CN114437793A - Method and system for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil - Google Patents
Method and system for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil Download PDFInfo
- Publication number
- CN114437793A CN114437793A CN202011189039.4A CN202011189039A CN114437793A CN 114437793 A CN114437793 A CN 114437793A CN 202011189039 A CN202011189039 A CN 202011189039A CN 114437793 A CN114437793 A CN 114437793A
- Authority
- CN
- China
- Prior art keywords
- waste
- oil
- reactor
- hydrogenation
- reaction
- 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.)
- Granted
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 112
- 239000004033 plastic Substances 0.000 title claims abstract description 76
- 229920003023 plastic Polymers 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000010920 waste tyre Substances 0.000 title claims abstract description 48
- 239000002994 raw material Substances 0.000 title claims abstract description 34
- 238000001833 catalytic reforming Methods 0.000 title claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 128
- 238000006243 chemical reaction Methods 0.000 claims abstract description 121
- 239000003054 catalyst Substances 0.000 claims abstract description 105
- 239000012535 impurity Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 61
- 239000007791 liquid phase Substances 0.000 claims abstract description 37
- 239000012071 phase Substances 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 114
- 229910052751 metal Inorganic materials 0.000 claims description 52
- 239000002184 metal Substances 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000005194 fractionation Methods 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 230000000382 dechlorinating effect Effects 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 13
- 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
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000926 separation method 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
- -1 VIB metals Chemical class 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 239000003223 protective agent Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000010813 municipal solid waste Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 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
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 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
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 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
- 238000005695 dehalogenation reaction Methods 0.000 claims description 3
- 238000011049 filling Methods 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
- 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
- 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
- 239000011248 coating agent Substances 0.000 claims 2
- 238000000576 coating method Methods 0.000 claims 2
- 239000003502 gasoline Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 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
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 241000219793 Trifolium Species 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 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
- 230000007774 longterm Effects 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
- 238000007670 refining Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000010779 crude oil Substances 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
- 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
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite 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
- 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
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material 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
-
- 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
-
- 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
- C10G2300/1007—Used oils
-
- 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
Abstract
The invention relates to a method and a system for preparing catalytic reforming raw materials from waste plastic oil and/or waste tire oil. The method comprises the following steps of contacting waste plastic oil and/or waste tire oil with a waste hydrogenation catalyst in a impurity removal reactor, carrying out impurity removal reaction under the impurity removal reaction condition, allowing obtained reaction effluent to enter a hydrofining reactor, contacting the reaction effluent with a hydrofining catalyst, carrying out reaction, separating the reaction effluent to obtain a gas-phase material and a liquid-phase material, fractionating the obtained liquid-phase material to obtain naphtha fraction, wherein the naphtha fraction is a catalytic reforming raw material. The invention can effectively remove impurities in the waste plastic oil and/or the waste tire oil, provides qualified raw materials for catalytic reforming, and 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 preparing a catalytic reforming raw material 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 preparing catalytic reforming raw materials from the waste plastic oil and/or the waste tire oil.
In a first aspect of the present invention, there is provided a process for producing a catalytic reforming feedstock from waste plastic oil and/or waste tire oil, comprising:
(1') optionally performing a pre-fractionation unit, and cutting the waste plastic oil and/or waste tire oil raw material in the pre-fractionation unit to obtain light fractions with the final distillation point of less than 180 ℃;
(1) a impurity removal unit, namely, the waste plastic oil and/or waste tire oil raw material or the light fraction obtained in the step (1') enters a impurity removal reactor to contact with a waste hydrogenation catalyst in the presence of hydrogen, and impurity removal reaction is carried out under the impurity removal reaction condition, wherein the silicon content of a 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 hydrofining unit, wherein the reaction effluent obtained in the step (1) enters a hydrofining reactor, contacts with a hydrofining catalyst, and is subjected to hydrofining reaction under the hydrofining reaction condition, and the reaction effluent is separated to obtain a gas-phase material and a liquid-phase material;
(3) and (3) a fractionation unit, wherein the liquid phase material obtained in the step (2) enters the fractionation unit, and at least naphtha fraction is obtained after fractionation, wherein the naphtha fraction contains less than 0.5 mu g/g of sulfur, less than 0.5 mu g/g of nitrogen and less than 0.5gBr/100g of bromine and is used as a catalytic reforming raw material.
In one embodiment of the invention, the waste plastic oil is a hydrocarbon material obtained by converting waste plastic through one or more of thermal cracking, catalytic cracking and dissolving 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. 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 the thermal cracking reaction refer 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.
By "optional" is meant in the present invention in the alternative, by which is meant that the prefractionation unit is an optional unit. In one embodiment of the invention, a prefractionation unit, a dehalogenation unit, a hydrofinishing unit, and a fractionation unit are included. Cutting the waste plastic oil and/or waste tire oil raw material in a pre-fractionation unit to obtain light fraction with the final distillation point less than 180 ℃, and enabling the obtained light fraction to enter a impurity removal reactor to contact with a waste hydrogenation catalyst to perform impurity removal reactions such as dechlorination, demetalization, desilication and the like under the impurity removal reaction condition.
In one embodiment of the present invention, in the optional prefractionation unit of step (1'), the waste plastic oil and/or waste tire oil feedstock is cut to obtain light fractions with an end point of less than 160 ℃.
In one embodiment of the invention, the de-impurity reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. Filling waste hydrogenation catalysts in the fixed bed hydrogenation reactor and/or the moving bed reactor, and carrying out desilication, dechlorination, demetalization and other impurity removal reactions on the fed materials by at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor; the feed is waste plastic oil and/or waste tire oil or light fraction obtained by a pre-fractionation unit.
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. The waste hydrogenation catalyst and the dechlorinating agent are mechanically mixed 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: partial pressure of hydrogen 05 to 20.0MPa, the reaction temperature of 60 to 450 ℃ and the volume space velocity of 0.1 to 30h-1The volume ratio of hydrogen to oil is 5-1000 Nm3/m3。
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-1The volume ratio of hydrogen to oil is 10-800 Nm3/m3。
In the hydrofining unit in the step (2), the reaction effluent obtained in the impurity removing unit in the step (1) directly enters a hydrofining reactor, and is in contact reaction with a hydrofining catalyst under the hydrofining reaction condition to remove impurities such as sulfur, nitrogen and the like, and olefin is subjected to hydrogenation saturation.
In one embodiment of the present invention, the hydrofinishing reaction conditions are: hydrogen partial pressure of 1.0-20.0 MPa, reaction temperature of 150-420 ℃ and volume space velocity of 0.5-20 h-1The volume ratio of hydrogen to oil is 10-1000 Nm3/m3；
The preferred hydrofining reaction conditions are: hydrogen partial pressure of 1.0-12 MPa, reaction temperature of 200-400 ℃ and volume space velocity of 0.5-15 h-1The volume ratio of hydrogen to oil is 50-800 Nm3/m3。
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.
And separating the reaction effluent obtained by the hydrorefining reactor to obtain a gas-phase material and a liquid-phase material. And fractionating the obtained liquid phase material in a fractionating unit to obtain at least naphtha fraction. The fractionating unit is provided with a stripping tower and/or a fractionating tower with a stripping function.
In one embodiment of the invention, the naphtha fraction obtained has a sulfur content of < 0.5. mu.g/g, a nitrogen content of < 0.5. mu.g/g, a bromine number of <0.5 gBr/100g, a silicon content of < 1. mu.g/g, a chlorine content of < 0.5. mu.g/g, a metal content of < 1. mu.g/g, an aromatic hydrocarbon content of > 35% by mass, and is a high-quality catalytic reforming material.
In another aspect, the invention provides a system for use in any of the above processes, comprising an optional prefractionation unit, a dehazing unit, a hydrofinishing unit, a fractionation unit;
the pre-fractionation unit is provided with at least one waste plastic oil and/or waste tire oil inlet and at least one light fraction outlet;
the method comprises the following steps that a dehairing unit is provided with a dehairing reactor filled with waste hydrogenation catalysts, the dehairing reactor is provided with at least one waste plastic oil and/or waste tire oil inlet or light fraction inlet and at least one reaction effluent outlet, and the waste hydrogenation catalysts are one or more of protective agents used to the last stage of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, catalysts at the last stage, regenerated protective agents and regenerated catalysts;
the reaction effluent outlet of the impurity removal unit is communicated with the feeding inlet of the hydrofining unit, the hydrofining unit is provided with a hydrofining reactor filled with hydrofining catalyst, the reaction effluent outlet of the hydrofining reactor is communicated with the inlet of the separation unit, and the separation unit is provided with at least one gas phase material outlet and at least one liquid phase material outlet;
the fractionating unit is provided with a liquid-phase material inlet and at least one naphtha fraction outlet, and the liquid-phase material outlet of the separating unit is communicated with the liquid-phase material inlet of the fractionating 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.
Drawings
FIG. 1 is a schematic diagram of one embodiment of the method for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil provided by the invention.
FIG. 2 is a schematic diagram of one embodiment of the method for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil provided by the invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings, but the invention is not limited thereby.
FIG. 1 is a schematic diagram of one embodiment of the method for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil provided by the present invention, as shown in FIG. 1, the waste plastic oil and/or waste tire oil raw material from a pipeline 1 is cut in a prefractionator 22 to obtain light fraction and heavy fraction, which are respectively extracted through a pipeline 23 and a pipeline 24.
After the pressure of the light fraction from the pipeline 23 is increased by the feed pump 2, the light fraction from the pipeline 3, new hydrogen from the pipeline 17 and circulating hydrogen from the pipeline 16 enter the heating furnace 4 for heating, the heated mixed hydrogen material enters the impurity removal unit through the pipeline 5, 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 the 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.
The reaction effluent obtained from the impurity removing unit enters a hydrofining reactor 12 through pipelines 10 and 11 to contact with a hydrofining catalyst for reaction, the reaction effluent enters a high-pressure separator 14 through a pipeline 13 for gas-liquid separation, the obtained liquid phase material is pumped out through a pipeline 18, and the obtained gas phase material is pressurized by a recycle hydrogen compressor 15 and then returns to the inlet of the heating furnace 4 through a pipeline 16.
Fig. 2 is a schematic diagram of one embodiment of the method for preparing catalytic reforming raw materials from waste plastic oil and/or waste tire oil provided by the present invention, as shown in fig. 2, after the pressure of the waste plastic oil and/or waste tire oil from a pipeline 1 is raised by a feed pump 2, the waste plastic oil and/or waste tire oil from the pipeline 3, new hydrogen from a pipeline 17 and circulating hydrogen from a pipeline 16 enter a heating furnace 4 for heating, the heated hydrogen-mixed material enters a impurity removal unit through a pipeline 5, the impurity removal unit is provided with two fixed bed hydrogenation reactors 8 and 9 connected in parallel, a catalyst bed a is arranged in the fixed bed hydrogenation reactor 8, the fixed bed hydrogenation reactor 9 is filled with waste hydrogenation catalysts in a grading manner, and a catalyst bed 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.
The reaction effluent obtained from the impurity removing unit enters a hydrofining reactor 12 through pipelines 10 and 11 to contact with a hydrofining catalyst for reaction, the reaction effluent enters a high-pressure separator 14 through a pipeline 13 for gas-liquid separation, the obtained liquid phase material is pumped out through a pipeline 18, and the obtained gas phase material is pressurized by a recycle hydrogen compressor 15 and then returns to the inlet of the heating furnace 4 through a pipeline 16.
The liquid phase material from the pipeline 18 enters a fractionating tower 19, and after fractionation, a naphtha fraction is obtained and is extracted through a pipeline 20, and a heavy fraction is obtained and is extracted through a pipeline 21.
The invention is further illustrated by the following examples, without any intention to limit the invention thereto.
In the examples, the silicon content in hydrocarbon materials was determined by the method of single wavelength dispersive X-ray fluorescence (SH/T0993-2019) for determination of silicon content in gasoline and related products.
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 D used in the examples had a support of alumina, butterfly shape, equivalent diameter of 1.6mm and a 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;
the carrier of the gasoline hydrogenation final-stage catalyst E used in the embodiment is alumina and butterfly-shaped, the equivalent diameter is 1.6mm, and the composition comprises: 10 weight percent of molybdenum oxide, 3.5 weight percent of cobalt oxide, 8.0 weight percent of carbon and 7.0 weight percent of sulfur;
in the last-stage catalyst F for diesel hydrorefining used in the examples, the carrier was alumina, butterfly-shaped, the equivalent diameter was 1.6mm, and the composition included: 26 weight percent of molybdenum oxide, 4.0 weight percent of nickel oxide, 20 weight percent of carbon and 15 weight percent of sulfur.
The hydrorefining catalyst G used in the examples had alumina as the carrier, clover, equivalent diameter of 1.6mm, and comprised: 19 percent of tungsten oxide, 2.0 percent of nickel oxide and 0.4 percent of cobalt oxide.
The properties of the used raw materials are shown in table 1, wherein the raw material H is waste plastic oil, the raw material I is a mixed raw material of the waste plastic oil and the waste tire oil, and the mixing ratio is 40: 60 weight portions, and the raw material J is waste tire oil.
Examples 1 to 3
Cutting the waste plastic oil and/or waste tire oil raw material in a pre-fractionation unit to obtain light fraction; the obtained light fraction enters a impurity removal reactor to contact with a waste hydrogenation catalyst in the presence of hydrogen, impurity removal reaction is carried out under the impurity removal reaction condition, the obtained reaction effluent enters a hydrofining reactor to contact with a hydrofining catalyst, hydrofining reaction is carried out under the hydrofining reaction condition, and a gas-phase material and a liquid-phase material are obtained after the reaction effluent is separated; the obtained liquid phase material enters a fractionation unit, and naphtha fraction is obtained after fractionation, wherein the specific reaction conditions and the product properties are shown in Table 2.
As shown in Table 2, the resulting naphtha fraction had a sulfur content of < 0.5. mu.g/g, a nitrogen content of < 0.5. mu.g/g, a bromine number of <0.5 gBr/100g, and was a high-quality catalytic reforming material,
examples 4 to 7
The method comprises the following steps that waste plastic oil and/or waste tire oil raw materials enter a impurity removal reactor to be in contact with a waste hydrogenation catalyst in the presence of hydrogen, impurity removal reaction is carried out under the impurity removal reaction condition, obtained reaction effluent enters a hydrofining reactor to be in contact with a hydrofining catalyst, hydrofining reaction is carried out under the hydrofining reaction condition, and gas-phase materials and liquid-phase materials are obtained after the reaction effluent is separated; the obtained liquid phase material enters a fractionation unit, and at least naphtha fraction is obtained after fractionation, wherein the specific reaction conditions and product properties are shown in Table 3.
As shown in Table 3, the resulting naphtha fraction had a sulfur content of < 0.5. mu.g/g, a nitrogen content of < 0.5. mu.g/g, and a bromine number of <0.5 gBr/100g, and was a high-quality catalytic reforming material.
TABLE 1
TABLE 2
TABLE 3
Example 8
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 4.
When the reactor 1 is operated for 800h, the metal content of the liquid phase material in the reaction effluent is more than 5 mug/g, and the reactor 2 is switched to, and the metal content of the liquid phase material is reduced to less than 1 mug/g. The reactor 1 is replaced with catalyst and the cycle achieves long-term operation.
TABLE 4
Example 9
In this example, the dehydrogenation unit was equipped with two fixed bed hydrogenation reactors 1 and 2 in parallel, using feed H as the feed, and the catalyst loading, the dehydrogenation reaction conditions and the reaction results are shown in table 5.
When the reactor 1 is operated for 400 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 impurity removal 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 5
Example 10
The catalyst loading, the impurity removal reaction conditions and the reaction results of the impurity removal unit moving bed reactor of this example using feed H are shown in Table 6.
As can be seen from Table 6, when the method of the present invention is adopted to treat the raw material H with high impurity content in the impurity removal unit by using the moving bed, the silicon content of the obtained liquid phase reaction effluent is less than 1 mu g/g, the chlorine content is less than 0.5 mu g/g, the metal content is less than 5 mu g/g, and the agent consumption is 10.3 kg/ton oil.
TABLE 6
| Desertisation unit | Moving bed reactor |
| Catalyst and process for preparing same | D |
| Raw oil | Starting material H |
| Reaction pressure, Mpa | 1.6 |
| Reaction temperature of | 380 |
| Hydrogen to oil ratio, Nm3/m3 | 300 |
| Consumption of agent, kg/ton oil | 10.3 |
| Liquid phase reaction effluent | |
| Silicon content, μ g/g | <1 |
| Chlorine content,. mu.g/g | <0.5 |
| Metal content,. mu.g/g | <5 |
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 (25)
1. A method for preparing catalytic reforming raw materials from waste plastic oil and/or waste tire oil comprises the following steps:
(1') optionally performing a pre-fractionation unit, and cutting the waste plastic oil and/or waste tire oil raw material in the pre-fractionation unit to obtain light fractions with the final distillation point of less than 180 ℃;
(1) a impurity removal unit, namely, the waste plastic oil and/or waste tire oil raw material or the light fraction obtained in the step (1') enters a impurity removal reactor to contact with a waste hydrogenation catalyst in the presence of hydrogen, and impurity removal reaction is carried out under the impurity removal reaction condition, wherein the silicon content of a 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 hydrofining unit, wherein the reaction effluent obtained in the step (1) enters a hydrofining reactor, contacts with a hydrofining catalyst, and is subjected to hydrofining reaction under the hydrofining reaction condition, and the reaction effluent is separated to obtain a gas-phase material and a liquid-phase material;
(3) and (3) a fractionation unit, wherein the liquid phase material obtained in the step (2) enters the fractionation unit, and at least naphtha fraction is obtained after fractionation, wherein the naphtha fraction contains less than 0.5 mu g/g of sulfur, less than 0.5 mu g/g of nitrogen and less than 0.5gBr/100g of bromine and is used as a catalytic reforming raw material.
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 in the optional prefractionation unit of step (1'), the scrap plastic oil and/or scrap tire oil feedstock is cut to obtain a light fraction with an end point of < 160 ℃.
7. 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.
8. 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.
9. The method of claim 8, wherein the silicon saturation or metal saturation on the spent hydrogenation catalyst in the dehalogenation reactor is deemed to be when the liquid phase feed in the reaction effluent has a silicon content of 1 μ g/g or greater or a metal content of 5 μ g/g or greater.
10. 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.
11. The method of claim 10, wherein the equivalent diameter of the spent hydrogenation catalyst is 0.5 to 16 mm.
12. The method of claim 10, 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.
13. The method of claim 12, 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.
14. The method of claim 12, 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.
15. 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.
16. The process of claim 15, 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.
17. The process according to claim 1 or 15, wherein the chlorine content in the liquid phase material in the reaction effluent of step (1) is less than 0.5 μ g/g.
18. The method of claim 1, wherein the step of applying the coating comprises applying a coating to the substrateThe 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-1The volume ratio of hydrogen to oil is 5-1000 Nm3/m3(ii) a 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-1The volume ratio of hydrogen to oil is 10-800 Nm3/m3。
19. 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.
20. The process according to claim 19, 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 are molybdenum and/or tungsten, and the group VIII metals 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.
21. The method of claim 1, wherein the hydrofinishing reaction conditions of step (2) are: hydrogen partial pressure of 1.0-20.0 MPa, reaction temperature of 150-420 ℃ and volume space velocity of 0.5-20 h-1The volume ratio of hydrogen to oil is 10-1000 Nm3/m3(ii) a The preferred hydrofining reaction conditions are: hydrogen partial pressure of 1.0-12 MPa, reaction temperature of 200-400 ℃ and volume space velocity of 0.5-15 h-1The volume ratio of hydrogen to oil is 50-800 Nm3/m3。
22. The process according to claim 1, characterized in that the naphtha fraction obtained in step (3) has a chlorine content of <0.5 μ g/g and a metal content of <1 μ g/g.
23. A system for use in any of the methods of claims 1-22, comprising an optional prefractionation unit, a dehazing unit, a hydrofinishing unit, a fractionation unit;
the pre-fractionation unit is provided with at least one waste plastic oil and/or waste tire oil inlet and at least one light fraction outlet;
the method comprises the following steps that a dehairing unit is provided with a dehairing reactor filled with waste hydrogenation catalysts, the dehairing reactor is provided with at least one waste plastic oil and/or waste tire oil inlet or light fraction inlet and at least one reaction effluent outlet, and the waste hydrogenation catalysts are one or more of protective agents used to the last stage of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, catalysts at the last stage, regenerated protective agents and regenerated catalysts;
the reaction effluent outlet of the impurity removal unit is communicated with the feeding inlet of the hydrofining unit, the hydrofining unit is provided with a hydrofining reactor filled with hydrofining catalyst, the reaction effluent outlet of the hydrofining reactor is communicated with the inlet of the separation unit, and the separation unit is provided with at least one gas phase material outlet and at least one liquid phase material outlet;
the fractionating unit is provided with a liquid-phase material inlet and at least one naphtha fraction outlet, and the liquid-phase material outlet of the separating unit is communicated with the liquid-phase material inlet of the fractionating unit.
24. The system of claim 23, wherein the de-impurity reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor.
25. The system of claim 23, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011189039.4A CN114437793B (en) | 2020-10-30 | 2020-10-30 | Method and system for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011189039.4A CN114437793B (en) | 2020-10-30 | 2020-10-30 | Method and system for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114437793A true CN114437793A (en) | 2022-05-06 |
| CN114437793B CN114437793B (en) | 2023-11-10 |
Family
ID=81357238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011189039.4A Active CN114437793B (en) | 2020-10-30 | 2020-10-30 | Method and system for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114437793B (en) |
Citations (6)
| 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 |
| CN101591565A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of hydrofinishing process of inferior patrol |
| CN101845323A (en) * | 2010-05-14 | 2010-09-29 | 大连理工大学 | Process for producing petrol and diesel oil by plastic oil |
| 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 |
| WO2020130880A1 (en) * | 2018-12-20 | 2020-06-25 | Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз") | Guard bed catalyst for hydrotreatment of silicon-containing hydrocarbon feedstock |
-
2020
- 2020-10-30 CN CN202011189039.4A patent/CN114437793B/en active Active
Patent Citations (6)
| 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 |
| CN101591565A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of hydrofinishing process of inferior patrol |
| CN101845323A (en) * | 2010-05-14 | 2010-09-29 | 大连理工大学 | Process for producing petrol and diesel oil by plastic oil |
| 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 |
| WO2020130880A1 (en) * | 2018-12-20 | 2020-06-25 | Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз") | Guard bed catalyst for hydrotreatment of silicon-containing hydrocarbon feedstock |
Non-Patent Citations (1)
| Title |
|---|
| 陈宗杰等: "塑料油加氢脱氯催化剂性能", 《工业催化》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114437793B (en) | 2023-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5567022B2 (en) | Process for producing high added value aromatics and olefins from light cycle oils in fluidized bed catalytic cracking process | |
| CN103305269B (en) | Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar | |
| EP2831200A1 (en) | Methods and apparatuses for processing renewable feedstocks | |
| KR20230128045A (en) | Method for treating plastic pyrolysis oil including hydrogenation step | |
| CN115141645B (en) | Method and system for producing diesel oil from waste plastic oil and/or waste tire oil | |
| CN114437763B (en) | Method and system for hydrotreatment pretreatment of waste plastic oil and/or waste tire oil | |
| CN116323864A (en) | Method for processing pyrolysis oil by recycling fuel from plastics and/or solids loaded with impurities | |
| CN114437775B (en) | Method and system for producing aromatic hydrocarbon extraction raw material from waste plastic oil and/or waste tire oil | |
| CN114437793B (en) | Method and system for preparing catalytic reforming raw material from waste plastic oil and/or waste tire oil | |
| CN103289741B (en) | A combined method of hydrotreating-catalytic cracking-PSA purification for heavy oil | |
| CN102585898A (en) | High-nitrogen high-aromatic-oil two-stage method hydrocarbon hydrogenation method | |
| CN114806632B (en) | Method and system for producing vehicle fuel from waste plastic oil and/or waste tire oil | |
| CN114806633B (en) | Method and system for producing clean diesel oil from waste plastic oil and/or waste tire oil | |
| CN114437776B (en) | Method and system for preparing cracking raw material from waste plastic oil and/or waste tire oil | |
| CN114437825B (en) | Method and system for preparing aromatic extraction raw material from waste plastic oil and/or waste tire oil | |
| CN114437794B (en) | Method and system for processing waste plastic oil and/or waste tire oil | |
| CN114437764B (en) | Desilication method and system for siliceous hydrocarbon raw material | |
| CN104560153A (en) | Method for producing clean fuel oil employing ethylene bottom oil and heavy benzol | |
| CN103789035A (en) | Method for heavy benzene hydrogenation to produce clean fuel oil | |
| CN103540358A (en) | Residual oil conversion-aromatic hydrocarbon extraction combined process | |
| CN114958422B (en) | Dechlorination method of chlorine-containing raw oil | |
| CN117004433A (en) | Method for dechlorinating waste plastic oil and/or waste tire oil | |
| CN111849552B (en) | Coal tar full-fraction hydrogenation upgrading method and system | |
| CN207175874U (en) | A kind of device of middle coalite tar pretreatment hydrofinishing PSA production gasoline and diesel oil | |
| AU2022270874A1 (en) | Integrated method for processing pyrolysis oils of plastics and/or solid recovered fuels loaded with impurities |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |