the pyrolysis oil of the waste plastics, regenerate the activity of the molybdenum-based hydrogenation catalyst deactivated in the refining process.
(S3) step: the by-product of the hydrotreatment is removed from the product of (S2) to obtain a refined oil, and finally a high-quality refined oil reduced in impurities can be obtained from the mixed oil fraction.
As described above, the by-products are generated by reacting the impurity chlorine (Cl), nitrogen (N), sulfur (S), or oxygen (O) contained in the waste plastic pyrolysis oil with hydrogen (H 2), and specifically, the by-products may include hydrogen sulfide gas (H 2 S), hydrogen chloride (HCl), ammonia (NH 3), water vapor (H 2 O), etc., and further, may include unreacted hydrogen (H 2), trace methane (CH 4), ethane (C 2H5), etc.
As a method of removing the by-product, for example, the by-product may be removed from the product of (S2) by a method of discharging (exhausting) a mixed gas, which is described only as an example of the method, to which the present invention is not limited. By this method, a high quality refined oil with reduced impurities can be finally obtained from the mixed oil fraction.
In one exemplary embodiment of the present invention, hydrogen sulfide gas (H 2 S) may be separated from the by-product of the hydrotreatment removed in (S3) and then supplied again. Specifically, for the hydrogen sulfide gas (H 2 S) contained in the reaction gas of (S2), the hydrogen sulfide gas (H 2 S) is separated from the by-product of the hydrotreatment removed in (S3) by the adsorption removal step, and then supplied again to be used as the hydrogen sulfide gas (H 2 S) of (S2). In the adsorption removal step, an adsorbent such as zeolite, carbon, and alumina may be used to separate hydrogen sulfide gas (H 2 S) from the by-products, and hydrogen gas (H 2) may also be separated.
In an exemplary embodiment of the present invention, the hydrotreatment of (S2) may be performed at a pressure of 200 bar or less. When performed at a pressure of 200 bar or less, the generation of NH 4 Cl impurities can be suppressed, thereby suppressing the pressure difference increase rate (DIFFERENTIAL PRESSURE INCREASE RATE) in the reactor and improving the reaction stability. Specifically, it may be performed at a pressure of 150 bar or less, more specifically, 100 bar or less, and without limitation, at a pressure of 60 bar or more.
In one exemplary embodiment of the present invention, the hydrotreatment of (S2) may be performed at a temperature above 300 ℃ and less than 450 ℃. When this range is satisfied, the hydrotreating efficiency can be improved. Specifically, it may be performed at a temperature of 320 to 430 ℃, more specifically, it may be performed at a temperature of 350 to 400 ℃.
In one exemplary embodiment of the present invention, the hydrotreating of (S2) may be performed at a Liquid Hourly Space Velocity (LHSV) of from 0.1 hour -1 to 5 hours -1. When the LHSV satisfies this range, refined oil from which impurities such as chlorine, nitrogen, or metals are removed can be obtained more stably. In particular, it may be performed at an LHSV of 0.3 hours -1 to 3 hours -1, more particularly at an LHSV of 0.5 hours -1 to 1.5 hours -1.
In one exemplary embodiment of the present invention, the refined oil obtained by the refining method of the pyrolysis oil of waste plastics may include less than 10ppm of chlorine (Cl), less than 100ppm of nitrogen (N), and less than 50ppm of sulfur (S). Further, the refined oil obtained may include less than 3 weight percent olefins and less than 0.5 weight percent conjugated dienes.
The above-described method for refining waste plastic pyrolysis oil may be performed by pyrolysis oil refining equipment.
The pyrolysis oil refining apparatus may include a mixer in which the waste plastic pyrolysis oil and the sulfur source are introduced and mixed to prepare a mixed oil fraction; and a reactor in which the mixed oil fraction is introduced from the mixer, a reaction gas including hydrogen (H 2) is introduced, and hydrotreating is performed in the presence of a molybdenum-based hydrogenation catalyst. Further, the configuration of the refining apparatus is not necessarily limited thereto, and the refining apparatus may be configured by including or changing other conventionally known configurations.
The mixer may comprise a conventional mixer for uniform mixing. The pyrolysis oil and sulfur source are introduced into a mixer and stirred to produce a uniform mixed oil fraction.
The reactor may comprise a reaction zone in which a molybdenum-based hydrogenation catalyst is provided. In the reaction zone, dechlorination, denitrification, desulfurization or demetallization reactions may be performed. The mixed oil fraction is introduced into a reactor, hydrotreated in the presence of a hydrotreating catalyst, and a reaction for removing part of olefins and metal impurities can be performed simultaneously.
The reactor is provided with a gas outlet to which the by-product of the hydrotreatment can be discharged (discharged).
In addition, the refining apparatus may further include a gas separation unit in which a byproduct is introduced and hydrogen sulfide gas (H 2 S) is separated from the hydrotreated byproduct; and a recycle line in which the hydrogen sulfide gas (H 2 S) separated from the gas separation unit is supplied again to the reactor. The gas separation unit may include an adsorbent, and separate hydrogen sulfide gas (H 2 S) from the by-product with the adsorbent. In addition, unreacted hydrogen (H 2) may be separated.
As shown in fig. 4, the hydrogen sulfide gas (H 2 S) separated from the gas separation unit may be supplied again to the reactor through a recycle line. In addition, unreacted hydrogen (H 2) may be supplied again to the reactor through a recycle line. Although not shown in fig. 4, the recycle line in which the hydrogen sulfide gas (H 2 S) and the hydrogen gas (H 2) are recycled may further include a washing unit in which washing is performed with water. By further including the washing unit, impurities such as hydrogen chloride (HCl) and ammonia (NH 3) remaining in the hydrogen sulfide gas (H 2 S) and the hydrogen gas (H 2) are dissolved in water and removed so that the high-purity hydrogen sulfide gas (H 2 S) and the hydrogen gas (H 2) can be supplied again to the reactor.
In addition, the present invention provides a continuous operation method of a waste plastic pyrolysis oil refining apparatus, comprising: (S1) mixing the waste plastic pyrolysis oil with a sulfur source to prepare a mixed oil fraction; (S2) hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) and hydrogen sulfide gas (H 2 S) in the presence of a molybdenum-based sulfide hydrogenation catalyst at a pressure of 200 bar or less; and (S3) removing the hydrotreated by-product from the product of (S2) to obtain a refined oil, wherein the hydrogen sulfide gas (H 2 S) in (S2) is separated from the hydrotreated by-product of (S3) and fed again.
The hydrotreatment can be carried out at a pressure of 200 bar or less. When performed at a pressure of 200 bar or less, the generation of NH 4 Cl impurities can be suppressed, thereby suppressing the rate of increase in the pressure difference in the reactor and improving the reaction stability. Specifically, it may be performed at a pressure of 150 bar or less, more specifically, 100 bar or less, and without limitation, at a pressure of 60 bar or more.
The hydrogen sulfide gas (H 2 S) included in the reaction gas may be used as a sulfur source and, together with the sulfur source mixed with the waste plastic pyrolysis oil, regenerate the activity of the molybdenum-based hydrogenation catalyst deactivated in the reaction process.
The hydrogen sulfide gas (H 2 S) may be separated from the by-products of the hydrotreatment removed in (S3) and then supplied again. Specifically, for the hydrogen sulfide gas (H 2 S) contained in the reaction gas of (S2), the hydrogen sulfide gas (H 2 S) is separated from the by-product of the hydrotreatment removed in (S3) by the adsorption removal step, and then supplied again to be used as the hydrogen sulfide gas (H 2 S) of (S2). The amount of hydrogen sulfide gas (H 2 S) separately fed can be reduced to improve the process efficiency, and the cost of disposing of the by-products of the hydrogenation reaction can be reduced to improve the economic viability.
In one exemplary embodiment of the invention, the activity of the molybdenum-based sulfide hydrogenation catalyst may be maintained by continuously feeding sulfur from a sulfur source. The sulfur source is used as a sulfur source for continuously supplying a sulfur component in the refining process, and can suppress deactivation of the molybdenum-based sulfide hydrogenation catalyst and regenerate the catalytic activity. With the regeneration of catalytic activity, the waste plastic pyrolysis oil refining equipment can stably and continuously run for a long time.
In an exemplary embodiment of the invention, the mixed oil fraction may include greater than 100ppm sulfur. When the content of the sulfur component is 100ppm or less, the content of the sulfur component provided is small, so that the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may not be significant. Specifically, the content of the sulfur component may be 800ppm or more, more specifically 8000ppm or more, and not limitatively 200000ppm or less.
In an exemplary embodiment of the invention, the sulfur source may include a sulfur-containing oil fraction. The sulfur-containing oil fraction refers to an oil fraction formed from sulfur-containing hydrocarbons obtained from crude oil as a raw material. The sulfur-containing oil fraction is not particularly limited as long as it is a sulfur-containing oil fraction, and may be, for example, light gas oil, straight run naphtha, vacuum naphtha, pyrolysis naphtha, straight run kerosene, vacuum kerosene, pyrolysis kerosene, straight run diesel, vacuum diesel, pyrolysis diesel, sulfur-containing waste tire oil fraction, or the like, or any mixture thereof.
In an exemplary embodiment of the present invention, the content of the sulfur-containing oil fraction may be less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil. Specifically, the sulfur-containing oil fraction may be present in an amount of less than 70 parts by weight, more specifically, less than 50 parts by weight, and more than 25 parts by weight, without limitation. Since the content of the sulfur-containing oil fraction is less than 100 parts by weight, nitrogen (N) impurities can be effectively removed even if hydrotreating is performed at a low pressure of 100 bar or less. When the content of the sulfur-containing oil fraction is more than 100 parts by weight, the nitrogen (N) impurity removal efficiency is lowered in the hydrotreating performed at a low pressure of 100 bar or less. Further, when the hydrotreatment is performed at a high pressure of 100 bar or more to remove impurities, the NH 4 Cl yield increases, thereby deteriorating the reaction stability (deteriorate).
In one exemplary embodiment of the present invention, the sulfur source may include one or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds. Specifically, the sulfur source may include one or a mixture of two or more selected from dimethyl disulfide, dimethyl sulfide, polysulfide, dimethyl sulfoxide (DMSO), methyl methanesulfonate, ethyl methanesulfonate, propyl sulfonate, propenyl sulfonate, propenyl cyano ethane sulfonate, vinyl sulfate, dicycloglyoxal sulfate, and methyl sulfate, and is not limited thereto.
The content of the sulfur-containing organic compound may be 1 to 25 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil. Specifically, the content of the sulfur-containing organic compound may be 5 to 20 parts by weight, more specifically, 10 to 15 parts by weight. When the content of the sulfur-containing organic compound is less than 1 part by weight, the content of the sulfur component is small, so that the effect of preventing deactivation of the molybdenum-based hydrogenation catalyst may not be significant.
For matters not further described in the continuous operation method for the waste plastic pyrolysis oil refining apparatus, reference is made to the above description of the waste plastic pyrolysis oil refining method.
Hereinafter, the present invention will be described in detail by way of examples, however, the examples are for describing the content of the present invention in more detail, and the scope of the claims is not limited to the following examples.
Example 1
Light gas oil (R-LGO) having a specific gravity of 0.85851, specifically, a sulfur-containing oil fraction containing 20000ppm sulfur was used as a sulfur source.
A hydrocarbon oil mixture containing nitrogen (N) at 200ppm or more, chlorine (Cl) at 30ppm or more, an olefin at 20% by volume or more, and a high concentration impurity of a conjugated diene at 1% by volume or more is used as the waste plastic pyrolysis oil.
70 Parts by weight of a sulfur-containing oil fraction was placed in a mixer with respect to 100 parts by weight of waste plastic pyrolysis oil to prepare a mixed oil fraction. The mixed oil fraction produced by the mixer was placed in a reactor, a reaction gas including hydrogen (H 2) was placed in the reactor, and the reactor was operated to conduct hydrotreatment. Specifically, the mixed oil fraction was placed in a reactor, and then hydrotreated with a reaction gas including hydrogen (H 2) at 350℃and 60 bar in the presence of a NiMoS/gamma-Al 2O3 hydrotreating catalyst. Byproducts were produced by hydrotreating and included hydrogen sulfide gas (H 2 S), hydrogen chloride (HCl), ammonia (NH 3), water vapor (H 2 O), and trace amounts of methane (CH 4) and ethane (C 2H6). The by-product is discharged to the gas outlet of the reactor, and finally high-quality refined oil from which impurities are removed is obtained from the reactor.
Example 2
The hydrotreating was performed under the same conditions as in example 1, except that the hydrotreating was performed under 380 ℃ in the presence of a hydrotreating catalyst. In addition, byproducts in the fluid removed from the reactor are placed in a gas separation unit. Hydrogen sulfide gas (H 2 S) and hydrogen gas (H 2) are separated from the byproducts by zeolite adsorbents in a gas separation unit. The reaction was performed under the same conditions as in example 1, except that the above-described separated hydrogen sulfide gas (H 2 S) and hydrogen gas (H 2) were supplied again to the reactor through the recycle line to be contained in the reaction gas and used, thereby finally obtaining purified oil from which impurities were removed.
Example 3
Refined oil from which impurities were removed was finally obtained by carrying out the reaction under the same conditions as in example 1, except that 50 parts by weight of the sulfur-containing oil fraction was put into a mixer with respect to 100 parts by weight of the waste plastic pyrolysis oil.
Example 4
Refined oil from which impurities had been removed was finally obtained by carrying out the reaction under the same conditions as in example 1, except that the hydrotreatment was carried out in the presence of a hydrotreating catalyst at 320℃and 90 bar.
Example 5
A high-quality refined oil from which impurities had been removed was finally obtained by carrying out the reaction under the same conditions as in example 1, except that a sulfur-containing oil fraction containing 50000ppm of sulfur was used as a sulfur source.
Example 6
A high-quality refined oil from which impurities had been removed was finally obtained by carrying out the reaction under the same conditions as in example 1, except that a sulfur-containing oil fraction containing 2000ppm of sulfur was used as a sulfur source.
Example 7
A high-quality refined oil from which impurities had been removed was finally obtained by carrying out the reaction under the same conditions as in example 2, except that a sulfur-containing oil fraction containing 2000ppm of sulfur was used.
Example 8
A high-quality refined oil from which impurities had been removed was finally obtained by carrying out the reaction under the same conditions as in example 3, except that a sulfur-containing oil fraction containing 2000ppm of sulfur was used.
Example 9
A high-quality refined oil from which impurities had been removed was finally obtained by carrying out the reaction under the same conditions as in example 5, except that a sulfur-containing oil fraction containing 5000ppm of sulfur was used.
Comparative example 1
Refined oil from which impurities were removed was finally obtained by performing the reaction under the same conditions as in example 1, except that only waste plastic pyrolysis oil was used.
Comparative example 2
A high-quality refined oil from which impurities had been removed was finally obtained by carrying out the reaction under the same conditions as in example 1, except that a sulfur-containing oil fraction containing 50ppm of sulfur was used as a sulfur source.
Evaluation example
Measurement method
The chlorine (Cl) content (ppm) in the final obtained refined oil was measured by ICP and XRF analysis methods and shown.
Total nitrogen% sulfur (TNS element) analysis was performed on the refined oil, and the catalytic activity retention time was measured in hours based on the time when the nitrogen content in the refined oil exceeded 10ppm and shown.
The measurement results are shown in table 1 below.
TABLE 1
With reference to the table 1 of the drawings,
It was confirmed that in examples 1 to 5, the catalyst activity retention time was all 1100 hours or more, and therefore, high catalyst activity was retained for a long period of time, and in examples 6 to 9, the catalyst activity retention time was also as long as 500 hours or more. Specifically, in example 2, it has been confirmed that the retention time of the catalytic activity is as high as 1560 hours, which is thought to be mainly due to the use of 100 parts by weight of waste plastic pyrolysis oil and 70 parts by weight of sulfur-containing oil fraction containing 20000ppm sulfur, and the use of H 2+H2 S as a reaction gas. Specifically, in example 5, it was also confirmed that the retention time of the catalytic activity was as high as 1560 hours, which is thought to be mainly due to the use of 100 parts by weight of waste plastic pyrolysis oil and 70 parts by weight of sulfur-containing oil fraction containing 50000ppm of sulfur.
However, in comparative example 1, when the hydrotreatment was performed under the same conditions as in example 1, except that only the waste plastic pyrolysis oil was used, it was confirmed that the catalytic activity retention time was remarkably short to 295 hours, and when the sulfur-containing oil fraction containing 50ppm of sulfur was also used in comparative example 2, it was confirmed that the catalytic activity was reduced due to the lack of the sulfur source, so that the catalytic activity retention time was remarkably shortened to 300 hours.
While the exemplary embodiments of the present invention have been described above, the present invention is not limited to the exemplary embodiments, but may be embodied in various forms different from each other, and it will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It should be understood, therefore, that the above-described exemplary embodiments are not limiting in all respects but rather illustrative.
Claims (19)
1. A method for refining waste plastic pyrolysis oil, the method comprising:
(S1) mixing the waste plastic pyrolysis oil with a sulfur source to prepare a mixed oil fraction;
(S2) hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) in the presence of a molybdenum-based hydrogenation catalyst; and
(S3) removing the by-product of the hydrotreatment from the product of (S2) to obtain a refined oil.
2. The method for refining waste plastic pyrolysis oil according to claim 1, wherein the sulfur source includes a sulfur-containing oil fraction.
3. The method for refining waste plastic pyrolysis oil according to claim 1, wherein the mixed oil fraction includes sulfur of 100ppm or more.
4. The method for refining waste plastic pyrolysis oil according to claim 2, wherein the content of the sulfur-containing oil fraction is less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil.
5. The method for refining waste plastic pyrolysis oil according to claim 2, wherein the content of the sulfur-containing oil fraction is less than 50 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil.
6. The method for refining waste plastic pyrolysis oil according to claim 1, wherein the sulfur source comprises one or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds.
7. The method for refining waste plastic pyrolysis oil according to claim 1, wherein the reaction gas of (S2) includes hydrogen sulfide gas (H 2 S).
8. The method for refining waste plastic pyrolysis oil according to claim 7, wherein hydrogen sulfide gas (H 2 S) is separated from the hydrotreating byproduct removed in (S3) and then supplied again.
9. The method for refining waste plastic pyrolysis oil according to claim 1, wherein the molybdenum-based hydrogenation catalyst is a catalyst in which molybdenum-based metal or any one or two or more metals selected from nickel, cobalt and tungsten are included and molybdenum-based metal are supported on a carrier.
10. The method for refining waste plastic pyrolysis oil according to claim 1, wherein the molybdenum-based hydrogenation catalyst comprises a molybdenum-based sulfide hydrogenation catalyst.
11. The method for refining waste plastic pyrolysis oil according to claim 1, wherein (S2) is performed at a pressure of 200 bar or less.
12. The method for refining waste plastic pyrolysis oil according to claim 1, wherein (S2) is performed at a temperature of 300 ℃ or more and less than 450 ℃.
13. The method for refining waste plastic pyrolysis oil according to claim 1, wherein (S2) is performed at a Liquid Hourly Space Velocity (LHSV) of 0.1 hour -1 to 5 hours -1.
14. A continuous operation method of waste plastic pyrolysis oil refining equipment, the method comprising:
(S1) mixing the waste plastic pyrolysis oil with a sulfur source to prepare a mixed oil fraction;
(S2) hydrotreating the mixed oil fraction with a reaction gas comprising hydrogen (H 2) and hydrogen sulfide gas (H 2 S) in the presence of a molybdenum-based sulfide hydrogenation catalyst at a pressure of 200 bar or less; and
(S3) removing the by-product of the hydrotreatment from the product of (S2) to obtain a refined oil,
Wherein hydrogen sulfide gas (H 2 S) of (S2) is separated from by-products of the hydrotreatment of (S3) and fed again.
15. The continuous operation method of a waste plastic pyrolysis oil refining apparatus according to claim 14, wherein sulfur is continuously supplied from the sulfur source to maintain the activity of the molybdenum-based sulfide hydrogenation catalyst.
16. The continuous operation method of a waste plastic pyrolysis oil refining apparatus according to claim 14, wherein the mixed oil fraction includes sulfur of 100ppm or more.
17. The continuous operation method of a waste plastic pyrolysis oil refining apparatus of claim 14 wherein the sulfur source comprises a sulfur-containing oil fraction.
18. The continuous operation method of a waste plastic pyrolysis oil refining apparatus according to claim 17, wherein the content of the sulfur-containing oil fraction is less than 100 parts by weight based on 100 parts by weight of the waste plastic pyrolysis oil.
19. The continuous operation method of a waste plastic pyrolysis oil refining apparatus according to claim 14, wherein the sulfur source comprises one or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds.
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| Application Number | Priority Date | Filing Date | Title |
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| KR10-2021-0157620 | 2021-11-16 | ||
| KR1020210157620A KR20230071424A (en) | 2021-11-16 | 2021-11-16 | Refining method of waste plastic pyrolysis oil using sulfur source and molybdenum-based hydrogenation catalyst, and continuous operation method thereof |
| PCT/KR2022/018108 WO2023090854A1 (en) | 2021-11-16 | 2022-11-16 | Refining method of waste plastic pyrolysis oil using sulfur source and molybdenum-based hydrogenation catalyst, and continuous operation method thereof |
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| CN118215723A true CN118215723A (en) | 2024-06-18 |
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| EP (1) | EP4408955A1 (en) |
| KR (1) | KR20230071424A (en) |
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| EP4424796A1 (en) * | 2023-03-02 | 2024-09-04 | OMV Downstream GmbH | Process for purifying a synthetic crude oil stream |
| EP4424797A1 (en) * | 2023-03-02 | 2024-09-04 | OMV Downstream GmbH | Process for purifying a synthetic crude oil stream |
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| JP3776335B2 (en) | 2001-07-25 | 2006-05-17 | 独立行政法人科学技術振興機構 | Method for simultaneous removal of chlorine and nitrogen in oil |
| US7214309B2 (en) * | 2004-09-10 | 2007-05-08 | Chevron U.S.A. Inc | Process for upgrading heavy oil using a highly active slurry catalyst composition |
| EP2504412B1 (en) * | 2009-11-24 | 2015-09-23 | Shell Internationale Research Maatschappij B.V. | Process for catalytic hydrotreatment of a pyrolysis oil |
| CN104927914A (en) * | 2014-03-23 | 2015-09-23 | 何巨堂 | Higher aromatic hydrogenation method with low-hydrogen-oil-ratio pre-hydrogenation process with hydrogen-donor hydrocarbon |
| FI20195446A1 (en) * | 2019-05-28 | 2020-11-29 | Neste Oyj | Alkali-enhanced hydrothermal purification of plastic pyrolysis oils |
| WO2021204821A1 (en) * | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Purification of waste plastic based oil via first a trap and second via an hydrotreatment |
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| WO2023090854A1 (en) | 2023-05-25 |
| KR20230071424A (en) | 2023-05-23 |
| EP4408955A1 (en) | 2024-08-07 |
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