CN114806633A - Method and system for producing clean diesel oil from waste plastic oil and/or waste tire oil - Google Patents
Method and system for producing clean diesel oil from waste plastic oil and/or waste tire oil Download PDFInfo
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- CN114806633A CN114806633A CN202110123999.9A CN202110123999A CN114806633A CN 114806633 A CN114806633 A CN 114806633A CN 202110123999 A CN202110123999 A CN 202110123999A CN 114806633 A CN114806633 A CN 114806633A
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- Prior art keywords
- hydrogenation
- oil
- waste
- reactor
- catalyst
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- 239000002699 waste material Substances 0.000 title claims abstract description 99
- 239000004033 plastic Substances 0.000 title claims abstract description 68
- 229920003023 plastic Polymers 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000010920 waste tyre Substances 0.000 title claims abstract description 38
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 136
- 238000006243 chemical reaction Methods 0.000 claims abstract description 126
- 239000012535 impurity Substances 0.000 claims abstract description 73
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 47
- 239000003502 gasoline Substances 0.000 claims abstract description 18
- 239000003921 oil Substances 0.000 claims description 118
- 239000003054 catalyst Substances 0.000 claims description 108
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 230000000382 dechlorinating effect Effects 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 238000006298 dechlorination reaction Methods 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 10
- 238000004227 thermal cracking Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 239000003223 protective agent Substances 0.000 claims description 9
- -1 VIB metals Chemical class 0.000 claims description 8
- 238000004523 catalytic cracking Methods 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 239000010813 municipal solid waste Substances 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000012271 agricultural production Methods 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 13
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005695 dehalogenation reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003869 coulometry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000011344 liquid material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 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
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Images
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/205—Metal content
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/701—Use of spent catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method and a system for producing clean diesel oil from waste plastic oil and/or waste tire oil. And carrying out impurity removal reaction on the waste plastic oil and/or the waste tire oil in an impurity removal unit, allowing the obtained reaction effluent to enter a hydrogenation unit for carrying out hydrofining and hydrocracking reactions, and separating reaction products to obtain a gasoline fraction, a diesel fraction and a tail oil fraction. The invention can effectively remove impurities in the waste plastic oil and/or the waste tire oil, and is combined with the hydrogenation unit to obtain clean diesel oil products to the maximum extent. The invention has low cost and long operation period.
Description
Technical Field
The invention relates to the technical field of hydrocarbon raw material treatment, in particular to a method and a system for producing clean diesel oil from waste plastic oil and/or waste tire oil.
Background
Along with the continuous development of the urbanization process of China, the urban population rises year by year, the living standard of people is continuously improved, the yield of urban domestic garbage is also continuously increased, and the current urban garbage treatment method mainly comprises landfill, incineration and the like. There are a series of subsequent environmental problems whether incineration or landfill.
The chemical conversion method can convert the plastic waste into industrial raw materials or fuel oil with utilization value, not only can eliminate environmental pollution, but also can realize sustainable development and utilization of resources, and is an effective way for treating white pollution. At present, the waste plastic oil refining industry has a global flowering situation in China, some enterprises build pyrolysis demonstration devices with smaller scale, but the problem of high value utilization of waste plastic pyrolysis products is still to be effectively solved.
The difference between the waste plastic oil and the waste tire oil converted by various processes and the traditional petroleum-based oil products is large, the impurity content is high, particularly the silicon content is high, and great troubles are brought to subsequent processing. At present, the deep processing of the waste plastic oil and the waste tire oil is less researched, a lot of researches focus on the influence of chlorine impurities in the waste plastic oil on the post-processing of the waste plastic oil, and the influence of other impurities, such as silicon impurities and metal impurities, contained in the waste plastic oil and the serious influence of the impurities on the subsequent processing technology are not realized.
CN104611060A discloses a method for producing clean fuel oil by using waste plastics and high aromatic components. After the high aromatic components are mixed with the waste plastic oil, the mixture firstly passes through a thermal cracking reaction zone, and the thermal cracking reaction zone adopts a mode of combining gradual temperature rise and constant temperature operation; and the obtained pyrolysis gas enters a catalytic reaction zone to contact with a catalyst in the catalytic reaction zone to perform catalytic reaction, and the obtained reaction effluent is subjected to gas-liquid separation to obtain a gas product and a liquid-phase oil product.
CN104726134A discloses a method for producing high-quality gasoline and diesel oil by using chlorine-containing plastic oil. The method is characterized in that chlorine-containing plastic oil is injected into a high-temperature dechlorination tower filled with active aluminum oxide for high-temperature dechlorination, a small amount of NaOH aqueous solution is sprayed on the top of the high-temperature dechlorination tower, and the dechlorinated plastic oil enters a catalytic distillation tower filled with a molecular sieve/aluminum oxide catalyst for reaction and rectification; the plastic oil after catalytic distillation enters a hydrofining tower under pressure, distillate oil after hydrofining is distilled under normal pressure and cut into gasoline and diesel oil according to the distillation temperature, and heavy oil at the bottom of the tower is mixed with chlorine-containing plastic oil as a raw material for re-reaction. The dechlorination catalyst and the sulfide catalyst used in the invention are prepared by selecting a proper method according to the composition and the performance of the plastic oil.
CN102942951A discloses a method for preparing clean diesel oil by a plastic oil hydrogenation method, which comprises the following steps: a. mixing plastic oil and hydrogen, and introducing the mixture into a pre-hydrogenation reactor filled with a hydrogenation protection catalyst for chemical reaction; b. the effluent of the pre-hydrogenation reactor enters a hot high-pressure separator for separation and stripping, and the effluent at the bottom of the hot high-pressure separator and the gas at the top of a cold high-pressure separator enter a main hydrogenation reactor for chemical reaction; c. the effluent of the main hydrogenation reactor enters a cold high-pressure separator for gas-liquid separation, the effluent at the bottom of the cold high-pressure separator enters a cold low-pressure separator for mixing with the light oil extracted from the middle part of the cold high-pressure separator and then enters a fractionating tower for separation, and clean diesel oil fraction with the sulfur content of less than 5 mu g/g and the cetane number of more than 50 can be extracted from the lateral line of the fractionating tower.
CN102226103A discloses a method for producing gasoline and diesel oil by using plastic oil. The process is characterized in that plastic oil is used as a raw material, distillation and hydrofining are carried out to produce high-quality gasoline and diesel oil, the plastic oil is distilled to obtain a fraction with the temperature of less than 300 ℃ and a fraction with the temperature of more than 300 ℃, then the fraction with the temperature of less than 300 ℃ is subjected to hydrofining reaction on a sulfide catalyst, monoolefine olefin compounds are removed through monoolefine olefin hydrofining saturation reaction, and the gasoline and diesel oil mixed oil with no peculiar smell and high quality is produced through desulfurization, nitrogen removal and colloid removal, and then the gasoline and diesel oil distillate oil is obtained through distillation. And the distillate with the temperature of more than 300 ℃ after distillation is subjected to reactive distillation and then is subjected to hydrofining or is mixed with the plastic oil for re-reaction. The sulfide catalyst used in the invention is prepared by selecting a proper carrier through a liquid phase method according to the composition and the performance of the pyrolysis plastic oil.
The prior art mainly focuses on the processes of dechlorination and refining of the waste plastic oil, and it is not recognized that the silicon-containing compounds in the waste plastic oil can generate serious toxic effects on the hydrogenation catalyst in the prior art and the catalysts in other subsequent processes, so that the subsequent processing process has short operation period or cannot realize industrial operation at all in fact.
Disclosure of Invention
The invention aims to solve the problem of short processing period when the prior art processes the raw materials of the waste plastic oil and/or the waste tire oil, and aims to provide a method and a system for producing clean diesel oil from the waste plastic oil and/or the waste tire oil.
The first aspect of the invention provides a method for producing clean diesel oil by using waste plastic oil and/or waste tire oil, which comprises the following steps:
(1) a impurity removing unit, wherein the waste plastic oil and/or waste tire oil raw material enters a impurity removing reactor to contact with a waste hydrogenation catalyst in the presence of hydrogen, and impurity removing reaction is carried out under the impurity removing reaction condition, and the silicon content of the liquid phase material in the obtained reaction effluent is less than 1 mu g/g, and the metal content is less than 5 mu g/g;
(2) a hydrogenation unit, wherein the reaction effluent obtained in the step (1) enters a hydrofining reactor, contacts a hydrofining catalyst in the presence of hydrogen, and carries out hydrofining reaction under the hydrofining reaction condition, the reaction effluent of the hydrofining reactor enters a hydrocracking reactor and contacts a hydrocracking catalyst, and carries out hydrocracking reaction under the hydrocracking reaction condition, and the reaction effluent of the hydrocracking reactor is separated to at least obtain a gasoline fraction, a diesel fraction and a tail oil fraction; part or all of the tail oil fraction is returned to the inlet of the impurity removing unit and/or the inlet of the hydrogenation unit.
In one embodiment of the invention, the waste plastic oil is a hydrocarbon material obtained by one or more conversion methods of thermal cracking, catalytic cracking and solution liquefaction of waste plastics; the distillation range of the waste plastic oil is 30-700 ℃, the silicon content is less than 10000 mug/g, the chlorine content is less than 10000 mug/g, and the metal content is less than 10000 mug/g. The waste plastic oil comprises 5-80% by volume of olefin, preferably 5-60%, less than 90% by volume of aromatic hydrocarbon, preferably 2-60%, and less than 90% by volume of paraffin, preferably 5-60%.
In the invention, the waste plastics are one or more of waste plastics in fresh domestic garbage, waste plastics in industrial and agricultural production and waste plastics in aged garbage, and the type of the waste plastics is one or more selected from PE, PP, PS and PVC.
In one embodiment of the invention, the waste tire oil is a hydrocarbon material obtained by one or more conversion methods of thermal cracking, catalytic cracking and solution liquefaction of waste tires; the distillation range of the waste tire oil is 30-700 ℃, the silicon content is less than 10000 mug/g, the chlorine content is less than 10000 mug/g, and the metal content is less than 10000 mug/g. The waste tire oil comprises 5-80% by volume of olefin, preferably 5-60% by volume of aromatic hydrocarbon, less than 90% by volume of aromatic hydrocarbon, preferably 2-60% by volume of paraffin, and less than 90% by volume of paraffin, preferably 5-60% by volume of paraffin.
In the present invention, the waste tires are various waste tires prepared from natural rubber and/or synthetic rubber.
In the present invention, the thermal cracking and thermal cracking reaction refers to a reaction in which hydrocarbon molecules including waste plastics and waste tires are decomposed into smaller molecules under the condition of air isolation under a high temperature condition. Depending on the reaction temperature, thermal cracking is performed at 600 ℃ or lower, and thermal cracking is performed at 600 ℃ or higher.
In the present invention, the catalytic cracking and catalytic cracking reaction refers to a reaction in which hydrocarbon molecules, including waste plastics and waste tires, are decomposed into smaller molecules under high temperature conditions in the presence of a catalyst. According to the difference in the reaction products, the reaction using low-carbon olefins (ethylene, propylene, butylene) as the target product is called catalytic cracking reaction, and the reaction using motor gasoline as the target product is called catalytic cracking reaction.
In the present invention, the solution-liquefaction reaction refers to a reaction in which waste plastics and waste tires are converted from a solid state to a liquid state in the presence of solvent naphtha and/or an organic solvent.
In one embodiment of the present invention, in the dehalogenation unit, the dehalogenation reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. Waste hydrogenation catalysts are filled in the fixed bed hydrogenation reactors and/or the moving bed reactors, and waste plastic oil and/or waste tire oil is fed to pass through at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor to carry out desilication, dechlorination, demetalization and other impurity removal reactions.
In an embodiment of the present invention, the impurity removing reactor is two or more fixed bed hydrogenation reactors connected in parallel, each reactor is filled with a waste hydrogenation catalyst, the feed material passes through at least one of the fixed bed hydrogenation reactors to perform impurity removing reaction, and when the waste hydrogenation catalyst in the fixed bed hydrogenation reactor is saturated with silicon or metal, the feed material is switched to other fixed bed hydrogenation reactors.
In one embodiment of the invention, the silicon saturation or metal saturation on the spent hydrogenation catalyst in the dehairing reactor is considered when the liquid phase feed in the reaction effluent has a silicon content of 1 μ g/g or more or a metal content of 5 μ g/g or more.
In an embodiment of the invention, the waste hydrogenation catalyst is one or more selected from a protective agent used to the end stage of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, a catalyst at the end stage, a regenerated protective agent and a regenerated catalyst.
In one embodiment of the present invention, the equivalent diameter of the spent hydrogenation catalyst is 0.5 to 16mm, preferably 1 to 10 mm. The shape of the waste hydrogenation catalyst is not limited at all, and for example, the shape of the waste hydrogenation catalyst comprises a spherical shape and various different shapes such as a strip-shaped clover, a butterfly shape, a Raschig ring and a honeycomb shape.
In an embodiment of the invention, the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 0 to 50 wt% of hydrogenation active metal oxide, 0 to 50 wt% of carbon, and 0 to 40 wt% of sulfur, wherein the hydrogenation active metal is selected from one or more of group VIII metals and group VIB metals.
In one embodiment of the present invention, the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 0 to 50 wt% of molybdenum oxide and/or tungsten oxide, 0 to 40 wt% of nickel oxide and/or cobalt oxide, 0 to 30 wt% of carbon, and 0 to 30 wt% of sulfur.
In an embodiment of the invention, the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 1 to 40 wt% of hydrogenation active metal oxide, and 20 wt% or less of carbon, wherein the hydrogenation active metal is selected from one or more of group VIII metals and group VIB metals.
In one embodiment of the invention, a plurality of waste hydrogenation catalysts are loaded in a layered manner, and along the material flowing direction, the equivalent diameter of the waste hydrogenation catalysts is gradually reduced, the pore diameter is gradually reduced, and the content of active metals is gradually increased.
In one embodiment of the invention, a dechlorinating agent is also filled in the impurity removing reactor, and the filling volume ratio of the dechlorinating agent to the waste catalyst is 1-80: 20 to 99 parts. The waste hydrogenation catalyst and the dechlorinating agent are uniformly mixed and filled or are filled in layers.
In one embodiment of the invention, the waste hydrogenation catalyst and the dechlorinating agent are filled in layers, and the dechlorinating agent is filled at the downstream of the waste hydrogenation catalyst according to the material flow direction.
In one embodiment of the present invention, the dechlorinating agent is one or more, and when the dechlorinating agent is plural, the dechlorinating agent may be loaded in a graded combination or mixed loading.
In one embodiment of the present invention, the hydrogenation reactor is at least one moving bed hydrogenation reactor, and the moving bed hydrogenation reactor is filled with a waste hydrogenation catalyst and a dechlorinating agent. And mechanically mixing the waste hydrogenation catalyst and the dechlorinating agent according to a certain proportion.
In one embodiment of the invention, the dechlorination agent comprises at least one group IA metal compound and/or at least one group IIA metal compound, optionally one or several metal oxides selected from Cu, Fe, Zn, and a carrier and/or a binder;
the carrier and/or the binder are/is selected from one or more of silica, alumina, silica-alumina, zirconia and clay. The clay is selected from one or more of kaolin, illite, montmorillonite and bentonite; the kaolin comprises halloysite.
In the invention, the optional one or more metal oxides selected from Cu, Fe and Zn mean that one or more metal oxides selected from Cu, Fe and Zn are optional components of the dechlorinating agent.
In the present invention, the dechlorination agent is preferably a high temperature dechlorination agent and/or a medium temperature dechlorination agent. The invention has no limitation to high-temperature dechlorinating agents and medium-temperature dechlorinating agents, and the invention can be realized by using conventional high-temperature dechlorinating agents and medium-temperature dechlorinating agents. Further preferred are high temperature dechlorinating agents and/or medium temperature dechlorinating agents with a large chlorine capacity.
In one embodiment of the present invention, the chlorine content in the liquid phase feed in the reaction effluent of step (1) is less than 0.5. mu.g/g.
In one embodiment of the present invention, the dehalogenation reaction conditions are: hydrogen partial pressure of 0.5-20.0 MPa, reaction temperature of 60-450 ℃ and volume space velocity of 0.1-30 h -1 The volume ratio of hydrogen to oil is 5-1000 Nm 3 /m 3 。
The preferable reaction conditions for removing impurities are: hydrogen partial pressure of 1-12 MPa, reaction temperature of 100-400 ℃ and volume space velocity of 0.2-20 h -1 The volume ratio of hydrogen to oil is 10-800 Nm 3 /m 3 。
In the hydrogenation unit in the step (2), the reaction effluent obtained in the impurity removal unit in the step (1) directly enters a hydrofining reactor, and is contacted with a hydrofining catalyst under the hydrofining reaction condition to carry out hydrodesulfurization, hydrodenitrogenation, olefin hydrogenation saturation and other reactions. The reaction effluent directly enters a hydrocracking reactor and contacts with a hydrocracking catalyst to carry out hydrocracking reaction under the hydrocracking reaction condition.
In one embodiment of the present invention, the hydrofining reaction conditions in step (2) are: hydrogen partial pressure of 0.5-20.0 MPa, reaction temperature of 60-450 ℃ and volume space velocity of 0.1-30 h -1 The volume ratio of hydrogen to oil is 5-1200 Nm 3 /m 3 ；
The preferred hydrofining reaction conditions are: hydrogen partial pressure of 1.0-18.0 MPa, reaction temperature of 100-400 ℃ and volume space velocity of 0.5-15 h -1 The volume ratio of hydrogen to oil is 50-1000 Nm 3 /m 3 。
In one embodiment of the invention, the hydrofining catalyst comprises a hydrogenation metal active component and a carrier, and the content of the hydrogenation metal active component is 5-50 wt% in terms of oxide based on the total weight of the hydrofining catalyst.
In a preferred case, the hydrogenation metal active component is at least one selected from group VIB metal elements and at least one selected from group VIII metal elements, the group VIB metal elements are molybdenum and/or tungsten, and the group VIII metal elements are cobalt and/or nickel; based on the total weight of the hydrofining catalyst, the content of the VIB group metal element is 4-40 wt%, preferably 8-35 wt%, and the content of the VIII group metal element is 1-10 wt%, preferably 2-5 wt%, calculated by oxides.
In one embodiment of the present invention, the hydrocracking reaction conditions in step (2) are: hydrogen partial pressure of 0.5-20.0 MPa, reaction temperature of 60-550 ℃ and volume space velocity of 0.1-30 h -1 The volume ratio of hydrogen to oil is 5-1200 Nm 3 /m 3 ；
The preferable hydrocracking reaction conditions are as follows: hydrogen partial pressure of 3.0-18.0 MPa, reaction temperature of 100-450 ℃ and volume space velocity of 0.5-15 h -1 The volume ratio of hydrogen to oil is 50-1000 Nm 3 /m 3 。
In one embodiment of the invention, the hydrocracking catalyst in the step (2) comprises a carrier and a hydrogenation metal active component, and the content of the hydrogenation metal active component is 5-50 wt% calculated by oxide based on the total amount of the hydrocracking catalyst;
the hydrogenation metal active component is at least one selected from VIB group metal elements and at least one selected from VIII group metal elements;
the hydrocracking catalyst carrier comprises a molecular sieve and alumina, and the content of the molecular sieve is 1-50 wt% based on the total weight of the carrier.
In one embodiment of the invention, the molecular sieve is selected from one or more of USY, Beta, ZSM-5, Y, LAY.
In the invention, reaction effluent obtained by a hydrocracking reactor is separated to at least obtain gasoline fraction, diesel oil fraction and tail oil fraction; part or all of the tail oil fraction is returned to the inlet of the impurity removing unit and/or the inlet of the hydrocracking unit.
In one embodiment of the invention, the initial boiling point of the obtained tail oil fraction is 350-380 ℃.
In the invention, the sulfur content of the obtained diesel oil fraction is less than 10 mug/g, and other indexes all meet the standard requirements of national six clean diesel oil. The yield of the diesel oil fraction is not less than 70 wt%, preferably not less than 75 wt%, based on the mass of the 180 ℃ upper fraction in the feedstock.
In another aspect, the invention provides a system for use in any of the above processes, comprising a dehazing unit, a hydrogenating unit;
the method comprises the following steps that a impurity removing unit is provided with a impurity removing reactor filled with waste hydrogenation catalysts, the impurity removing reactor is provided with at least one waste plastic oil and/or waste tire oil inlet and at least one reaction effluent outlet, and the waste hydrogenation catalysts are one or more of protective agents and catalysts used to the last stage of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, and regenerated protective agents and regenerated catalysts;
the reaction effluent outlet of the impurity removal unit is communicated with the feed inlet of the hydrogenation unit, the hydrogenation unit is provided with a hydrofining reactor filled with a hydrofining catalyst and a hydrocracking reactor filled with a hydrocracking catalyst, the reaction effluent outlet of the hydrofining reactor is communicated with the feed inlet of the hydrocracking reactor, the reaction effluent outlet of the hydrocracking reactor is communicated with the inlet of the separation unit, the separation unit is provided with at least one gas-phase material outlet, at least one gasoline fraction outlet, at least one diesel fraction outlet and at least one tail oil fraction outlet, the outlet of the tail oil fraction is communicated with the feed inlet of the impurity removal unit, and the outlet of the tail oil fraction is communicated with the feed inlet of the hydrogenation unit. .
In one embodiment of the invention, the dehazing reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor.
In one embodiment of the invention, the impurity removing reactor is more than two fixed bed hydrogenation reactors connected in parallel, each fixed bed hydrogenation reactor is filled with a waste hydrogenation catalyst, and each fixed bed hydrogenation reactor is provided with at least one feeding inlet and at least one reaction effluent outlet.
The invention has the characteristics that:
1. the invention can process the waste plastic oil and the waste tire oil converted by various processes, and the clean diesel oil product which meets the national diesel oil standard is obtained after the waste plastic oil and the waste tire oil are processed by the impurity removing unit and the hydrogenation unit.
2. The impurity removing unit effectively removes impurities in the waste plastic oil and the waste tire oil, particularly silicon impurities, chlorine impurities and metal impurities, and avoids the influence of the impurities on a hydrogenation refining catalyst in a hydrogenation refining unit, so that the whole operation period is prolonged.
3. The invention uses waste hydrogenation catalyst, which has low cost and good impurity removing effect. In the preferred embodiment of the invention, the pretreatment is carried out by adopting a moving bed or two fixed bed reactors which are switched in parallel and in turn, so that the aims of long-period deep desilication, demetallization and dechlorination are fulfilled.
Drawings
FIG. 1 is a schematic diagram of one embodiment of the method for producing clean diesel oil from waste plastic oil and/or waste tire oil provided by the invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings, but the invention is not limited thereto.
FIG. 1 is a schematic diagram of one embodiment of a method for producing clean diesel oil from waste plastic oil and/or waste tire oil provided by the invention. As shown in fig. 1, after the waste plastic oil and/or waste tire oil from a pipeline 1 is pressurized by a feed pump 2, new hydrogen from a pipeline 17 and circulating hydrogen from a pipeline 16 are mixed together from a pipeline 3, and then the mixture enters a heating furnace 5 from a pipeline 4 to be heated, the heated mixed hydrogen material enters a impurity removal unit, the impurity removal unit is provided with two fixed bed hydrogenation reactors 8 and 9 which are connected in parallel, a catalyst bed layer a is arranged in the fixed bed hydrogenation reactor 8 and is filled with waste hydrogenation catalysts in a grading manner, a catalyst bed layer B is arranged in the fixed bed hydrogenation reactor 9 and is filled with waste hydrogenation catalysts in a grading manner. In one embodiment, the mixed hydrogen material enters the fixed bed hydrogenation reactor 8 through the pipeline 6, contacts with the waste hydrogenation catalyst which is loaded in a grading way, and carries out a impurity removal reaction under the impurity removal reaction condition, and at the moment, the fixed bed hydrogenation reactor 9 is used for standby. When the waste hydrogenation catalyst in the fixed bed hydrogenation reactor 8 is saturated with silicon or metal, the hydrogen-mixed material enters the fixed bed hydrogenation reactor 9 through the pipeline 7 for reaction, the fixed bed hydrogenation reactor 8 is cut into a reaction system, and then the waste hydrogenation catalyst in the catalyst bed A is replaced.
Reaction effluent obtained from the impurity removing unit enters a hydrofining reactor 12 through pipelines 10 and 11, contacts with a hydrofining catalyst to react, enters a hydrocracking reactor 14 through a pipeline 13, contacts with a hydrocracking catalyst to react, enters a high-pressure separator 19 through a pipeline 18 to carry out gas-liquid separation, gas-phase material obtained is pressurized through a recycle hydrogen compressor 15 and then returns to an inlet of a heating furnace 5 through a pipeline 16, liquid-phase material obtained enters a fractionating tower 21 through a pipeline 20, gasoline fraction, diesel fraction and tail oil fraction are obtained after cutting, and are respectively extracted through pipelines 20, 23 and 24. Part or all of the tail oil fraction is returned to the inlet of the furnace 5 and/or the inlet of the hydrofinishing reactor 12 via line 25.
The invention will now be further illustrated with reference to the following examples, without thereby being restricted thereto.
In the examples, the silicon content in the hydrocarbon material was determined by the method of single wavelength dispersive X-ray fluorescence for determination of silicon content in gasoline and related products (SH/T0993-2019).
In the examples, the chlorine content in the liquid material was measured by coulometry, specifically by the method of determining the total chlorine content in crude oil by coulometry (RIPP 64-90) in petrochemical analysis methods (RIPP test methods). The used instrument is a microcoulomb analyzer, and the sample is a liquid material.
The dechlorinating agent used in the examples was an industrially practical dechlorinating agent RDY-100 produced by Jinan Ruitong industries, Ltd.
The reforming prehydrogenation end-stage catalyst E used in the examples had a support of alumina, butterfly shape, equivalent diameter of 1.6mm and active composition comprising: 18 percent of tungsten oxide, 2 percent of nickel oxide, 0.04 percent of cobalt oxide, 5.0 percent of carbon and 6 percent of sulfur;
in the gasoline hydrogenation final-stage catalyst F used in the examples, the carrier is alumina, butterfly-shaped, the equivalent diameter is 1.6mm, and the active composition comprises: 10 percent of molybdenum oxide, 3.5 percent of cobalt oxide, 8.0 percent of carbon and 7.0 percent of sulfur;
the final-stage hydrogenation catalyst G used in the example is a final-stage catalyst of a residual oil hydrogenation protective agent, the carrier is alumina, Raschig rings, the equivalent diameter is 6.0mm, and the active components comprise: 2 percent of molybdenum oxide, 0.5 percent of nickel oxide, 40 percent of carbon and 5 percent of sulfur;
in the hydrorefining catalyst C used in the examples, the carrier was alumina, butterfly-shaped, the equivalent diameter was 1.6mm, and the active metal composition was: 26 weight percent of molybdenum oxide and 4.0 weight percent of nickel oxide;
the catalyst D prepared by cracking used in the examples, the carrier is alumina and Beta molecular sieve, the butterfly shape, the equivalent diameter is 1.6mm, the active metal composition is: tungsten oxide 24.5 wt%, nickel oxide 6.3 wt%.
The properties of the raw materials are shown in table 1, wherein the raw materials H and I are waste plastic oil, and J is waste tire oil.
Examples 1 to 3
The method comprises the steps of enabling a waste plastic oil raw material to enter a impurity removal reactor to be in contact with a waste hydrogenation catalyst in the presence of hydrogen, conducting impurity removal reaction under impurity removal reaction conditions, enabling obtained reaction effluent to enter a hydrofining reactor to be in contact with a hydrofining catalyst, conducting hydrofining reaction under hydrofining reaction conditions, enabling reaction effluent of the hydrofining reactor to enter a hydrocracking reactor to be in contact with a hydrocracking catalyst, conducting hydrocracking reaction under hydrocracking reaction conditions, enabling reaction effluent of the hydrocracking reactor to pass through a high-pressure separator to be subjected to gas-liquid separation to obtain gas-phase material flow and liquid-phase material flow, enabling obtained liquid-phase material flow to enter a fractionating tower to be fractionated to obtain gasoline fraction, diesel fraction and tail oil fraction, and enabling all the tail oil fraction and the waste plastic oil raw material to enter the impurity removal reactor together after being mixed. The reaction conditions used are shown in Table 2, and the product yields and properties of the diesel fractions obtained are shown in Table 3.
As shown in Table 3, the obtained diesel fraction had low sulfur and high cetane number, and was a clean diesel product of good quality.
Examples 4 to 5
The method comprises the steps of enabling a waste plastic oil raw material and a waste tire oil raw material to enter a impurity removal reactor to be in contact with a waste hydrogenation catalyst in the presence of hydrogen, conducting impurity removal reaction under impurity removal reaction conditions, enabling obtained reaction effluent to enter a hydrofining reactor to be in contact with a hydrofining catalyst, conducting hydrofining reaction under hydrofining reaction conditions, enabling reaction effluent of the hydrofining reactor to enter a hydrocracking reactor to be in contact with a hydrocracking catalyst, conducting hydrocracking reaction under hydrocracking reaction conditions, enabling reaction effluent of the hydrocracking reactor to pass through a high-pressure separator to be subjected to gas-liquid separation to obtain a gas-phase material flow and a liquid-phase material flow, enabling the obtained liquid-phase material flow to enter a fractionating tower to be fractionated to obtain a gasoline fraction, a diesel fraction and a tail oil fraction, and mixing all the tail oil fraction and reaction effluent of a impurity removal unit, and enabling the mixture to enter the hydrofining reactor. The reaction conditions used are shown in Table 4, and the product yields and properties of the diesel fraction obtained are shown in Table 5.
As shown in Table 5, the obtained diesel fraction had low sulfur and high cetane number, and was a clean diesel product of good quality.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
Example 6
In this example, the impurity removal unit is provided with two fixed bed hydrogenation reactors 1 and 2 connected in parallel, and the raw material I is used as a feed, and the catalyst loading condition, impurity removal reaction conditions and reaction results are shown in table 6.
When the reactor 1 is operated for 250 hours, the silicon content of the liquid phase material in the reaction effluent is more than 1 mu g/g, the reactor 2 is switched to carry out the impurity removing reaction, and the silicon content of the liquid phase material is reduced to be less than 1 mu g/g. The reactor 1 is replaced with catalyst and the cycle achieves long-term operation.
TABLE 6
Example 7
In this example, the mobile bed reactor was used as the impurity removal unit, and the raw material J was used as a feed, and the catalyst loading, impurity removal reaction conditions and reaction results are shown in Table 7.
As can be seen from Table 7, the process of the present invention, using a moving bed in the de-impurity unit, treated feedstock J with a high impurity content, resulted in a first liquid phase material with a silicon content of less than 1. mu.g/g, a chlorine content of less than 0.5. mu.g/g, a metal content of less than 5. mu.g/g, and a dosage consumption of 3.2 kg/ton oil.
TABLE 7
It should be noted that the above-mentioned embodiments are only arbitrary embodiments of the present invention, and are not intended to limit the present invention, and those skilled in the art can make various modifications and variations. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (26)
1. A method for producing clean diesel oil by using waste plastic oil and/or waste tire oil comprises the following steps:
(1) a impurity removing unit, wherein the waste plastic oil and/or waste tire oil raw material enters a impurity removing reactor to contact with a waste hydrogenation catalyst in the presence of hydrogen, and impurity removing reaction is carried out under the impurity removing reaction condition, and the silicon content of the liquid phase material in the obtained reaction effluent is less than 1 mu g/g, and the metal content is less than 5 mu g/g;
(2) a hydrogenation unit, wherein the reaction effluent obtained in the step (1) enters a hydrofining reactor, contacts a hydrofining catalyst in the presence of hydrogen, and carries out hydrofining reaction under the hydrofining reaction condition, the reaction effluent of the hydrofining reactor enters a hydrocracking reactor and contacts a hydrocracking catalyst, and carries out hydrocracking reaction under the hydrocracking reaction condition, and the reaction effluent of the hydrocracking reactor is separated to at least obtain a gasoline fraction, a diesel fraction and a tail oil fraction; part or all of the tail oil fraction is returned to the inlet of the impurity removing unit and/or the inlet of the hydrogenation unit.
2. The method of claim 1, wherein the waste plastic oil is a hydrocarbon material obtained by one or more conversion methods of thermal cracking, catalytic cracking and solution liquefaction; the distillation range of the waste plastic oil is 30-700 ℃, the silicon content is less than 10000 mug/g, the chlorine content is less than 10000 mug/g, and the metal content is less than 10000 mug/g.
3. The method according to claim 2, wherein the waste plastics is one or more of waste plastics in fresh domestic garbage, waste plastics in industrial and agricultural production, and waste plastics in aged garbage, and the kind of waste plastics is one or more selected from PE, PP, PS, and PVC.
4. The method of claim 1, wherein the waste tire oil is a hydrocarbon material obtained by one or more conversion methods of thermal cracking, catalytic cracking and solution liquefaction of waste tires; the distillation range of the waste tire oil is 30-700 ℃, the silicon content is less than 10000 mug/g, the chlorine content is less than 10000 mug/g, and the metal content is less than 10000 mug/g.
5. The method according to claim 4, wherein the junked tires are various waste tires made of natural rubber and/or synthetic rubber.
6. The process according to claim 1, characterized in that the de-impurity reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor.
7. The method according to claim 1, wherein the impurity removing reactor is more than two fixed bed hydrogenation reactors connected in parallel, each reactor is filled with waste hydrogenation catalyst, the feeding material passes through at least one fixed bed hydrogenation reactor to carry out impurity removing reaction, and when the waste hydrogenation catalyst in the fixed bed hydrogenation reactor is saturated with silicon or metal, the feeding material is switched to other fixed bed hydrogenation reactors.
8. The method of claim 7, wherein the silicon saturation or metal saturation of the spent hydrogenation catalyst in the dehairing reactor is determined when the silicon content of the first liquid phase feed is greater than or equal to 1 μ g/g or the metal content is greater than or equal to 5 μ g/g.
9. The method according to claim 1, wherein the waste hydrogenation catalyst is one or more selected from the group consisting of a protective agent used to the end stage of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, a catalyst at the end stage, a regenerated protective agent and a regenerated catalyst.
10. The method of claim 9, wherein the equivalent diameter of the spent hydrogenation catalyst is 0.5 to 16 mm.
11. The method of claim 9, wherein the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 0 to 50 wt% of hydrogenation active metal oxide, 0 to 50 wt% of carbon, and 0 to 40 wt% of sulfur, and the hydrogenation active metal is selected from one or more of group VIII metals and group VIB metals.
12. The method of claim 11, wherein the spent hydrogenation catalyst comprises, based on the total weight of the spent hydrogenation catalyst, 0 to 50 wt% molybdenum oxide and/or tungsten oxide, 0 to 40 wt% nickel oxide and/or cobalt oxide, 0 to 30 wt% carbon, and 0 to 30 wt% sulfur.
13. The method of claim 11, wherein the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 1 to 40 wt% of hydrogenation active metal oxide, and 20 wt% or less of carbon, and the hydrogenation active metal is selected from one or more of group VIII metals and group VIB metals.
14. The method according to claim 1, wherein a dechlorinating agent is also filled in the impurity removing reactor, and the filling volume ratio of the dechlorinating agent to the waste catalyst is 1-80: 20 to 99 parts.
15. The process of claim 14, wherein the dechlorination agent comprises at least one group IA metal compound and/or at least one group IIA metal compound, optionally one or more metal oxides selected from Cu, Fe, Zn, and a support and/or a binder;
the carrier and/or the binder are/is selected from one or more of silica, alumina, silica-alumina, zirconia and clay.
16. The method as set forth in claim 1 or 14, wherein the chlorine content in the first liquid-phase material of the step (1) is less than 0.5 μ g/g.
17. The method of claim 1, wherein step (1)) The impurity removing reaction conditions are as follows: hydrogen partial pressure of 0.5-20.0 MPa, reaction temperature of 60-450 ℃ and volume space velocity of 0.1-30 h -1 The volume ratio of hydrogen to oil is 5-1000 Nm 3 /m 3 ；
The preferable reaction conditions for removing impurities are: hydrogen partial pressure of 1-12 MPa, reaction temperature of 100-400 ℃ and volume space velocity of 0.2-20 h -1 The volume ratio of hydrogen to oil is 10-800 Nm 3 /m 3 。
18. The method according to claim 1, wherein the hydrofining catalyst in the step (2) comprises a hydrogenation metal active component and a carrier, and the content of the hydrogenation metal active component is 5-50 wt% in terms of oxide based on the total weight of the hydrofining catalyst.
19. The process according to claim 18, wherein the hydrogenation metal active component is at least one element selected from group VIB metals and at least one element selected from group VIII metals, the group VIB metals being molybdenum and/or tungsten, the group VIII metals being cobalt and/or nickel; based on the total weight of the hydrofining catalyst, the content of the VIB group metal element is 4-40 wt%, preferably 8-35 wt%, and the content of the VIII group metal element is 1-10 wt%, preferably 2-5 wt%, calculated by oxides.
20. The method of claim 1, wherein the hydrofinishing reaction conditions of step (2) are: hydrogen partial pressure of 0.5-20.0 MPa, reaction temperature of 60-450 ℃ and volume space velocity of 0.1-30 h -1 The volume ratio of hydrogen to oil is 5-1200 Nm 3 /m 3 ；
The preferred hydrofining reaction conditions are: hydrogen partial pressure of 1.0-18.0 MPa, reaction temperature of 100-400 ℃ and volume space velocity of 0.5-15 h -1 The volume ratio of hydrogen to oil is 50-1000 Nm 3 /m 3 。
21. The process of claim 1, wherein the hydrocracking catalyst in step (2) comprises a carrier and a hydrogenation metal active component, and the hydrogenation metal active component is contained in an amount of 5 to 50 wt% in terms of oxide, based on the total amount of the hydrocracking catalyst;
the hydrogenation metal active component is at least one selected from VIB group metal elements and at least one selected from VIII group metal elements;
the hydrocracking catalyst carrier comprises a molecular sieve and alumina, and the content of the molecular sieve is 1-50 wt% based on the total weight of the carrier.
22. The method according to claim 1, wherein the hydrocracking reaction conditions in step (2) are: hydrogen partial pressure of 0.5-20.0 MPa, reaction temperature of 60-550 ℃ and volume space velocity of 0.1-30 h -1 The volume ratio of hydrogen to oil is 5-1200 Nm 3 /m 3 ；
The preferable hydrocracking reaction conditions are as follows: hydrogen partial pressure of 3.0-18.0 MPa, reaction temperature of 100-450 ℃ and volume space velocity of 0.5-15 h -1 The volume ratio of hydrogen to oil is 50-1000 Nm 3 /m 3 。
23. The method of claim 1, wherein the initial boiling point of the tail oil fraction is 350 to 380 ℃.
24. A system for use in any of the methods of claims 1-23, comprising a dehazing unit, a hydrogenating unit;
the method comprises the following steps that a impurity removing unit is provided with a impurity removing reactor filled with waste hydrogenation catalysts, the impurity removing reactor is provided with at least one waste plastic oil and/or waste tire oil inlet and at least one reaction effluent outlet, and the waste hydrogenation catalysts are one or more of protective agents and catalysts used to the last stage of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, and regenerated protective agents and regenerated catalysts;
the reaction effluent outlet of the impurity removal unit is communicated with the feed inlet of the hydrogenation unit, the hydrogenation unit is provided with a hydrofining reactor filled with a hydrofining catalyst and a hydrocracking reactor filled with a hydrocracking catalyst, the reaction effluent outlet of the hydrofining reactor is communicated with the feed inlet of the hydrocracking reactor, the reaction effluent outlet of the hydrocracking reactor is communicated with the inlet of the separation unit, the separation unit is provided with at least one gas-phase material outlet, at least one gasoline fraction outlet, at least one diesel fraction outlet and at least one tail oil fraction outlet, the outlet of the tail oil fraction is communicated with the feed inlet of the impurity removal unit, and the outlet of the tail oil fraction is communicated with the feed inlet of the hydrogenation unit.
25. The system of claim 24, wherein the de-impurity reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor.
26. The system of claim 24, wherein the impurity removal reactor is more than two fixed bed hydrogenation reactors connected in parallel, each fixed bed hydrogenation reactor is filled with a waste hydrogenation catalyst, and each fixed bed hydrogenation reactor is provided with at least one feeding inlet and at least one reaction effluent outlet.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101343565A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrogenation purification method for siliceous distillate |
| US20160264874A1 (en) * | 2015-03-10 | 2016-09-15 | Sabic Global Technologies, B.V. | Robust Integrated Process for Conversion of Waste Plastics to Final Petrochemical Products |
| CN107892990A (en) * | 2017-11-14 | 2018-04-10 | 新疆聚力环保科技有限公司 | A kind of method of waste mineral oil perhydro type regeneration production top-grade lubricating oil base oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343565A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrogenation purification method for siliceous distillate |
| US20160264874A1 (en) * | 2015-03-10 | 2016-09-15 | Sabic Global Technologies, B.V. | Robust Integrated Process for Conversion of Waste Plastics to Final Petrochemical Products |
| CN107892990A (en) * | 2017-11-14 | 2018-04-10 | 新疆聚力环保科技有限公司 | A kind of method of waste mineral oil perhydro type regeneration production top-grade lubricating oil base oil |
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