EP3356496B1 - A catalytic process for reducing chloride content of a hydrocarbon feed stream - Google Patents
A catalytic process for reducing chloride content of a hydrocarbon feed stream Download PDFInfo
- Publication number
- EP3356496B1 EP3356496B1 EP16774820.1A EP16774820A EP3356496B1 EP 3356496 B1 EP3356496 B1 EP 3356496B1 EP 16774820 A EP16774820 A EP 16774820A EP 3356496 B1 EP3356496 B1 EP 3356496B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- chloride
- feed stream
- less
- hydrocarbon feed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 126
- 229930195733 hydrocarbon Natural products 0.000 title claims description 124
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 123
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims description 96
- 238000000034 method Methods 0.000 title claims description 48
- 230000008569 process Effects 0.000 title claims description 41
- 230000003197 catalytic effect Effects 0.000 title description 11
- 239000003054 catalyst Substances 0.000 claims description 261
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 52
- 229910052593 corundum Inorganic materials 0.000 claims description 37
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 37
- 238000000197 pyrolysis Methods 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 150000001805 chlorine compounds Chemical class 0.000 claims description 24
- 238000009835 boiling Methods 0.000 claims description 10
- 239000012815 thermoplastic material Substances 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005336 cracking Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 claims description 4
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 claims description 4
- NDTCXABJQNJPCF-UHFFFAOYSA-N chlorocyclopentane Chemical compound ClC1CCCC1 NDTCXABJQNJPCF-UHFFFAOYSA-N 0.000 claims description 4
- CRNIHJHMEQZAAS-UHFFFAOYSA-N tert-amyl chloride Chemical compound CCC(C)(C)Cl CRNIHJHMEQZAAS-UHFFFAOYSA-N 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 26
- 239000003921 oil Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 25
- 229910052717 sulfur Inorganic materials 0.000 description 22
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 20
- 239000011593 sulfur Substances 0.000 description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 241000894007 species Species 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 229910003294 NiMo Inorganic materials 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- -1 polyethylene Polymers 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000013502 plastic waste Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 238000003379 elimination reaction Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 4
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 3
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000011143 downstream manufacturing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004801 Chlorinated PVC Substances 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 2
- 229910017752 Cu-Zn Inorganic materials 0.000 description 2
- 229910017943 Cu—Zn Inorganic materials 0.000 description 2
- XYWDPYKBIRQXQS-UHFFFAOYSA-N Diisopropyl sulfide Chemical compound CC(C)SC(C)C XYWDPYKBIRQXQS-UHFFFAOYSA-N 0.000 description 2
- ZERULLAPCVRMCO-UHFFFAOYSA-N Dipropyl sulfide Chemical compound CCCSCCC ZERULLAPCVRMCO-UHFFFAOYSA-N 0.000 description 2
- 241001671865 Erimyzon oblongus Species 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 1
- LZAZXBXPKRULLB-UHFFFAOYSA-N Diisopropyl disulfide Chemical compound CC(C)SSC(C)C LZAZXBXPKRULLB-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 1
- 150000004662 dithiols Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- 229930192474 thiophene Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 1
Images
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
- 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
- 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
-
- 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
- C10G45/10—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 platinum group 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/10—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including alkaline treatment as the refining step in the absence of hydrogen
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
Definitions
- the present invention relates to a process of reducing the chloride content of a hydrocarbon feed stream comprising a chloride containing pyrolysis oil by contacting the hydrocarbon feed stream with a catalyst in the presence of hydrogen gas.
- Plastic waste may be converted into useful liquids, gas fuels or commodity chemicals using a pyrolysis process.
- plastic waste may contain polyvinylchloride (PVC) which leads to the formation organic chlorides during the pyrolysis process.
- PVC polyvinylchloride
- the organic chlorides may then form HCl in downstream processes, which can cause corrosion of equipment and may also act as a poison for catalysts used in the downstream processes.
- the removal of organic chlorides, and thus HCl, from plastic waste derived feedstocks is important and typically an acceptable concentration of total chloride in many chemical industries for example, hydrogen/ammonia, is less than 1 ppm ( US7501112 B2 ) or even 1 ppb ( AIChE Journal, 51 (2005) 2016-2023 ) depending on the sensitivity towards chloride of catalysts used in the downstream processes.
- the concentration of organic chlorides in plastic feed pyrolysis products can be high, for example close to 2000 ppmw ( Applied Catalysis A: General, 207 (2001) 79-84 ) or greater than 2,000 ppmw ( Fuel Processing Technology, 92 (2011) 253-260 ), depending on the amount of PVC present in the feedstock or the method used to process the plastic waste.
- the concentration of chloride refers to the amount of chloride relative to the total weight of the hydrocarbon feed.
- Lingaiah et. al (Applied Catalysis A: General, 207 (2001) 79-84 ) have used Fe 2 O 3 to remove organic chloride from the pyrolysis oil at 350°C.
- Lopez et. al have used ( Fuel Processing Technology, 92 (2011) 253-260 ) CaCO 3 as a scavenger to react with organic chloride formed during the plastic waste pyrolysis.
- CN 104 815 681 A describes a hydrodechlorination catalyst comprising, by mass, 18-28% of molybdenum trioxide, 3-10% of phosphorus oxide, 2-8% of nickel oxide, and the balance being aluminum oxide or aluminum oxide and silicon oxide.
- the preparation method of the hydrodechlorination catalyst comprises: (a) preparation of a catalyst carrier, (b) preparation an active component solution, (c) dipping, (d) drying and (e) roasting.
- the hydrodechlorination catalyst is applied to removal of organic chlorides in pyrolysis oil generated by waste tire pyrolysis.
- an objective of the present invention is to provide a process of reducing the chloride content of a hydrocarbon feed stream comprising a chloride containing pyrolysis oil by contacting the hydrocarbon feed stream with a catalyst in the presence of hydrogen gas.
- the present invention relates to a process for reducing a chloride content of a hydrocarbon feed stream involving i) cracking a chloride containing thermoplastic material for obtaining a chloride containing pyrolysis oil; ii) contacting a hydrocarbon feed stream comprising a chloride containing pyrolysis oil with a catalyst on a catalyst support, the catalyst being Cu and Zn on an alumina support, in the presence of hydrogen gas at a temperature of 60-300°C and a pressure of 25-35 bars to reduce one or more organic chloride compounds present in the hydrocarbon feed stream and form a hydrocarbon product stream and HCl; iii) removing the HCl from the hydrocarbon product stream, wherein the chloride containing pyrolysis oil has a boiling point of less than 400°C, wherein the hydrocarbon product stream has a chloride content of greater than 2000 ppmw and less than 5000 ppmw relative to the total weight of the hydrocarbon feed stream; and wherein the molar ratio of the hydrogen gas
- the one or more organic chloride compounds is at least one selected from the group consisting of p-chlorotoluene, chlorobenzene, chlorocyclopentane, 1-chlorooctane, and 2-chloro-2-methylbutane.
- the catalyst is present in a catalyst chamber within a reactor vessel, and the contacting includes feeding the hydrocarbon feed stream into the catalyst chamber of the reactor vessel with a weight hourly space velocity of 1-6 h -1 .
- the catalyst Cu and Zn has a largest dimension of 100 ⁇ m - 3 mm.
- the chloride containing pyrolysis oil has a low boiling fraction with a boiling point of less than 190°C.
- the removing includes one or more of stripping, washing, and neutralizing the HCl from the hydrocarbon product stream.
- the hydrocarbon feed stream has a chloride content of greater than 2000 ppmw and less than 5000 ppmw relative to the total weight of the hydrocarbon feed stream and the hydrocarbon product stream has a chloride content of less than 10 ppmw relative to the total weight of the hydrocarbon product stream.
- the present invention relates to a process for reducing a chloride content of a hydrocarbon feed stream comprising a chloride containing pyrolysis oil with a catalyst Cu and Zn on an alumina support, in the presence of hydrogen gas to reduce one or more organic chloride compounds present in the hydrocarbon feed stream and form a hydrocarbon product stream and HCl, wherein the chloride containing pyrolysis oil is obtained by cracking a chloride containing thermoplastic material.
- thermoplastic material is a polymeric material that becomes pliable or moldable above a specific temperature.
- a "thermoplastic material” may refer to virgin plastic materials, scrap plastic materials generated during the processing of plastic materials into desired articles, or plastic materials which remain after an article has performed its intended function.
- Exemplary polymeric plastic materials include materials comprising polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polychloroprene, nylon, polyvinyl chloride (PVC), polyacrylonitrile (PAN), or polyurethane (PU).
- a chloride containing thermoplastic material is a particular type of polymeric material that contains chloride, or a polymeric material that has been chlorinated, for example polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), neoprene, and the like.
- PVC polyvinyl chloride
- CPVC chlorinated polyvinyl chloride
- neoprene neoprene
- a chloride containing pyrolysis oil is a pyrolysis oil product that contains one or more organic chloride compounds obtained by cracking a feedstock containing a chloride containing thermoplastic material.
- the organic chloride compounds may include aromatic chloride compounds and aliphatic chloride compounds.
- Exemplary organic chloride compounds include p-chlorotoluene, chlorobenzene, chlorocyclopentane, 1-chlorooctane, 2-chloro-2-methylbutane, and derivatives and mixtures thereof.
- the chloride containing pyrolysis oil has a boiling point of less than 400°C, preferably less than 390°C, preferably less than 380°C, preferably less than 370°C, preferably less than 360°C, preferably less than 350°C, preferably less than 340°C, preferably less than 330°C, preferably less than 320°C, preferably less than 310°C, preferably less than 300°C, preferably less than 290°C, preferably less than 280°C, preferably less than 270°C, preferably less than 260°C, preferably less than 250°C, preferably less than 240°C, preferably less than 230°C, preferably less than 220°C, preferably less than 210°C, preferably less than 200°C, preferably less than 190°C.
- the chloride containing pyrolysis oil has a low boiling fraction and the low boiling fraction has a boiling point of less than 190°C, less than 189°C, less than 188°C, less than 187°C, less than 186°C, less than 185°C, less than 184°C, less than 183°C, less than 182°C, less than 181°C, less than 180°C.
- 80°C-190°C 100°C-180°C, 120°C-175°C, 125°C-170°C.
- the hydrocarbon feed stream of the present disclosure includes one or more hydrocarbon compounds, such as C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 etc. containing compounds.
- the hydrocarbon feed stream may contain aliphatic hydrocarbon compounds, including, but not limited to, ethane, propane, butane, isobutane, pentane, hexane, heptane, octane, as well as higher molecular weight aliphatic hydrocarbon compounds nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and isomers and derivatives (e.g. unsaturated derivatives) thereof.
- aliphatic hydrocarbon compounds including, but not limited to, ethane, propane, butane, isobutane, pentane, hexane, heptane, octane, as well as higher molecular weight aliphatic hydrocarbon compounds nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexa
- the hydrocarbon feed stream may also contain aromatic hydrocarbon compounds, such as benzene, styrene, xylene, toluene, ethyl benzene, indene, naphthalene, isomers and derivatives thereof, and the like.
- aromatic hydrocarbon compounds such as benzene, styrene, xylene, toluene, ethyl benzene, indene, naphthalene, isomers and derivatives thereof, and the like.
- the hydrocarbon feed stream comprises at least 100 ppm, at least 200 ppm, at least 500 ppm, at least 1,000 ppm, at least 1,500 ppm, at least 2,000 ppm, at least 2,500 ppm, at least 3,000 ppm, at least 3,500 ppm, at least 4,000 ppm, and no more than 10,000 ppm, no more than 9,000 ppm, no more than 8,000 ppm, no more than 7,000 ppm, no more than 6,000 ppm, no more than 5,000 ppm of the chloride containing pyrolysis oil or alternatively the organic chloride compounds.
- the hydrocarbon feed stream comprises about 3,500-4,500 ppm of chloride.
- a sulfided catalyst comprises at least one selected from the group consisting of CoMo, NiMo, and Ni/Al 2 O 3 .
- the sulfided catalyst is CoMo
- the bimetallic CoMo catalyst has a Co:Mo ratio of 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8.
- the sulfided catalyst is NiMo
- the bimetallic NiMo catalyst has a Ni:Mo ratio of 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8.
- sulfided catalysts may also be incorporated into the sulfided catalysts to form bimetallic or multimetallic catalysts.
- chromium and/or tungsten may also be present in the sulfided catalyst to form, for example a NiMoW catalyst.
- the sulfided catalyst is relatively more selective towards the reduction of chloride from organic chloride compounds and relatively less selective for converting olefin-containing compounds into to saturated compounds.
- catalysts may also be used in the chloride removal process in addition to the sulfided catalysts.
- exemplary other catalysts include Pt or Pd-supported on alumina catalysts, and the like.
- the sulfided catalysts may be supported on a catalyst support or unsupported catalysts.
- a catalyst support refers to a high surface area material to which a catalyst is affixed.
- the support may be inert or may participate in catalytic reactions.
- the reactivity of heterogeneous catalysts and nanomaterial-based catalysts occurs at the surface atoms. Consequently great effort is made to maximize the surface area of a catalyst by distributing it over the support.
- Catalyst supports that may be used include various kinds of carbon, alumina, silica, silica-alumina (including conventional silica-alumina, silica-coated alumina, and alumina-coated silica), titania, zirconia, cationic clays or anionic clays such as saponite, bentonite, kaoline, sepiolite or hydotalcite, and the like.
- the catalyst support is aluminum oxide (i.e. alumina).
- the catalyst support may be comprised of a plurality of different crystallographic phases.
- the catalyst support may comprise ( ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , ⁇ -Al 2 O 3 , and ⁇ -Al 2 O 3 , or mixtures thereof.
- the surface area preferably may be in the range of 100-400 m 2 /g, or 150-350 m 2 /g, measured by the B.E.T. method.
- the pore volume of the alumina in one embodiment is in the range of 0.5-1.5 ml/g measured by nitrogen adsorption.
- the catalyst support material may have less catalytic activity than the bulk catalyst composition or no catalytic activity at all. Consequently, by adding a catalyst support material, the activity of the bulk catalyst composition may be reduced. Therefore, the amount of catalyst support material present may depend on the desired activity of the final catalyst composition. Catalyst support amounts from 0-99.9 wt% of the total catalyst composition (i.e.
- the total weight of the catalyst, for example CoMo or Ni, and the catalyst support, for example alumina can be present, or in the range of more than 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt% and less than 99 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%.
- the catalyst composition may comprise 10-25 wt% Mo, 2-10 wt% Co, and 50-80 wt% Al 2 O 3 .
- the catalyst composition may comprise 10-20 wt% Ni, 2-10 wt% Mo, and 50-80% Al 2 O 3 .
- the catalyst composition may include 10-20 wt% Ni and 80-90 wt% Al 2 O 3 .
- the catalyst support may be composited with the catalytic metal (i.e. Cu and Zn) by any impregnation technique, which is known to those of ordinary skill in the art.
- the catalyst used to dechlorinate the hydrocarbon stream may be made by co-precipitating the catalytic metal ( i . e . Cu and Zn) with the catalyst support using any co-precipitation method/technique known to those of ordinary skill in the art.
- the catalyst and any catalyst support present may be housed within a reactor vessel 103 in the form of a catalyst bed, for example a moving, fluidized, or preferably a fixed bed. Therefore, the contacting may involve feeding the hydrocarbon feed stream comprising the chloride containing pyrolysis oil, which is obtained by cracking a chloride containing thermoplastic material, through or over a catalyst bed in a reactor vessel 103 containing the catalyst and optionally a catalyst support, where the feeding is performed in the presence of hydrogen gas 102 to reduce one or more organic chloride compounds present in the hydrocarbon feed stream 101 and form a hydrocarbon product stream 106 and HCl 105.
- the hydrocarbon feed stream comprising the chloride containing pyrolysis oil, which is obtained by cracking a chloride containing thermoplastic material
- the hydrocarbon feed stream 101 and the hydrogen gas 102 may be mixed prior to entering the reactor vessel 103, or alternatively mixed while inside the reactor vessel 103.
- the hydrocarbon feed stream 101 and the hydrogen gas 102 may be mixed by joining their respective feed lines (as depicted in Fig. 1 ) or through the use of a three-way flow control valve (as depicted in Fig. 2 ).
- the reactor vessel is constructed with materials that are resistant to acidic corrosion, such as corrosion caused by HCl.
- the reactor vessel may comprise ceramic materials, glass, quartz, and/or alloy materials such as Inconel.
- the sulfided catalyst may be uniformly distributed throughout a matrix of catalyst support, where the concentration of the sulfided catalyst differs by no more than 5%, by no more than 4%, by no more than 3%, by no more than 2%, by no more than 1% by weight at any given cross section throughout the catalyst bed.
- the sulfided catalyst may be non-uniformly distributed throughout the catalyst support, and may form a gradient across the catalyst bed (i.e. where the concentration at the bottom of the catalyst bed differs by more than 5% from the concentration of the sulfided catalyst at the top of the catalyst bed).
- the catalyst bed may include two or more different sulfided catalysts (e.g. Ni/Al 2 O 3 and CoMo catalysts) or at least one sulfided catalyst and at least one additional catalyst type (e.g. CoMo and Pd/Pt catalyst).
- two different catalysts are evenly dispersed within a catalyst support.
- the catalyst bed comprises a plurality of divided layers, each divided layer comprising a different catalyst or concentration of catalyst, such that a hydrocarbon feed stream being fed through the catalyst bed passes sequentially through each divided layer. The ratio of the two or more different sulfided catalysts (i.e.
- the contacting involves feeding the hydrocarbon feed stream sequentially through a first reactor vessel having a first catalyst (e.g. the sulfided catalyst) then through a second reactor vessel having a second catalyst (e.g. noble metal catalyst).
- a first catalyst e.g. the sulfided catalyst
- a second catalyst e.g. noble metal catalyst
- a catalyst bed comprising a plurality of various catalysts may be more efficient at removing chloride from the pyrolysis oil.
- a catalyst bed having CoMo which efficiently reduces aromatic chlorides, may provide an advantage in removing chloride from a hydrocarbon feed stream having both aromatic and aliphatic chlorides over a catalyst bed having only one type of catalyst.
- the catalyst used to remove chloride is generally comprised of porous metal and/or support components having a suitable pore volume and pore size, such as, for example, a pore volume of 0.05-1 ml/g, or of 0.1-0.94 ml/g, or of 0.1-0.8 ml/g or of 0.1-0.6 ml/g determined by nitrogen adsorption. Pores with a diameter smaller than 1 nm may be but are generally not present.
- the catalysts may generally have a surface area of at least 10 m 2 /g, or at least 50 m 2 /g, or at least 100 m 2 /g, or at least 150 m 2 /g or at least 200 m 2 /g determined via the Brunauer-Emmett-Teller (B.E.T.) method.
- B.E.T. Brunauer-Emmett-Teller
- the sulfided catalyst may be in the form of any shape, for example, a sphere or substantially spherical (i.e. oblong), a cylinder, a slab or rectangular, an extrudate with a quadralobe cross section, an extrudate with a trilobe cross section, etc.
- the sulfided catalyst has a largest dimension of 100 ⁇ m to 3 mm, 120 ⁇ m to 2.8 mm, 140 ⁇ m to 2.6 mm, 160 ⁇ m to 2.4 mm, 180 ⁇ m to 2.2 mm.
- the sulfided catalyst has a largest dimension of about 100-500 ⁇ m, preferably 110-490 ⁇ m, preferably 120-480 ⁇ m, preferably 130-470 ⁇ m, preferably 140-460 ⁇ m, preferably 150-450 ⁇ m, preferably 160-440 ⁇ m, preferably 170-430 ⁇ m, preferably 180-420 ⁇ m, 190-410 ⁇ m, preferably 200-405 ⁇ m, preferably 212-400 ⁇ m, preferably 220-380 ⁇ m, preferably 230-370 ⁇ m, more preferably 240-360 ⁇ m.
- the sulfided catalyst may have different dimensions than those stated above and still function as intended in the process for reducing a chloride content of the hydrocarbon feed stream.
- the sulfided catalyst may have a largest dimension of up to 4 mm, up to 3.8 mm, up to 3.6 mm, up to 3.4 mm, up to 3.2 mm, up to 3.0 mm.
- the sulfided catalyst may be in the form of a sphere (or may be substantially spherical) having a largest diameter of greater than 0.5 mm and less than 4 mm, less than 3.8 mm, less than 3.6 mm, less than 3.4 mm, less than 3.2 mm, less than 3.0 mm, less than 2.8 mm, less than 2.6 mm, less than 2.4 mm, less than 2.2 mm, less than 2.0 mm.
- the sulfided catalyst may be an extrudated catalyst in the form of a cylinder (or alternatively a slab) having a largest diameter (or a longest cross sectional dimension in the case of a slab shape) of 2.0-4.0 mm, preferably 2.0-3.8 mm, preferably 2.2-3.6 mm, preferably 2.4-3.4 mm, preferably 2.6-3.2 mm.
- the sulfided catalyst is present in a catalyst chamber within the reactor vessel, and the contacting includes feeding the hydrocarbon feed stream into the catalyst chamber of the reactor vessel with a weight hourly space velocity (WHSV) of 0.5 h -1 to 6 h -1 , 0.8 h -1 to 5.5 h -1 , 1 h -1 to 5 h -1 , 1.5 h -1 to 4.5 h -1 .
- WHSV weight hourly space velocity
- the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than about 1 hour, less than about 40 minutes, less than about 30 minutes, less than about 15 minutes, less than about 10 minutes.
- the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than 20 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes. For example, from about 1 minute to about 20 minutes.
- the shortest residence time the hydrocarbon feed stream is present in the reactor vessel will be the time taken for the hydrocarbon feed stream to be transported from the inlet of the reactor vessel to the outlet of the reactor vessel.
- the molar ratio of the hydrogen gas to the hydrocarbon feed stream during the contacting is 10:1 to 1:1.5, preferably 9:1 to 1:1.5, preferably 8:1 to 1:1.5, preferably 7:1 to 1:1.5, preferably 6:1 to 1:1.5, preferably 5:1 to 1:1.5, preferably 4:1 to 1:1.5, preferably 3:1 to 1:1.5, preferably 2:1 to 1:1.5, preferably 1.5:1 to 1:1.5, preferably 1.4:1 to 1:1.4, more preferably 1.3:1 to 1:1.3, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1. While it may be advantageous to use a molar ratio of hydrogen gas to the hydrocarbon feed stream that is about 1:1, the use of a higher ratio (i.e.
- hydrogen gas that exits the reactor vessel after the contacting may be recirculated back into the reactor vessel, after appropriate separation of the hydrogen gas from the hydrocarbon product stream.
- the hydrocarbon feed stream is contacted to the sulfided catalyst at a temperature of 60-400°C, 70-390°C, 80-380°C and a pressure of 25-35, 26-34, 27-33, 28-32, 29-31 barg.
- the sulfided catalyst may be sulfided ex-situ, whereby the catalyst is sulfided with a sulfur containing material.
- the sulfiding process may take place outside of the reactor vessel, where the catalyst is treated with a sulfur containing material, and then loaded into the catalyst bed of the reactor vessel.
- the catalyst may be sulfided in-situ by first loading the catalyst into the catalyst chamber where the contacting is to take place, then treating the loaded catalyst with the sulfur containing material. This sulfiding process may be performed to increase the catalytic activity of the catalyst or to attenuate the catalytic properties of the catalyst (e.g. change the selectivity properties or the activity of the catalyst).
- the hydrocarbon feed stream further comprises up to 200 ppmw, preferably up to 190 ppmw, preferably up to 180 ppmw, preferably up to 170 ppmw, preferably up to 160 ppmw, preferably up to 150 ppmw, preferably up to 140 ppmw, preferably up to 130 ppmw, preferably up to 120 ppmw, preferably up to 100 ppmw, preferably up to 90 ppmw, preferably up to 80 ppmw, preferably up to 70 ppmw, preferably up to 60 ppmw, preferably up to 50 ppmw, preferably up to 40 ppmw, preferably up to 30 ppmw of a sulfur containing material relative to the total weight of the hydrocarbon feed stream.
- up to 200 ppmw preferably up to 190 ppmw, preferably up to 180 ppmw, preferably up to 170 ppmw, preferably up to 160 ppmw, preferably up to 150 ppm
- the catalyst is sulfided during the contacting with the sulfur containing material present in the hydrocarbon feed stream so as to maintain the catalyst in a sulfided form.
- the catalyst prior to the contacting with the hydrocarbon feed stream may be in a non-sulfided form, or may be sulfided, and the sulfur containing material present in the hydrocarbon feed stream and/or the chloride containing pyrolysis oil maintains the catalyst in a sulfided form throughout the chloride removal process.
- the process further comprises contacting a sulfur stream comprising no more than 8 wt%, no more than 7 wt%, no more than 6 wt%, no more than 5 wt%, no more than 4 wt%, no more than 3 wt%, no more than 2 wt%, no more than 1 wt% of a sulfur containing material relative to the total weight of the sulfur stream with a catalyst comprising at least one of Co, Mo, and Ni to form the sulfided catalyst prior to the contacting of the hydrocarbon feed stream (i.e. a sulfiding process to form the sulfided catalyst).
- the sulfur containing material that can be used to sulfide the catalyst prior to the contacting, to sulfide the catalyst during the contacting, or to maintain the sulfided catalyst in a sulfided form during the contacting includes H 2 S, carbon disulfide, dimethyl disulfide, ethyl disulfide, propyl disulfide, isopropyl disulfide, butyl disulfide, tertiary butyl disulfide, thianaphthene, thiophene, secondary dibutyl disulfide, thiols, sulfur containing hydrocarbon oils and sulfides such as methyl sulfide, ethyl sulfide, propyl sulfide, isopropyl sulfide, butyl sulfide, secondary dibutyl sulfide, tertiary butyl sulfide, dithiols, sulfur-
- any other organic sulfur source that can be converted to H 2 S over the catalyst in the presence of hydrogen can be used.
- the catalyst may also be activated by an organo sulfur process as described in US 4,530,917 and other processes described therein and this description is incorporated by reference into this specification.
- the sulfur containing material is dimethyl disulfide.
- the sulfur stream of the present disclosure may include one or more hydrocarbon compounds, such as C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , etc., aliphatic hydrocarbon compounds, including, but not limited to, ethane, propane, butane, isobutane, pentane, hexane, heptane, octane, as well as higher molecular weight aliphatic hydrocarbon compounds nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and isomers and derivatives (e.g.
- the sulfiding process may involve heating the CoMo, NiMo, and/or Ni/Al 2 O 3 catalyst in an inert atmosphere up to 180°C, 190°C, or up to 200°C, reducing the catalysts with H 2 at this elevated temperature, then contacting the sulfur stream to the reduced catalyst at a temperature up to 320°C, up to 340°C, or up to 350°C.
- the process also involves removing the HCl from the hydrocarbon product stream.
- the removing includes one or more of stripping, washing, and neutralizing the HCl from the hydrocarbon product stream.
- the process involves stripping the HCl away from the hydrocarbon product stream, for example through distillation.
- the process involves washing and/or neutralizing the HCl from the hydrocarbon product stream or from an off-gas stripped from the hydrocarbon product stream. For example, washing may involve trapping the generated HCl in water to form an acidic aqueous solution. This product may be a saturated HCl solution (36 wt% HCl).
- the HCl contains trace amounts of hydrocarbons, which is known to those of ordinary skill in the art as co-product HCl.
- the neutralizing may involve, for example, contacting the hydrocarbon product stream or the HCl that has been stripped from the hydrocarbon product stream with a neutralizing agent in solid, liquid, or solution form (e.g. amines, hydroxide, carbonates, etc.).
- Removing the HCl 105 from the hydrocarbon product stream 106 may be performed using a separator 104 ( Fig. 1 and Fig. 2 ).
- the separator may be a distillation apparatus, a neutralization chamber, a scrubbing chamber, and the like.
- the hydrocarbon product stream has a lower chloride content than the hydrocarbon feed stream, based on the total weight of the chloride and the total weight of the hydrocarbon feed stream.
- the hydrocarbon feed stream has a chloride content of greater than 2,000, greater than 2,500, greater than 3,000, greater than 3,500, or greater than 4,000 ppmw, and less than 5,000, less than 4,800, less than 4,600, or less than 4,400 ppmw, relative to the total weight of the hydrocarbon feed stream.
- the hydrocarbon product stream has a chloride content of less than 100 ppmw, less than 80 ppmw, less than 60 ppmw, less than 40 ppmw, less than 20 ppmw, less than 15 ppmw, less than 10 ppmw, less than 5 ppmw, or less than 1 ppmw relative to the total weight of the hydrocarbon product stream. Therefore, the process may remove up to 90%, up to 91%, up to 92%, up to 93%, up to 94%, up to 95%, up to 96%, up to 97%, up to 98%, up to 99%, up to 99.5%, up to 99.9% of the chloride content in the hydrocarbon feed stream.
- the present invention relates to a process for reducing a chloride content of a hydrocarbon feed stream involving contacting a hydrocarbon feed stream comprising a chloride containing pyrolysis oil with a catalyst Cu and Zn on an Al 2 O 3 catalyst support in the presence of hydrogen gas to reduce one or more organic chloride compounds present in the hydrocarbon feed stream and form a hydrocarbon product stream and HCl, wherein the chloride containing pyrolysis oil is obtained by cracking a chloride containing thermoplastic material.
- the process also involves removing the HCl from the hydrocarbon product stream as described according to the first aspect.
- the total catalyst composition may contain 0.5-99.5%, preferably 20-99%, preferably 40-98%, preferably 60-97%, preferably 80-96%, more preferably 90-95% catalyst support by weight relative to the total weight of the catalyst composition.
- the total catalyst composition (the Cu and Zn and the Al 2 O 3 catalyst support) may contain 0.5-5%, 0.7-4%, 0.8-3%, 0.9-2% catalytic metal (i.e. Cu and Zn) by weight relative to the total weight of the catalyst composition. Additional metals based on elements from Group 6, 8, 9, 10, or 11 of the Periodic Table of Elements may also be incorporated into the catalyst to form bimetallic or multimetallic catalysts.
- the catalysts Cu and Zn are relatively more selective towards the reduction of chloride from organic chloride compounds and relatively less selective for converting olefin-containing compounds into to saturated compounds. Unlike the sulfided catalysts described herein, the catalysts Cu and Zn are substantially free of sulfur.
- the catalyst composition may include 30-70 wt% Cu, 20-50 wt% Zn, and 5-50 wt% Al 2 O 3 .
- the catalyst Cu and Zn is present in a catalyst chamber within a reactor vessel, and the contacting includes feeding the hydrocarbon feed stream into the catalyst chamber of the reactor vessel with a weight hourly space velocity of 1-6 h -1 , 1-5.5 h -1 , 1-5 h -1 .
- the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than about 1 hour, less than about 40 minutes, less than about 30 minutes, less than about 15 minutes, less than about 10 minutes.
- the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than 20 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes. For example, from about 1 minute to about 20 minutes.
- the shortest residence time the hydrocarbon feed stream is present in the reactor vessel will be the time taken for the hydrocarbon feed stream to be transported from the inlet of the reactor vessel to the outlet of the reactor vessel.
- the catalyst i.e. the catalytic metal
- the catalyst may be uniformly distributed throughout a matrix of catalyst support, where the concentration of the Cu and Zn catalyst differs by no more than 5%, by no more than 4%, by no more than 3%, by no more than 2%, by no more than 1% by weight at any given cross section throughout the catalyst bed.
- the catalyst i.e. the catalytic metal
- the catalyst bed may include two or more different catalysts or at least one catalyst Cu and Zn and at least one additional catalyst type (e.g. Pd on Al 2 O 3 and Ni/Mo).
- two catalysts are evenly dispersed within a catalyst support.
- the catalyst bed comprises a plurality of divided layers, each divided layer comprising a different catalyst or concentration of catalyst, such that a hydrocarbon feed stream being fed through the catalyst bed passes sequentially through each divided layer. The ratio of the two or more different catalysts (i.e.
- the ratio of first catalyst to the second catalyst), or the ratio of at least one catalyst to the at least one additional catalyst may range from 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8, 7:1 to 1:7, 6:1 to 1:6.
- the contacting involves feeding the hydrocarbon feed stream through a reactor vessel having a catalyst (e.g. the Cu and Zn catalyst) then through a second reactor vessel having a second catalyst. It may be advantageous for the chloride removal process to include more than one type of catalyst, since catalysts have varying selectivity towards various substrates.
- the chloride containing pyrolysis oil may contain a plurality of organic chloride compounds
- a catalyst bed comprising a plurality of various catalysts may be more efficient at removing chloride from the pyrolysis oil, since each catalyst may be more reactive towards different organic chloride compounds.
- the catalyst Cu and Zn may be in the form of any shape, for example, a sphere or substantially spherical (i.e. oblong), a cylinder, a slab or rectangular, an extrudate with a quadralobe cross section, an extrudate with a trilobe cross section, etc.
- the catalyst Cu and Zn has a largest dimension of 100 ⁇ m to 3 mm, 120 ⁇ m to 2.8 mm, 140 ⁇ m to 2.6 mm, 160 ⁇ m to 2.4 mm, 180 ⁇ m to 2.2 mm.
- the catalyst Cu and Zn has a largest dimension of 100-500 ⁇ m, preferably 110-490 ⁇ m, preferably 120-480 ⁇ m, preferably 130-470 ⁇ m, preferably 140-460 ⁇ m, preferably 150-450 ⁇ m, preferably 160-440 ⁇ m, preferably 170-430 ⁇ m, preferably 180-420 ⁇ m, 190-410 ⁇ m, preferably 200-405 ⁇ m, preferably 212-400 ⁇ m, preferably 220-380 ⁇ m, preferably 230-370 ⁇ m, more preferably 240-360 ⁇ m.
- the catalyst Cu and Zn may have different dimensions than those stated above and still function as intended in the process for reducing a chloride content of the hydrocarbon feed stream.
- the catalyst Cu and Zn may have a largest dimension of up to 4 mm, up to 3.8 mm, up to 3.6 mm, up to 3.4 mm, up to 3.2 mm, up to 3.0 mm.
- the catalyst may be in the form of a sphere (or may be substantially spherical) having a largest diameter of greater than 0.5 mm and less than 4 mm, less than 3.8 mm, less than 3.6 mm, less than 3.4 mm, less than 3.2 mm, less than 3.0 mm, less than 2.8 mm, less than 2.6 mm, less than 2.4 mm, less than 2.2 mm, less than 2.0 mm.
- the catalyst may be an extrudated catalyst in the form of a cylinder (or alternatively a slab) having a largest diameter (or a longest cross sectional dimension in the case of a slab shape) of 2.0-4.0 mm, preferably 2.0-3.8 mm, preferably 2.2-3.6 mm, preferably 2.4-3.4 mm, preferably 2.6-3.2 mm.
- the catalyst Cu and Zn may be activated prior to the contacting by reducing the catalyst in the presence of H 2 and heating to a temperature of up to 400°C, up to 380°C, up to 350°C or up to 300°C.
- the hydrocarbon feed stream is contacted to the catalyst Cu and Zn at a temperature of 60-300°C, preferably 70-290°C, more preferably 80-280°C and a pressure of 25-35, 26-34, 27-33, 28-32, 29-31 bars.
- the hydrocarbon feed stream may be fed into the catalyst bed at a feed rate ranging WHSV from 0.5 h -1 to 6 h -1 , 0.8 h -1 to 5.5 h -1 , 1 h -1 to 5 h -1 , 1.5 h -1 to 4.5 h -1 .
- the hydrocarbon product stream has a lower chloride content than the hydrocarbon feed stream, based on the total weight of the chloride and the total weight of the hydrocarbon feed stream.
- the hydrocarbon feed stream has a chloride content of greater than 2,000, greater than 2,500, greater than 3,000, greater than 3,500, greater than 4,000 ppmw relative to the total weight of the hydrocarbon feed stream and the hydrocarbon product stream has a chloride content of less than 100 ppmw, less than 80 ppmw, less than 60 ppmw, less than 40 ppmw, less than 20 ppmw, less than 15 ppmw, less than 10 ppmw, less than 5 ppmw, less than 1 ppmw relative to the total weight of the hydrocarbon product stream.
- the process may remove up to 90%, up to 91%, up to 92%, up to 93%, up to 94%, up to 95%, up to 96%, up to 97%, up to 98%, up to 99%, up to 99.5%, up to 99.99%, up to 99.999% of the chloride content in the hydrocarbon feed stream.
- the liquid hydrocarbon feed was made by mixing different chloride containing compounds in n-hexadecane (H6703 Sigma-Aldrich, 99% purity) as solvent.
- the chloride containing compounds were: 0.29 wt% p-chlorotoluene (Sigma Aldrich-111929, 98% purity), 0.25 wt% chlorobenzene (Sigma Aldrich-319996, 99.5% purity), 0.24 wt% chlorocyclopentane (Sigma Aldrich-155136, 99% purity), 0.34 wt% 1-chlorooctane (Sigma Aldrich-125156, 99% purity) and 0.24 wt% 2-chloro-2-methylbutane (Sigma Aldrich-277029, 98% purity) based on the total feed including the solvent.
- the feed contained around 4000 ppmw of chloride (organic chloride) relative to total weight of the feed including the n-hexadecane solvent.
- the hydrodechlorination experiments were carried out in continuous flow fixed bed type reactors.
- the inside diameter of each reactor vessel was 5 mm.
- the experiments were carried at a pressure of 30 barg, in the temperature range 60-400°C, hydrogen to hydrocarbon molar ratio of 1 and WHSV of 1-6 h -1 .
- SiC and Al 2 O 3 were also tested in parallel during each experimental run in the reactor vessel.
- SiC was used to investigate the homogeneous elimination reaction of aliphatic chlorides at high temperatures.
- Al 2 O 3 was used to study the de-chlorination performance without any metal functionality, as all of the catalysts included an alumina support.
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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
- The present invention relates to a process of reducing the chloride content of a hydrocarbon feed stream comprising a chloride containing pyrolysis oil by contacting the hydrocarbon feed stream with a catalyst in the presence of hydrogen gas.
- The "background" description provided herein is for the purpose of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent it is described in this background section, as well as aspects of the description which may not otherwise qualify as prior art at the time of filing, are neither expressly or impliedly admitted as prior art against the present invention.
- Plastic waste may be converted into useful liquids, gas fuels or commodity chemicals using a pyrolysis process. However, plastic waste may contain polyvinylchloride (PVC) which leads to the formation organic chlorides during the pyrolysis process. The organic chlorides may then form HCl in downstream processes, which can cause corrosion of equipment and may also act as a poison for catalysts used in the downstream processes. Therefore, the removal of organic chlorides, and thus HCl, from plastic waste derived feedstocks is important and typically an acceptable concentration of total chloride in many chemical industries for example, hydrogen/ammonia, is less than 1 ppm (
US7501112 B2 ) or even 1 ppb (AIChE Journal, 51 (2005) 2016-2023) depending on the sensitivity towards chloride of catalysts used in the downstream processes. Further, the concentration of organic chlorides in plastic feed pyrolysis products can be high, for example close to 2000 ppmw (Applied Catalysis A: General, 207 (2001) 79-84) or greater than 2,000 ppmw (Fuel Processing Technology, 92 (2011) 253-260), depending on the amount of PVC present in the feedstock or the method used to process the plastic waste. Hereinafter, the concentration of chloride refers to the amount of chloride relative to the total weight of the hydrocarbon feed. Lingaiah et. al (Applied Catalysis A: General, 207 (2001) 79-84) have used Fe2O3 to remove organic chloride from the pyrolysis oil at 350°C. Lopez et. al have used (Fuel Processing Technology, 92 (2011) 253-260) CaCO3 as a scavenger to react with organic chloride formed during the plastic waste pyrolysis. -
CN 104 815 681 A - In view of the foregoing, an objective of the present invention is to provide a process of reducing the chloride content of a hydrocarbon feed stream comprising a chloride containing pyrolysis oil by contacting the hydrocarbon feed stream with a catalyst in the presence of hydrogen gas.
- The present invention relates to a process for reducing a chloride content of a hydrocarbon feed stream involving i) cracking a chloride containing thermoplastic material for obtaining a chloride containing pyrolysis oil; ii) contacting a hydrocarbon feed stream comprising a chloride containing pyrolysis oil with a catalyst on a catalyst support, the catalyst being Cu and Zn on an alumina support, in the presence of hydrogen gas at a temperature of 60-300°C and a pressure of 25-35 bars to reduce one or more organic chloride compounds present in the hydrocarbon feed stream and form a hydrocarbon product stream and HCl; iii) removing the HCl from the hydrocarbon product stream, wherein the chloride containing pyrolysis oil has a boiling point of less than 400°C, wherein the hydrocarbon product stream has a chloride content of greater than 2000 ppmw and less than 5000 ppmw relative to the total weight of the hydrocarbon feed stream; and wherein the molar ratio of the hydrogen gas to the hydrocarbon feed stream is 10:1 to 1:1.5, whereby the hydrocarbon product stream has a chloride content of less than 10 ppmw relative to the total weight of the hydrocarbon feed stream.
- In one embodiment, the one or more organic chloride compounds is at least one selected from the group consisting of p-chlorotoluene, chlorobenzene, chlorocyclopentane, 1-chlorooctane, and 2-chloro-2-methylbutane.
- In one embodiment, the catalyst is present in a catalyst chamber within a reactor vessel, and the contacting includes feeding the hydrocarbon feed stream into the catalyst chamber of the reactor vessel with a weight hourly space velocity of 1-6 h-1.
- In one embodiment, the catalyst Cu and Zn has a largest dimension of 100 µm - 3 mm.
- In one embodiment, the chloride containing pyrolysis oil has a low boiling fraction with a boiling point of less than 190°C.
- In one embodiment, the removing includes one or more of stripping, washing, and neutralizing the HCl from the hydrocarbon product stream.
- In the present invention, the hydrocarbon feed stream has a chloride content of greater than 2000 ppmw and less than 5000 ppmw relative to the total weight of the hydrocarbon feed stream and the hydrocarbon product stream has a chloride content of less than 10 ppmw relative to the total weight of the hydrocarbon product stream.
- The foregoing paragraphs have been provided by way of general introduction, and are not intended to limit the scope of the following claims. The described embodiments, together with further advantages, will be best understood by reference to the following detailed description taken in conjunction with the accompanying drawings.
- A more complete appreciation of the disclosure and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
-
Fig. 1 is an illustration of a process scheme for removing the organic chlorides present in the hydrocarbon feed stream. -
Fig. 2 is an illustration of a process scheme for removing the organic chlorides present in the hydrocarbon feed stream. -
Fig. 3 is a plot illustrating the conversion of different type of chloride species (total chloride 4,000 ppmw in the hydrocarbon feed stream) over the sulfided NiMo catalyst at WHSV of 2 h-1 at 300°C, a pressure of 30 barg and a molar ratio of hydrogen gas to hydrocarbon feed stream of 1:1 is used (out of the invention). -
Fig. 4 is a plot illustrating the conversion of different type of chloride species (total chloride 4,000 ppmw in the hydrocarbon feed stream) over the sulfided NiMo catalyst at WHSV of 2 h-1 at 200°C, a pressure of 30 barg, and a molar ratio of hydrogen gas to hydrocarbon feed stream of 1:1 is used (out of the invention). -
Fig. 5 is a plot illustrating the conversion of different type of chloride species (total chloride 4,000 ppmw in the hydrocarbon feed stream) over the Pd/Al2O3 catalyst at WHSV of 2 h-1 at 200°C, a pressure of 30 barg, and a molar ratio of hydrogen gas to hydrocarbon feed stream of 1:1 is used (out of the invention). -
Fig. 6 is a plot illustrating the conversion of different type of chloride species (total chloride 4,000 ppmw in the hydrocarbon feed stream) over the Cu-ZnO catalyst at WHSV of 2 h-1 at 200°C, a pressure of 30 barg, and a molar ratio of hydrogen gas to hydrocarbon feed stream of 1:1 is used. -
Fig. 7 is a plot illustrating the conversion of different type of chloride species (total chloride 4,000 ppmw in the hydrocarbon feed stream) over an inert SiC at WHSV of 1 h-1 at 200°C, a pressure of 30 barg, and a molar ratio of hydrogen gas to hydrocarbon feed stream of 1:1 is used. - Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views.
- The present invention relates to a process for reducing a chloride content of a hydrocarbon feed stream comprising a chloride containing pyrolysis oil with a catalyst Cu and Zn on an alumina support, in the presence of hydrogen gas to reduce one or more organic chloride compounds present in the hydrocarbon feed stream and form a hydrocarbon product stream and HCl, wherein the chloride containing pyrolysis oil is obtained by cracking a chloride containing thermoplastic material.
- A thermoplastic material is a polymeric material that becomes pliable or moldable above a specific temperature. As used herein, a "thermoplastic material" may refer to virgin plastic materials, scrap plastic materials generated during the processing of plastic materials into desired articles, or plastic materials which remain after an article has performed its intended function. Exemplary polymeric plastic materials include materials comprising polyethylene (PE), polypropylene (PP), polystyrene (PS), polyethylene terephthalate (PET), polychloroprene, nylon, polyvinyl chloride (PVC), polyacrylonitrile (PAN), or polyurethane (PU). A chloride containing thermoplastic material is a particular type of polymeric material that contains chloride, or a polymeric material that has been chlorinated, for example polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), neoprene, and the like.
- A chloride containing pyrolysis oil is a pyrolysis oil product that contains one or more organic chloride compounds obtained by cracking a feedstock containing a chloride containing thermoplastic material. In one embodiment, the organic chloride compounds may include aromatic chloride compounds and aliphatic chloride compounds. Exemplary organic chloride compounds include p-chlorotoluene, chlorobenzene, chlorocyclopentane, 1-chlorooctane, 2-chloro-2-methylbutane, and derivatives and mixtures thereof. The chloride containing pyrolysis oil has a boiling point of less than 400°C, preferably less than 390°C, preferably less than 380°C, preferably less than 370°C, preferably less than 360°C, preferably less than 350°C, preferably less than 340°C, preferably less than 330°C, preferably less than 320°C, preferably less than 310°C, preferably less than 300°C, preferably less than 290°C, preferably less than 280°C, preferably less than 270°C, preferably less than 260°C, preferably less than 250°C, preferably less than 240°C, preferably less than 230°C, preferably less than 220°C, preferably less than 210°C, preferably less than 200°C, preferably less than 190°C. In one embodiment, the chloride containing pyrolysis oil has a low boiling fraction and the low boiling fraction has a boiling point of less than 190°C, less than 189°C, less than 188°C, less than 187°C, less than 186°C, less than 185°C, less than 184°C, less than 183°C, less than 182°C, less than 181°C, less than 180°C. For example, 80°C-190°C, 100°C-180°C, 120°C-175°C, 125°C-170°C.
- In addition to the chloride containing pyrolysis oil, the hydrocarbon feed stream of the present disclosure includes one or more hydrocarbon compounds, such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16 etc. containing compounds. The hydrocarbon feed stream may contain aliphatic hydrocarbon compounds, including, but not limited to, ethane, propane, butane, isobutane, pentane, hexane, heptane, octane, as well as higher molecular weight aliphatic hydrocarbon compounds nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and isomers and derivatives (e.g. unsaturated derivatives) thereof. The hydrocarbon feed stream may also contain aromatic hydrocarbon compounds, such as benzene, styrene, xylene, toluene, ethyl benzene, indene, naphthalene, isomers and derivatives thereof, and the like. In one embodiment, the hydrocarbon feed stream comprises at least 100 ppm, at least 200 ppm, at least 500 ppm, at least 1,000 ppm, at least 1,500 ppm, at least 2,000 ppm, at least 2,500 ppm, at least 3,000 ppm, at least 3,500 ppm, at least 4,000 ppm, and no more than 10,000 ppm, no more than 9,000 ppm, no more than 8,000 ppm, no more than 7,000 ppm, no more than 6,000 ppm, no more than 5,000 ppm of the chloride containing pyrolysis oil or alternatively the organic chloride compounds. For example, the hydrocarbon feed stream comprises about 3,500-4,500 ppm of chloride.
- A sulfided catalyst, not according to the invention, comprises at least one selected from the group consisting of CoMo, NiMo, and Ni/Al2O3. In one embodiment, the sulfided catalyst is CoMo, and the bimetallic CoMo catalyst has a Co:Mo ratio of 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8. In one embodiment, the sulfided catalyst is NiMo, and the bimetallic NiMo catalyst has a Ni:Mo ratio of 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8. Additional metals based on elements from Group 6, 8, 9, 10, or 11 of the Periodic Table of Elements may also be incorporated into the sulfided catalysts to form bimetallic or multimetallic catalysts. For example, chromium and/or tungsten may also be present in the sulfided catalyst to form, for example a NiMoW catalyst. In one embodiment, the sulfided catalyst is relatively more selective towards the reduction of chloride from organic chloride compounds and relatively less selective for converting olefin-containing compounds into to saturated compounds.
- Other catalysts may also be used in the chloride removal process in addition to the sulfided catalysts. Exemplary other catalysts include Pt or Pd-supported on alumina catalysts, and the like.
- The sulfided catalysts may be supported on a catalyst support or unsupported catalysts. In the present disclosure a catalyst support refers to a high surface area material to which a catalyst is affixed. The support may be inert or may participate in catalytic reactions. The reactivity of heterogeneous catalysts and nanomaterial-based catalysts occurs at the surface atoms. Consequently great effort is made to maximize the surface area of a catalyst by distributing it over the support. Catalyst supports that may be used include various kinds of carbon, alumina, silica, silica-alumina (including conventional silica-alumina, silica-coated alumina, and alumina-coated silica), titania, zirconia, cationic clays or anionic clays such as saponite, bentonite, kaoline, sepiolite or hydotalcite, and the like. In the present invention, the catalyst support is aluminum oxide (i.e. alumina). The catalyst support may be comprised of a plurality of different crystallographic phases. Therefore, in terms of alumina, the catalyst support may comprise (α-Al2O3, γ-Al2O3, η-Al2O3, θ-Al2O3, χ-Al2O3, κ-Al2O3, and δ-Al2O3, or mixtures thereof. If alumina is applied as a support, the surface area preferably may be in the range of 100-400 m2/g, or 150-350 m2/g, measured by the B.E.T. method. The pore volume of the alumina in one embodiment is in the range of 0.5-1.5 ml/g measured by nitrogen adsorption.
- In one embodiment, the catalyst support material may have less catalytic activity than the bulk catalyst composition or no catalytic activity at all. Consequently, by adding a catalyst support material, the activity of the bulk catalyst composition may be reduced. Therefore, the amount of catalyst support material present may depend on the desired activity of the final catalyst composition. Catalyst support amounts from 0-99.9 wt% of the total catalyst composition (i.e. the total weight of the catalyst, for example CoMo or Ni, and the catalyst support, for example alumina) can be present, or in the range of more than 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, 40 wt% and less than 99 wt%, 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%. For example, for a CoMo catalyst, the catalyst composition may comprise 10-25 wt% Mo, 2-10 wt% Co, and 50-80 wt% Al2O3. For a NiMo catalyst, the catalyst composition may comprise 10-20 wt% Ni, 2-10 wt% Mo, and 50-80% Al2O3. For a Ni/Al2O3 catalyst, the catalyst composition may include 10-20 wt% Ni and 80-90 wt% Al2O3.
- In one embodiment, the catalyst support may be composited with the catalytic metal (i.e. Cu and Zn) by any impregnation technique, which is known to those of ordinary skill in the art. In an alternative embodiment, the catalyst used to dechlorinate the hydrocarbon stream may be made by co-precipitating the catalytic metal (i.e. Cu and Zn) with the catalyst support using any co-precipitation method/technique known to those of ordinary skill in the art.
- Referring now to
Fig. 1 andFig. 2 . In one or more embodiments, the catalyst and any catalyst support present may be housed within areactor vessel 103 in the form of a catalyst bed, for example a moving, fluidized, or preferably a fixed bed. Therefore, the contacting may involve feeding the hydrocarbon feed stream comprising the chloride containing pyrolysis oil, which is obtained by cracking a chloride containing thermoplastic material, through or over a catalyst bed in areactor vessel 103 containing the catalyst and optionally a catalyst support, where the feeding is performed in the presence ofhydrogen gas 102 to reduce one or more organic chloride compounds present in thehydrocarbon feed stream 101 and form ahydrocarbon product stream 106 andHCl 105. Thehydrocarbon feed stream 101 and thehydrogen gas 102 may be mixed prior to entering thereactor vessel 103, or alternatively mixed while inside thereactor vessel 103. When mixed prior to entering thereactor vessel 103, thehydrocarbon feed stream 101 and thehydrogen gas 102 may be mixed by joining their respective feed lines (as depicted inFig. 1 ) or through the use of a three-way flow control valve (as depicted inFig. 2 ). In one embodiment, the reactor vessel is constructed with materials that are resistant to acidic corrosion, such as corrosion caused by HCl. For example, the reactor vessel may comprise ceramic materials, glass, quartz, and/or alloy materials such as Inconel. In one embodiment, the sulfided catalyst may be uniformly distributed throughout a matrix of catalyst support, where the concentration of the sulfided catalyst differs by no more than 5%, by no more than 4%, by no more than 3%, by no more than 2%, by no more than 1% by weight at any given cross section throughout the catalyst bed. In an alternative embodiment, the sulfided catalyst may be non-uniformly distributed throughout the catalyst support, and may form a gradient across the catalyst bed (i.e. where the concentration at the bottom of the catalyst bed differs by more than 5% from the concentration of the sulfided catalyst at the top of the catalyst bed). - As an example, not covered by the present invention, the catalyst bed may include two or more different sulfided catalysts (e.g. Ni/Al2O3 and CoMo catalysts) or at least one sulfided catalyst and at least one additional catalyst type (e.g. CoMo and Pd/Pt catalyst). In one embodiment, two different catalysts are evenly dispersed within a catalyst support. In an alternative embodiment, the catalyst bed comprises a plurality of divided layers, each divided layer comprising a different catalyst or concentration of catalyst, such that a hydrocarbon feed stream being fed through the catalyst bed passes sequentially through each divided layer. The ratio of the two or more different sulfided catalysts (i.e. the ratio of first sulfided catalyst to the second sulfided catalyst), or the ratio of at least one sulfided catalyst to the at least one additional catalyst may range from 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8, 7:1 to 1:7, 6:1 to 1:6. In yet another example not according to the present invention, the contacting involves feeding the hydrocarbon feed stream sequentially through a first reactor vessel having a first catalyst (e.g. the sulfided catalyst) then through a second reactor vessel having a second catalyst (e.g. noble metal catalyst). It may be advantageous for the chloride removal process to include more than one type of catalyst, since catalysts have varying selectivity towards various substrates. Therefore, since the chloride containing pyrolysis oil may contain a plurality of organic chloride compounds, a catalyst bed comprising a plurality of various catalysts may be more efficient at removing chloride from the pyrolysis oil. For example, a catalyst bed having CoMo, which efficiently reduces aromatic chlorides, may provide an advantage in removing chloride from a hydrocarbon feed stream having both aromatic and aliphatic chlorides over a catalyst bed having only one type of catalyst.
- According to embodiments of the disclosure, the catalyst used to remove chloride is generally comprised of porous metal and/or support components having a suitable pore volume and pore size, such as, for example, a pore volume of 0.05-1 ml/g, or of 0.1-0.94 ml/g, or of 0.1-0.8 ml/g or of 0.1-0.6 ml/g determined by nitrogen adsorption. Pores with a diameter smaller than 1 nm may be but are generally not present. Further, the catalysts may generally have a surface area of at least 10 m2/g, or at least 50 m2/g, or at least 100 m2/g, or at least 150 m2/g or at least 200 m2/g determined via the Brunauer-Emmett-Teller (B.E.T.) method.
- The sulfided catalyst may be in the form of any shape, for example, a sphere or substantially spherical (i.e. oblong), a cylinder, a slab or rectangular, an extrudate with a quadralobe cross section, an extrudate with a trilobe cross section, etc. In one embodiment, the sulfided catalyst has a largest dimension of 100 µm to 3 mm, 120 µm to 2.8 mm, 140 µm to 2.6 mm, 160 µm to 2.4 mm, 180 µm to 2.2 mm. In some embodiments, the sulfided catalyst has a largest dimension of about 100-500 µm, preferably 110-490 µm, preferably 120-480 µm, preferably 130-470 µm, preferably 140-460 µm, preferably 150-450 µm, preferably 160-440 µm, preferably 170-430 µm, preferably 180-420 µm, 190-410 µm, preferably 200-405 µm, preferably 212-400 µm, preferably 220-380 µm, preferably 230-370 µm, more preferably 240-360 µm. However, the sulfided catalyst may have different dimensions than those stated above and still function as intended in the process for reducing a chloride content of the hydrocarbon feed stream. In one embodiment, the sulfided catalyst may have a largest dimension of up to 4 mm, up to 3.8 mm, up to 3.6 mm, up to 3.4 mm, up to 3.2 mm, up to 3.0 mm. For example, the sulfided catalyst may be in the form of a sphere (or may be substantially spherical) having a largest diameter of greater than 0.5 mm and less than 4 mm, less than 3.8 mm, less than 3.6 mm, less than 3.4 mm, less than 3.2 mm, less than 3.0 mm, less than 2.8 mm, less than 2.6 mm, less than 2.4 mm, less than 2.2 mm, less than 2.0 mm. In another example, the sulfided catalyst may be an extrudated catalyst in the form of a cylinder (or alternatively a slab) having a largest diameter (or a longest cross sectional dimension in the case of a slab shape) of 2.0-4.0 mm, preferably 2.0-3.8 mm, preferably 2.2-3.6 mm, preferably 2.4-3.4 mm, preferably 2.6-3.2 mm.
- In one embodiment, the sulfided catalyst is present in a catalyst chamber within the reactor vessel, and the contacting includes feeding the hydrocarbon feed stream into the catalyst chamber of the reactor vessel with a weight hourly space velocity (WHSV) of 0.5 h-1 to 6 h-1, 0.8 h-1 to 5.5 h-1, 1 h-1 to 5 h-1, 1.5 h-1 to 4.5 h-1. In one embodiment, the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than about 1 hour, less than about 40 minutes, less than about 30 minutes, less than about 15 minutes, less than about 10 minutes. Preferably the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than 20 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes. For example, from about 1 minute to about 20 minutes. The shortest residence time the hydrocarbon feed stream is present in the reactor vessel will be the time taken for the hydrocarbon feed stream to be transported from the inlet of the reactor vessel to the outlet of the reactor vessel.
- In one embodiment, the molar ratio of the hydrogen gas to the hydrocarbon feed stream during the contacting is 10:1 to 1:1.5, preferably 9:1 to 1:1.5, preferably 8:1 to 1:1.5, preferably 7:1 to 1:1.5, preferably 6:1 to 1:1.5, preferably 5:1 to 1:1.5, preferably 4:1 to 1:1.5, preferably 3:1 to 1:1.5, preferably 2:1 to 1:1.5, preferably 1.5:1 to 1:1.5, preferably 1.4:1 to 1:1.4, more preferably 1.3:1 to 1:1.3, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1. While it may be advantageous to use a molar ratio of hydrogen gas to the hydrocarbon feed stream that is about 1:1, the use of a higher ratio (i.e. increased amount of hydrogen), for example up to 10:1, up to 7:1, up to 5:1, up to 3:1 may still be utilized and the process will still proceed as intended. In one or more embodiments, hydrogen gas that exits the reactor vessel after the contacting may be recirculated back into the reactor vessel, after appropriate separation of the hydrogen gas from the hydrocarbon product stream.
- In one embodiment, the hydrocarbon feed stream is contacted to the sulfided catalyst at a temperature of 60-400°C, 70-390°C, 80-380°C and a pressure of 25-35, 26-34, 27-33, 28-32, 29-31 barg.
- In one embodiment, the sulfided catalyst may be sulfided ex-situ, whereby the catalyst is sulfided with a sulfur containing material. The sulfiding process may take place outside of the reactor vessel, where the catalyst is treated with a sulfur containing material, and then loaded into the catalyst bed of the reactor vessel. Alternatively, the catalyst may be sulfided in-situ by first loading the catalyst into the catalyst chamber where the contacting is to take place, then treating the loaded catalyst with the sulfur containing material. This sulfiding process may be performed to increase the catalytic activity of the catalyst or to attenuate the catalytic properties of the catalyst (e.g. change the selectivity properties or the activity of the catalyst).
- In one embodiment, the hydrocarbon feed stream further comprises up to 200 ppmw, preferably up to 190 ppmw, preferably up to 180 ppmw, preferably up to 170 ppmw, preferably up to 160 ppmw, preferably up to 150 ppmw, preferably up to 140 ppmw, preferably up to 130 ppmw, preferably up to 120 ppmw, preferably up to 100 ppmw, preferably up to 90 ppmw, preferably up to 80 ppmw, preferably up to 70 ppmw, preferably up to 60 ppmw, preferably up to 50 ppmw, preferably up to 40 ppmw, preferably up to 30 ppmw of a sulfur containing material relative to the total weight of the hydrocarbon feed stream. In one embodiment, the catalyst is sulfided during the contacting with the sulfur containing material present in the hydrocarbon feed stream so as to maintain the catalyst in a sulfided form. In this scenario, the catalyst prior to the contacting with the hydrocarbon feed stream may be in a non-sulfided form, or may be sulfided, and the sulfur containing material present in the hydrocarbon feed stream and/or the chloride containing pyrolysis oil maintains the catalyst in a sulfided form throughout the chloride removal process.
- The process, not according to the invention, further comprises contacting a sulfur stream comprising no more than 8 wt%, no more than 7 wt%, no more than 6 wt%, no more than 5 wt%, no more than 4 wt%, no more than 3 wt%, no more than 2 wt%, no more than 1 wt% of a sulfur containing material relative to the total weight of the sulfur stream with a catalyst comprising at least one of Co, Mo, and Ni to form the sulfided catalyst prior to the contacting of the hydrocarbon feed stream (i.e. a sulfiding process to form the sulfided catalyst). The sulfur containing material that can be used to sulfide the catalyst prior to the contacting, to sulfide the catalyst during the contacting, or to maintain the sulfided catalyst in a sulfided form during the contacting includes H2S, carbon disulfide, dimethyl disulfide, ethyl disulfide, propyl disulfide, isopropyl disulfide, butyl disulfide, tertiary butyl disulfide, thianaphthene, thiophene, secondary dibutyl disulfide, thiols, sulfur containing hydrocarbon oils and sulfides such as methyl sulfide, ethyl sulfide, propyl sulfide, isopropyl sulfide, butyl sulfide, secondary dibutyl sulfide, tertiary butyl sulfide, dithiols, sulfur-bearing gas oils, and the like. Any other organic sulfur source that can be converted to H2S over the catalyst in the presence of hydrogen can be used. The catalyst may also be activated by an organo sulfur process as described in
US 4,530,917 and other processes described therein and this description is incorporated by reference into this specification. In a preferred embodiment, the sulfur containing material is dimethyl disulfide. In addition to the sulfur containing material, the sulfur stream of the present disclosure may include one or more hydrocarbon compounds, such as C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, etc., aliphatic hydrocarbon compounds, including, but not limited to, ethane, propane, butane, isobutane, pentane, hexane, heptane, octane, as well as higher molecular weight aliphatic hydrocarbon compounds nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and isomers and derivatives (e.g. unsaturated derivatives) thereof, and/or aromatic hydrocarbon compounds, such as benzene, styrene, xylene, toluene, ethyl benzene, indene, naphthalene, isomers and derivatives thereof, and the like. The sulfiding process may involve heating the CoMo, NiMo, and/or Ni/Al2O3 catalyst in an inert atmosphere up to 180°C, 190°C, or up to 200°C, reducing the catalysts with H2 at this elevated temperature, then contacting the sulfur stream to the reduced catalyst at a temperature up to 320°C, up to 340°C, or up to 350°C. - The process also involves removing the HCl from the hydrocarbon product stream. In one embodiment, the removing includes one or more of stripping, washing, and neutralizing the HCl from the hydrocarbon product stream. In one embodiment, the process involves stripping the HCl away from the hydrocarbon product stream, for example through distillation. In one embodiment, the process involves washing and/or neutralizing the HCl from the hydrocarbon product stream or from an off-gas stripped from the hydrocarbon product stream. For example, washing may involve trapping the generated HCl in water to form an acidic aqueous solution. This product may be a saturated HCl solution (36 wt% HCl). In one embodiment, the HCl contains trace amounts of hydrocarbons, which is known to those of ordinary skill in the art as co-product HCl. The neutralizing may involve, for example, contacting the hydrocarbon product stream or the HCl that has been stripped from the hydrocarbon product stream with a neutralizing agent in solid, liquid, or solution form (e.g. amines, hydroxide, carbonates, etc.). Removing the
HCl 105 from thehydrocarbon product stream 106 may be performed using a separator 104 (Fig. 1 andFig. 2 ). The separator may be a distillation apparatus, a neutralization chamber, a scrubbing chamber, and the like. - In one embodiment, and as can be seen in
Fig. 3 andFig. 4 in terms of conversion, the hydrocarbon product stream has a lower chloride content than the hydrocarbon feed stream, based on the total weight of the chloride and the total weight of the hydrocarbon feed stream. In one embodiment, the hydrocarbon feed stream has a chloride content of greater than 2,000, greater than 2,500, greater than 3,000, greater than 3,500, or greater than 4,000 ppmw, and less than 5,000, less than 4,800, less than 4,600, or less than 4,400 ppmw, relative to the total weight of the hydrocarbon feed stream. In one embodiment, the hydrocarbon product stream has a chloride content of less than 100 ppmw, less than 80 ppmw, less than 60 ppmw, less than 40 ppmw, less than 20 ppmw, less than 15 ppmw, less than 10 ppmw, less than 5 ppmw, or less than 1 ppmw relative to the total weight of the hydrocarbon product stream. Therefore, the process may remove up to 90%, up to 91%, up to 92%, up to 93%, up to 94%, up to 95%, up to 96%, up to 97%, up to 98%, up to 99%, up to 99.5%, up to 99.9% of the chloride content in the hydrocarbon feed stream. - The present invention relates to a process for reducing a chloride content of a hydrocarbon feed stream involving contacting a hydrocarbon feed stream comprising a chloride containing pyrolysis oil with a catalyst Cu and Zn on an Al2O3 catalyst support in the presence of hydrogen gas to reduce one or more organic chloride compounds present in the hydrocarbon feed stream and form a hydrocarbon product stream and HCl, wherein the chloride containing pyrolysis oil is obtained by cracking a chloride containing thermoplastic material. The process also involves removing the HCl from the hydrocarbon product stream as described according to the first aspect.
- The total catalyst composition (the Cu and Zn and the Al2O3 catalyst support) may contain 0.5-99.5%, preferably 20-99%, preferably 40-98%, preferably 60-97%, preferably 80-96%, more preferably 90-95% catalyst support by weight relative to the total weight of the catalyst composition. The total catalyst composition (the Cu and Zn and the Al2O3 catalyst support) may contain 0.5-5%, 0.7-4%, 0.8-3%, 0.9-2% catalytic metal (i.e. Cu and Zn) by weight relative to the total weight of the catalyst composition. Additional metals based on elements from Group 6, 8, 9, 10, or 11 of the Periodic Table of Elements may also be incorporated into the catalyst to form bimetallic or multimetallic catalysts. In one embodiment, the catalysts Cu and Zn are relatively more selective towards the reduction of chloride from organic chloride compounds and relatively less selective for converting olefin-containing compounds into to saturated compounds. Unlike the sulfided catalysts described herein, the catalysts Cu and Zn are substantially free of sulfur.
- For a Cu/Zn/Al2O3 catalyst, the catalyst composition may include 30-70 wt% Cu, 20-50 wt% Zn, and 5-50 wt% Al2O3.
- In addition to the catalyst Cu and Zn, other catalysts may also be used in the chloride removal process. In this disclosure, SiC, an inert material, was used as blank run or as a comparative example.
- In one embodiment, the catalyst Cu and Zn is present in a catalyst chamber within a reactor vessel, and the contacting includes feeding the hydrocarbon feed stream into the catalyst chamber of the reactor vessel with a weight hourly space velocity of 1-6 h-1, 1-5.5 h-1, 1-5 h-1. In one embodiment, the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than about 1 hour, less than about 40 minutes, less than about 30 minutes, less than about 15 minutes, less than about 10 minutes. Preferably the hydrocarbon feed stream has a residence time in the reactor vessel/catalyst chamber of less than 20 minutes, less than 15 minutes, less than 10 minutes, less than 5 minutes. For example, from about 1 minute to about 20 minutes. The shortest residence time the hydrocarbon feed stream is present in the reactor vessel will be the time taken for the hydrocarbon feed stream to be transported from the inlet of the reactor vessel to the outlet of the reactor vessel.
- In one embodiment, the catalyst (i.e. the catalytic metal) may be uniformly distributed throughout a matrix of catalyst support, where the concentration of the Cu and Zn catalyst differs by no more than 5%, by no more than 4%, by no more than 3%, by no more than 2%, by no more than 1% by weight at any given cross section throughout the catalyst bed. In an alternative embodiment, the catalyst (i.e. the catalytic metal) may be non-uniformly distributed throughout the catalyst support, and may form a gradient across the catalyst bed (i.e. where the concentration at the bottom of the catalyst bed differs by more than 5% from the concentration of the catalyst at the top of the catalyst bed).
- In one embodiment, more than one catalyst may be used in the present process. As an example the catalyst bed may include two or more different catalysts or at least one catalyst Cu and Zn and at least one additional catalyst type (e.g. Pd on Al2O3 and Ni/Mo). In one embodiment, two catalysts are evenly dispersed within a catalyst support. In an alternative embodiment, the catalyst bed comprises a plurality of divided layers, each divided layer comprising a different catalyst or concentration of catalyst, such that a hydrocarbon feed stream being fed through the catalyst bed passes sequentially through each divided layer. The ratio of the two or more different catalysts (i.e. the ratio of first catalyst to the second catalyst), or the ratio of at least one catalyst to the at least one additional catalyst may range from 10:1 to 1:10, 9:1 to 1:9, 8:1 to 1:8, 7:1 to 1:7, 6:1 to 1:6. In yet another embodiment, the contacting involves feeding the hydrocarbon feed stream through a reactor vessel having a catalyst (e.g. the Cu and Zn catalyst) then through a second reactor vessel having a second catalyst. It may be advantageous for the chloride removal process to include more than one type of catalyst, since catalysts have varying selectivity towards various substrates. Therefore, since the chloride containing pyrolysis oil may contain a plurality of organic chloride compounds, a catalyst bed comprising a plurality of various catalysts may be more efficient at removing chloride from the pyrolysis oil, since each catalyst may be more reactive towards different organic chloride compounds.
- The catalyst Cu and Zn may be in the form of any shape, for example, a sphere or substantially spherical (i.e. oblong), a cylinder, a slab or rectangular, an extrudate with a quadralobe cross section, an extrudate with a trilobe cross section, etc. In one embodiment, the catalyst Cu and Zn has a largest dimension of 100 µm to 3 mm, 120 µm to 2.8 mm, 140 µm to 2.6 mm, 160 µm to 2.4 mm, 180 µm to 2.2 mm. In some embodiments, the catalyst Cu and Zn has a largest dimension of 100-500 µm, preferably 110-490 µm, preferably 120-480 µm, preferably 130-470 µm, preferably 140-460 µm, preferably 150-450 µm, preferably 160-440 µm, preferably 170-430 µm, preferably 180-420 µm, 190-410 µm, preferably 200-405 µm, preferably 212-400 µm, preferably 220-380 µm, preferably 230-370 µm, more preferably 240-360 µm. However, the catalyst Cu and Zn may have different dimensions than those stated above and still function as intended in the process for reducing a chloride content of the hydrocarbon feed stream. In one embodiment, the catalyst Cu and Zn may have a largest dimension of up to 4 mm, up to 3.8 mm, up to 3.6 mm, up to 3.4 mm, up to 3.2 mm, up to 3.0 mm. For example, the catalyst may be in the form of a sphere (or may be substantially spherical) having a largest diameter of greater than 0.5 mm and less than 4 mm, less than 3.8 mm, less than 3.6 mm, less than 3.4 mm, less than 3.2 mm, less than 3.0 mm, less than 2.8 mm, less than 2.6 mm, less than 2.4 mm, less than 2.2 mm, less than 2.0 mm. In another example, the catalyst may be an extrudated catalyst in the form of a cylinder (or alternatively a slab) having a largest diameter (or a longest cross sectional dimension in the case of a slab shape) of 2.0-4.0 mm, preferably 2.0-3.8 mm, preferably 2.2-3.6 mm, preferably 2.4-3.4 mm, preferably 2.6-3.2 mm.
- The catalyst Cu and Zn may be activated prior to the contacting by reducing the catalyst in the presence of H2 and heating to a temperature of up to 400°C, up to 380°C, up to 350°C or up to 300°C.
- The hydrocarbon feed stream is contacted to the catalyst Cu and Zn at a temperature of 60-300°C, preferably 70-290°C, more preferably 80-280°C and a pressure of 25-35, 26-34, 27-33, 28-32, 29-31 bars. The hydrocarbon feed stream may be fed into the catalyst bed at a feed rate ranging WHSV from 0.5 h-1 to 6 h-1, 0.8 h-1 to 5.5 h-1, 1 h-1 to 5 h-1, 1.5 h-1 to 4.5 h-1.
- In one embodiment, and as can be seen in
Fig. 6 in terms of conversion, the hydrocarbon product stream has a lower chloride content than the hydrocarbon feed stream, based on the total weight of the chloride and the total weight of the hydrocarbon feed stream. The hydrocarbon feed stream has a chloride content of greater than 2,000, greater than 2,500, greater than 3,000, greater than 3,500, greater than 4,000 ppmw relative to the total weight of the hydrocarbon feed stream and the hydrocarbon product stream has a chloride content of less than 100 ppmw, less than 80 ppmw, less than 60 ppmw, less than 40 ppmw, less than 20 ppmw, less than 15 ppmw, less than 10 ppmw, less than 5 ppmw, less than 1 ppmw relative to the total weight of the hydrocarbon product stream. Therefore, the process may remove up to 90%, up to 91%, up to 92%, up to 93%, up to 94%, up to 95%, up to 96%, up to 97%, up to 98%, up to 99%, up to 99.5%, up to 99.99%, up to 99.999% of the chloride content in the hydrocarbon feed stream. - The examples below are intended to further illustrate protocols for preparing, characterizing and using the catalysts in the process for reducing the chloride content of the hydrocarbon feed stream and are not intended to limit the scope of the claims.
- Hydrodechlorination experiments were carried out using hydrogenation catalysts as described in Table 1.
Table 1 CoMo catalyst: MoO3 (10-25 wt%), Co2O3 (2-10 wt%) and Al2O3 (50-80 wt%) NiMo catalyst: NiO (10-20 wt%), MoO3 (2-10 wt%) and Al2O3 (50-80 wt%) Ni/Al2O3 catalyst: NiO (10-20 wt%) and Al2O3 (80-90 wt%) Pt/Al2O3 catalyst: Pt (0.2-1.0 wt%) on Al2O3 (99 wt%) Pd/Al2O3 catalyst: Pd (0.1-0.5 wt%) on Al2O3 (99.5 wt%) Cu/Zn/Al2O3 catalyst: CuO (30-70 wt%), ZnO (20-50 wt%) and Al2O3 (5-50 wt.%) - The liquid hydrocarbon feed was made by mixing different chloride containing compounds in n-hexadecane (H6703 Sigma-Aldrich, 99% purity) as solvent. The chloride containing compounds were: 0.29 wt% p-chlorotoluene (Sigma Aldrich-111929, 98% purity), 0.25 wt% chlorobenzene (Sigma Aldrich-319996, 99.5% purity), 0.24 wt% chlorocyclopentane (Sigma Aldrich-155136, 99% purity), 0.34 wt% 1-chlorooctane (Sigma Aldrich-125156, 99% purity) and 0.24 wt% 2-chloro-2-methylbutane (Sigma Aldrich-277029, 98% purity) based on the total feed including the solvent. The feed contained around 4000 ppmw of chloride (organic chloride) relative to total weight of the feed including the n-hexadecane solvent.
- The hydrodechlorination experiments were carried out in continuous flow fixed bed type reactors. The inside diameter of each reactor vessel was 5 mm. The experiments were carried at a pressure of 30 barg, in the temperature range 60-400°C, hydrogen to hydrocarbon molar ratio of 1 and WHSV of 1-6 h-1. SiC and Al2O3 were also tested in parallel during each experimental run in the reactor vessel. SiC was used to investigate the homogeneous elimination reaction of aliphatic chlorides at high temperatures. Al2O3 was used to study the de-chlorination performance without any metal functionality, as all of the catalysts included an alumina support. In the case of catalysts CoMo, NiMo and Ni/Al2O3 the catalysts were sulfided using dimethyl disulfide (DMDS) in hexadecane. The DMDS solution in hexadecane consisted of 3wt. % S. The activation procedure of CoMo, NiMo and Ni/Al2O3 included heating in N2 up to 180°C, followed by reduction in H2 at 180°C for 1 h and spiked sulfur (DMDS) containing hexadecane at 120°C and heating in this mixture up to 345°C. In case of Pt/Al2O3, Pd/Al2O3 and Cu/ZnO catalysts, the activation was done by reducing the catalysts in-situ using hydrogen and heating to 400 °C at 5°C/min.
- All catalysts including inerts were used in the size fraction 212-400 µm. The analysis of product stream (gas and liquid phase) was performed using online GC-FID (gas phase) and offline GC-FID (liquid phase).
- Referring to
Fig. 3 : - Catalyst loading: 0.6426 g NiMo catalyst
- Catalyst pretreatment - Sulfided (Sulfided using 3 wt. % S (DMDS) in hexadecane up to 345°C after reduction with hydrogen up to 180°C.
- Feed (as described above) 4000 ppmw Cl and 3 wt. S in the form of DMDS
- Feed rate 1.27 g/h
- H2/HC ratio equals 1 (all the hydrocarbon feed including chloride species)
- Temperature = 300°C, Reactor Inlet Pressure = 30 barg.
- As can be seen from
Fig. 3 , all of the different types of chlorinated species are converted at a temperature of 300°C using the NiMo catalyst. - Referring to
Fig. 4 : - Catalyst loading: 0.6426 g NiMo catalyst
- Catalyst pretreatment - Sulfided (Sulfided using 3 wt. % S (DMDS) in hexadecane up to 345°C after reduction with hydrogen up to 180°C.
- Feed (as described above) 4000 ppmw Cl and 3 wt. S in the form of DMDS
- Feed rate 1.27 g/h
- H2/HC molar ratio = 1 (including n-hexadecane and chloride species)
- Temperature =200°C, Reactor Inlet Pressure = 30 barg.
- As can be seen from
Fig. 4 , all of the aliphatic chlorinated species are converted at a temperature of 200°C using the NiMo catalyst, while the aromatic chloride species are not. - Referring to
Fig. 5 : - Catalyst loading: 0.6417 g Pd catalyst
- Catalyst pretreatment - Catalyst reduced in hydrogen at 400°C
- Feed (as described above) 4000 ppmw Cl
- Feed rate = 1.28 g/h
- H2/HC molar ratio = 1 (including n-hexadecane and chloride species)
- Temperature = 200°C, Reactor Inlet Pressure = 30 barg.
- As can be seen from
Fig. 5 , all of the different types of chlorinated species are converted at a temperature of 200°C using the Pd/Al2O3 catalyst. This result is advantageous in that all aromatic chloride species are also converted at low temperature (200°C). - Referring to
Fig. 6 : - Catalyst loading: 0.6417 g Cu-Zn catalyst
- Catalyst pretreatment - Catalyst reduced in hydrogen at 400°C
- Feed (as described above) 4000 ppmw Cl
- Feed rate = 1.28 g/h
- H2/HC molar ratio = 1 (including n-hexadecane and chloride species)
- Temperature = 200°C, Reactor Inlet Pressure = 30 barg.
- As can be seen from
Fig. 6 , all of the aliphatic chlorinated species are converted at a temperature of 200°C using the Cu-Zn catalyst, while the aromatic chlorides are not completely converted at 200°C. - Referring to
Fig. 7 : - Catalyst loading: 1.283 g SiC (inert)
- Catalyst pretreatment ― SiC heated in hydrogen at 400°C
- Feed (as described above): 4000 ppmw Cl
- Feed rate = 1.28 g/h
- H2/HC molar ratio = 1 (including n-hexadecane and chloride species)
- Temperature =200°C, Reactor Inlet Pressure = 30 barg.
- To estimate non-catalytic dechlorination due to elimination reactions, an inert (SiC) was used. The conversions obtained due to elimination reactions are illustrated in
Fig. 7 . The secondary and tertiary chloride species show conversion, which may be due to elimination, at a temperature of 200°C using the SiC.
Claims (7)
- A process for reducing a chloride content of a hydrocarbon feed stream, comprising:cracking a chloride containing thermoplastic material for obtaining a chloride containing pyrolysis oil;contacting a hydrocarbon feed stream comprising a chloride containing pyrolysis oil with a catalyst on a catalyst support, the catalyst being Cu and Zn on an alumina support, in the presence of hydrogen gas at a temperature of 60-300°C and a pressure of 25-35 bars to reduce one or more organic chloride compounds present in the hydrocarbon feed stream and form a hydrocarbon product stream and HCl;removing the HCl from the hydrocarbon product stream;wherein the chloride containing pyrolysis oil has a boiling point of less than 400°C; wherein the hydrocarbon feed stream has a chloride content of greater than 2000 ppmw and less than 5000 ppmw relative to the total weight of the hydrocarbon feed stream; andwherein the molar ratio of the hydrogen gas to the hydrocarbon feed stream is 10:1 to 1:1.5,whereby the hydrocarbon product stream has a chloride content of less than 10 ppmw relative to the total weight of the hydrocarbon product stream.
- The process of claim 1, wherein the organic chloride compound is at least one selected from the group consisting of p-chlorotoluene, chlorobenzene, chlorocyclopentane, 1-chlorooctane, and 2-chloro-2-methylbutane.
- The process of claim 1, wherein
the Cu/Zn/Al2O3 catalyst includes 30-70 wt% Cu, 20-50 wt% Zn, and 5-50 wt% Al2O3. - The process of claim 1, wherein the catalyst is present in a catalyst chamber within a reactor vessel, and the contacting includes feeding the hydrocarbon feed stream into the catalyst chamber of the reactor vessel with a weight hourly space velocity of 1-6 h-1.
- The process of claim 1, wherein the catalyst has a largest dimension of 100 µm - 3 mm.
- The process of claim 1, wherein the chloride containing pyrolysis oil has a low boiling fraction with a boiling point of less than 190°C.
- The process of claim 1, wherein the removing includes one or more of stripping, washing, and neutralizing the HCl from the hydrocarbon product stream.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562254987P | 2015-11-13 | 2015-11-13 | |
PCT/US2016/053299 WO2017083018A1 (en) | 2015-11-13 | 2016-09-23 | A catalytic process for reducing chloride content of a hydrocarbon feed stream |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3356496A1 EP3356496A1 (en) | 2018-08-08 |
EP3356496B1 true EP3356496B1 (en) | 2021-12-01 |
Family
ID=57043056
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16774820.1A Active EP3356496B1 (en) | 2015-11-13 | 2016-09-23 | A catalytic process for reducing chloride content of a hydrocarbon feed stream |
Country Status (5)
Country | Link |
---|---|
US (1) | US20190062646A1 (en) |
EP (1) | EP3356496B1 (en) |
JP (1) | JP6824981B2 (en) |
CN (1) | CN108291156A (en) |
WO (1) | WO2017083018A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR110493A1 (en) | 2016-12-08 | 2019-04-03 | Shell Int Research | A METHOD FOR PRE-TREAT AND CONVERT HYDROCARBONS |
CN108435193B (en) * | 2018-04-12 | 2020-08-28 | 武汉科林化工集团有限公司 | Reproducible organochlorine removal catalyst and preparation method thereof |
JP7544741B2 (en) | 2019-04-18 | 2024-09-03 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Aliphatic Hydrocarbon Recovery |
CA3197080A1 (en) * | 2020-11-13 | 2022-05-19 | Lars Jorgensen | Process for treating a feedstock comprising halides |
CA3215431A1 (en) | 2021-04-14 | 2022-10-20 | Bryan A. Patel | Chloride removal for plastic waste conversion |
WO2023061798A1 (en) * | 2021-10-13 | 2023-04-20 | Basf Se | Process for purifying a pyrolysis oil and purification system |
CN118176279A (en) * | 2021-10-27 | 2024-06-11 | 巴斯夫欧洲公司 | Method for purifying pyrolysis oil |
AR129067A1 (en) * | 2022-04-14 | 2024-07-10 | Topsoe As | PRODUCTION OF HALIDE-FREE HYDROCARBONS |
CN117004433A (en) * | 2022-04-27 | 2023-11-07 | 中国石油化工股份有限公司 | Method for dechlorinating waste plastic oil and/or waste tire oil |
FR3144153A1 (en) | 2022-12-21 | 2024-06-28 | IFP Energies Nouvelles | METHOD FOR TREATING PLASTICS AND/OR TIRES PYROLYSIS OILS INCLUDING THE ELIMINATION OF HALIDES BY WASHING BEFORE A HYDROTREATMENT STEP |
FR3144155A1 (en) | 2022-12-21 | 2024-06-28 | IFP Energies Nouvelles | METHOD FOR TREATMENT OF PYROLYSIS OILS OF PLASTICS AND/OR TIRES INCLUDING THE ELIMINATION OF HALIDES PRIOR TO A HYDROTREATMENT STEP |
WO2024213735A1 (en) | 2023-04-13 | 2024-10-17 | Basf Se | Process for purifying a pyrolysis oil |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2548205B1 (en) | 1983-06-30 | 1985-11-29 | Eurecat Europ Retrait Catalys | PROCESS FOR PRESULFURIZING A HYDROCARBON PROCESSING CATALYST |
US6172275B1 (en) * | 1991-12-20 | 2001-01-09 | Kabushiki Kaisha Toshiba | Method and apparatus for pyrolytically decomposing waste plastic |
WO1999017876A1 (en) * | 1997-10-02 | 1999-04-15 | Akzo Nobel N.V. | Treatment to improve the durability of a hydrodechlorination catalyst and catalyst |
GB9920871D0 (en) | 1999-09-06 | 1999-11-10 | Ici Plc | Catalysts |
FR2940144B1 (en) * | 2008-12-23 | 2016-01-22 | Inst Francais Du Petrole | PROCESS FOR TRANSFORMING EXCELLENT QUALITY RENEWABLE FUEL ORIGLENT EFFLUENTS USING A MOLYBDENATED CATALYST |
US9139782B2 (en) * | 2011-02-11 | 2015-09-22 | E I Du Pont De Nemours And Company | Targeted pretreatment and selective ring opening in liquid-full reactors |
US9404045B2 (en) * | 2011-02-17 | 2016-08-02 | AMG Chemistry and Catalysis Consulting, LLC | Alloyed zeolite catalyst component, method for making and catalytic application thereof |
US9200207B2 (en) * | 2011-05-31 | 2015-12-01 | University Of Central Florida Research Foundation, Inc. | Methods of producing liquid hydrocarbon fuels from solid plastic wastes |
CN103980938A (en) * | 2014-05-26 | 2014-08-13 | 大连理工大学 | Method for producing clean fuel by adopting chlorine-containing plastic oil |
CN104815681B (en) * | 2015-03-13 | 2017-11-17 | 洛阳瑞泽石化工程有限公司 | A kind of Hydrodechlorinating catalyst and its preparation method and application |
CN105001910B (en) * | 2015-06-30 | 2016-09-28 | 洛阳瑞泽石化工程有限公司 | A kind of method of combination type hydrotreating tire pyrolysis oil |
-
2016
- 2016-09-23 EP EP16774820.1A patent/EP3356496B1/en active Active
- 2016-09-23 WO PCT/US2016/053299 patent/WO2017083018A1/en active Application Filing
- 2016-09-23 CN CN201680065937.4A patent/CN108291156A/en active Pending
- 2016-09-23 US US15/765,300 patent/US20190062646A1/en not_active Abandoned
- 2016-09-23 JP JP2018524433A patent/JP6824981B2/en active Active
Non-Patent Citations (1)
Title |
---|
None * |
Also Published As
Publication number | Publication date |
---|---|
US20190062646A1 (en) | 2019-02-28 |
CN108291156A (en) | 2018-07-17 |
EP3356496A1 (en) | 2018-08-08 |
JP6824981B2 (en) | 2021-02-03 |
JP2018537558A (en) | 2018-12-20 |
WO2017083018A1 (en) | 2017-05-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3356496B1 (en) | A catalytic process for reducing chloride content of a hydrocarbon feed stream | |
CN109642164B (en) | Integrated process configuration comprising pyrolysis, hydrocracking, hydrodealkylation and steam cracking steps | |
AU2004245280B2 (en) | Selective hydrogenation process and catalyst therefor | |
KR101452529B1 (en) | Process for removing oxygen, nitrogen oxides, acetylenes and/or dienes from hydrogen-rich olefin-comprising gas mixtures | |
Martino et al. | Hydrodechlorination of dichloromethane, trichloroethane, trichloroethylene and tetrachloroethylene over a sulfided Ni/Mo–γ-alumina catalyst | |
KR20070095408A (en) | Method for producing olefins | |
EP3083900B1 (en) | Hydrocarbon dehydrogenation sulfur management | |
US20180245006A1 (en) | Copper adsorbent for acetylene converter guard bed | |
Zhang et al. | Modification of Hβ zeolite by fluorine and its influence on olefin alkylation thiophenic sulfur in gasoline | |
CA2223651C (en) | Process for the hydrogenation of a thiophenic sulfur containing hydrocarbon feed | |
CA2602446C (en) | Process for the purification of benzene feedstock containing contaminating sulfur compounds | |
US20190270642A1 (en) | Catalytic conversion of dso in presence of water | |
Wang et al. | Catalytic hydrodesulfurization and hydrodenitrogenation over Co Mo on TiO2 ZrO2 V2O5 | |
CN105980049A (en) | Cleaning of liquid hydrocarbon streams by means of copper-containing sorbents | |
CN110072613B (en) | Catalyst system and process for converting hydrocarbon feedstock using the same | |
US11383225B2 (en) | Hydrocarbon conversion catalyst system | |
ES2804725T3 (en) | Catalyst system and process that uses the catalyst system | |
RU2309179C2 (en) | Method for hydrogenation of aromatic compounds in hydrocarbon raw containing thiophene compounds | |
CN102643154A (en) | Process for the removal of sulfur compounds from hydrocarbon feedstocks | |
TWI639468B (en) | Stabilized rhenium-based heterogeneous catalyst and use thereof | |
CN116889778A (en) | Method for removing odoriferous substances from hydrocarbon streams | |
JP2024540134A (en) | Process for refining pyrolysis oil | |
Ishigaki et al. | Difference of kinetics between powdered and pelletized catalysts in liquid-phase hydrogenation of 1-methylnaphthalene | |
US20140353209A1 (en) | Process for treating a naphtha stream |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20180504 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: HAKEEM, ABRAR A. Inventor name: GHOSH, ASHIM KUMAR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20190327 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20210506 |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTC | Intention to grant announced (deleted) | ||
INTG | Intention to grant announced |
Effective date: 20210713 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1451769 Country of ref document: AT Kind code of ref document: T Effective date: 20211215 Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602016066843 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: FP |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG9D |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1451769 Country of ref document: AT Kind code of ref document: T Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220301 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220301 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220302 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220401 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602016066843 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20220401 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
26N | No opposition filed |
Effective date: 20220902 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20220930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220923 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230620 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220930 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220923 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220930 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20160923 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20211201 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240927 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20240927 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240925 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20240926 Year of fee payment: 9 |