CN114437793B - 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
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- CN114437793B CN114437793B CN202011189039.4A CN202011189039A CN114437793B CN 114437793 B CN114437793 B CN 114437793B CN 202011189039 A CN202011189039 A CN 202011189039A CN 114437793 B CN114437793 B CN 114437793B
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- waste
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- 239000002699 waste material Substances 0.000 title claims abstract description 109
- 239000004033 plastic Substances 0.000 title claims abstract description 73
- 229920003023 plastic Polymers 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000002994 raw material Substances 0.000 title claims abstract description 36
- 239000010920 waste tyre Substances 0.000 title claims abstract description 33
- 238000001833 catalytic reforming Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 119
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 117
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- 239000012535 impurity Substances 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000007791 liquid phase Substances 0.000 claims abstract description 33
- 239000012071 phase Substances 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 110
- 229910052751 metal Inorganic materials 0.000 claims description 58
- 239000002184 metal Substances 0.000 claims description 50
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 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 27
- 230000000382 dechlorinating effect Effects 0.000 claims description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 23
- 229910052710 silicon Inorganic materials 0.000 claims description 23
- 239000010703 silicon Substances 0.000 claims description 23
- 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
- 238000005194 fractionation Methods 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 229910052799 carbon Inorganic materials 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
- 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
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 239000010813 municipal solid waste Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 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
- 238000004090 dissolution Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 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
- 239000003223 protective agent Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- -1 VIB metals Chemical class 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000009396 hybridization 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000012271 agricultural production Methods 0.000 claims description 2
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 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
- 238000009776 industrial production Methods 0.000 claims description 2
- 150000002739 metals Chemical class 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 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
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000006298 dechlorination reaction Methods 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000002156 mixing Methods 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003869 coulometry Methods 0.000 description 2
- 238000011161 development 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
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- 230000003009 desulfurizing effect 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
- 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
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum 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
- 150000003377 silicon compounds Chemical class 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
- 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
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a method and a system for preparing catalytic reforming raw materials from waste plastic oil and/or junked tire oil. Waste plastic oil and/or waste tire oil are/is contacted with a waste hydrogenation catalyst in a impurity removal reactor, impurity removal reaction is carried out under impurity removal reaction conditions, the obtained reaction effluent enters a hydrofining reactor, the reaction effluent is contacted with the hydrofining catalyst for reaction, gas phase materials and liquid phase materials are obtained after the reaction effluent is separated, and naphtha fractions are obtained by fractionating the obtained liquid phase materials, wherein the naphtha fractions are catalytic reforming raw materials. 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
With the continuous development of urban process in China, urban population rises year by year, the living standard of people is continuously improved, the yield of urban household garbage is continuously increased, and the current urban garbage treatment method mainly comprises landfill, incineration and the like. There are a series of subsequent environmental protection issues, whether incineration or landfill.
The chemical conversion method can convert the plastic garbage 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 developed a situation of blooming throughout China, and 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 waste plastic oil, the waste tire oil and the traditional petroleum-based oil converted by various processes have large difference, and the high impurity content, especially the high silicon content, brings great trouble to the subsequent processing. At present, few researches are conducted on deep processing of waste plastic oil and waste tire oil, and much research focuses on the influence of chlorine impurities in the waste plastic oil on post-processing of the waste plastic oil, and the situation that other impurities such as silicon impurities and metal impurities are also contained in the waste plastic oil is not realized, and the serious influence of the impurities on the subsequent processing technology is not realized.
CN104611060a discloses a method for producing clean fuel oil from waste plastics and high aromatic components. After the high aromatic component is mixed with the waste plastic oil, the waste plastic oil passes through a thermal cracking reaction zone, and the thermal cracking reaction zone adopts a mode of combining gradual heating and constant temperature operation; and (3) the obtained pyrolysis gas enters a catalytic reaction zone to be contacted with a catalyst in the catalytic reaction zone for catalytic reaction, and the obtained reaction effluent enters 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 from 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 hydrogenation refining tower through pressurization, the distillate oil after hydrogenation refining is distilled at a constant pressure, the distillate oil is cut into gasoline and diesel oil according to the distillation temperature, and the heavy oil at the bottom of the tower is mixed with the raw material chlorine-containing plastic oil for re-reaction. The dechlorination catalyst and the sulfide catalyst used in the invention are prepared by selecting proper methods according to the composition and the performance of the plastic oil.
CN102942951a discloses a method for preparing clean diesel oil by hydrogenation of plastic oil, which comprises the following steps: a. mixing the plastic oil and hydrogen, and entering a pre-hydrogenation reactor filled with a hydrogenation protecting catalyst for chemical reaction; b. the effluent of the pre-hydrogenation reactor enters a hot high-pressure separator for separation and gas stripping, and the effluent at the bottom of the hot high-pressure separator and the gas at the top of the 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 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 fractions with sulfur content less than 5 mug/g and cetane number higher 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 firstly, the plastic oil is distilled to obtain a fraction smaller than 300 ℃ and a fraction larger than 300 ℃, then the fraction smaller than 300 ℃ is hydrofined on a sulfide catalyst, the mono-olefin is removed through hydrogenation saturation reaction of mono-olefin, no peculiar smell is produced by desulfurizing, removing nitrogen and removing colloid, and the gasoline and diesel oil mixed oil with high quality is obtained through distillation. The distillate with the distillation temperature of more than 300 ℃ is subjected to reactive distillation and then hydrofining or mixing with plastic oil for re-reaction. The sulfide catalyst used in the invention is prepared by selecting a proper carrier according to the composition and the performance of the pyrolysis plastic oil through a liquid phase method.
The prior art mainly focuses on the dechlorination and refining processes of waste plastic oil, and is not aware that silicon compounds in the waste plastic oil can have serious toxic effects on the hydrogenation catalyst in the prior art and catalysts in other subsequent processes, so that the operation period of the subsequent processes is short, or industrial operation cannot be realized in fact.
Disclosure of Invention
The invention aims to solve the problem of short processing period when waste plastic oil and/or waste tire oil raw materials are processed in the prior art, and provides a method and a system for preparing catalytic reforming raw materials from the waste plastic oil and/or the waste tire oil.
The first aspect of the present invention provides a method for preparing a catalytic reforming raw material from waste plastic oil and/or junked tire oil, comprising:
(1') an optional prefractionation unit, and cutting the waste plastic oil and/or waste tire oil raw materials in the prefractionation unit to obtain light fraction with the final distillation point less than 180 ℃;
(1) The impurity removing unit, the waste plastic oil and/or the waste tire oil raw material, or the light fraction obtained in the step (1'), enters into an impurity removing reactor to contact with a waste hydrogenation catalyst in the presence of hydrogen, and the impurity removing reaction is carried out under the impurity removing reaction condition, wherein the silicon content of the liquid phase material in the obtained reaction effluent is less than 1 mug/g, and the metal content is less than 5 mug/g;
(2) A hydrofining unit, wherein the reaction effluent obtained in the step (1) enters a hydrofining reactor to be contacted with a hydrofining catalyst, and hydrofining reaction is carried out under the condition of hydrofining reaction, 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 sulfur content in the naphtha fraction is less than 0.5 mug/g, the nitrogen content is less than 0.5 mug/g, and the bromine valence is less than 0.5gBr/100g, and the naphtha fraction is a catalytic reforming raw material.
In one embodiment of the invention, the waste plastic oil is hydrocarbon materials obtained by one or more conversion methods of thermal cracking, catalytic cracking and dissolution liquefaction of waste plastic; 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 composition of the waste plastic oil comprises olefin with volume fraction of 5-80%, preferably 5-60%, aromatic hydrocarbon with volume fraction of less than 90%, preferably 2-60%, and alkane with volume fraction of less than 90%, preferably 5-60%.
In the invention, the waste plastic is one or more of waste plastic in fresh household garbage, waste plastic in industrial and agricultural production and waste plastic in aged garbage, and the waste plastic is one or more selected from PE, PP, PS, PVC.
In one embodiment of the invention, the junked tire oil is a hydrocarbon material obtained by one or more conversion methods of thermal cracking, catalytic cracking and dissolution liquefaction of junked 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 composition of the waste tire oil comprises 5-80% of olefin, preferably 5-60% of aromatic hydrocarbon, less than 90% of aromatic hydrocarbon, preferably 2-60% of aromatic hydrocarbon, and less than 90% of alkane, preferably 5-60% of alkane.
In the invention, the junked tires are various junked tires prepared from natural rubber and/or synthetic rubber.
In the invention, the thermal cracking and thermal cracking reaction refers to a reaction that hydrocarbon molecules including waste plastics and junked tires are decomposed into smaller molecules under the condition of isolating air at high temperature. Depending on the reaction temperature, 600℃or less will be referred to as thermal cracking reaction, and 600℃or more will be referred to as thermal cracking reaction.
In the present invention, the catalytic cracking and catalytic cracking reaction refers to a reaction in which hydrocarbon molecules including waste plastics and junked tires are decomposed into smaller molecules under high temperature conditions and in the presence of a catalyst. Depending on the reaction products, the reaction using low-carbon olefins (ethylene, propylene, and butene) as the target products is called a catalytic cracking reaction, and the reaction using motor gasoline as the target products is called a catalytic cracking reaction.
In the present invention, the dissolution and liquefaction reaction means a reaction in which waste plastics and junked tires are converted from a solid state to a liquid state in the presence of solvent oil and/or an organic solvent.
The meaning of "optional" in the present invention is optional, meaning that the optional prefractionation unit is an optional unit. In one embodiment of the present invention, a prefractionation unit, a depuration unit, a hydrofinishing unit, and a fractionation unit are included. Cutting the waste plastic oil and/or waste tire oil raw materials in a prefractionation unit to obtain light fraction with the final distillation point less than 180 ℃, and putting the light fraction into a impurity removal reactor to contact with a waste hydrogenation catalyst, and carrying out impurity removal reactions such as dechlorination, demetallization, desilication and the like under impurity removal reaction conditions.
In one embodiment of the invention, the waste plastic oil and/or junked tire oil feedstock is cut in the optional prefractionation unit of step (1') to obtain a light fraction having a final boiling point of < 160 ℃.
In one embodiment of the invention, the de-hybridization reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. Filling waste hydrogenation catalyst in the fixed bed hydrogenation reactor and/or the moving bed reactor, and carrying out desilication, dechlorination, demetallization and other impurity removal reactions on the feed through 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 prefractionation unit.
In one embodiment of the invention, the impurity removal reactor is more than two fixed bed hydrogenation reactors connected in parallel, each reactor is filled with a waste hydrogenation catalyst, the feed is subjected to impurity removal reaction through at least one fixed bed hydrogenation reactor, and when the waste hydrogenation catalyst in the fixed bed hydrogenation reactor is saturated with silicon or metal, the feed is switched to other fixed bed hydrogenation reactors.
In one embodiment of the invention, the spent hydrogenation catalyst in the dehazing reactor is considered to be saturated with silicon or with metal when the silicon content of the liquid phase material in the reaction effluent is greater than or equal to 1 μg/g or when the metal content is greater than or equal to 5 μg/g.
In one embodiment of the invention, the waste hydrogenation catalyst is one or more selected from the group consisting of a protecting agent used from the end of any fixed bed hydrogenation process device in the hydrocarbon oil processing field, a catalyst at the end of the fixed bed hydrogenation process device, a regenerated protecting agent and a regenerated catalyst.
In one embodiment of the invention, the equivalent diameter of the spent hydrogenation catalyst is from 0.5 to 16mm, preferably from 1 to 10mm. The shape of the waste hydrogenation catalyst is not limited, and for example, the shape of the waste hydrogenation catalyst comprises a sphere, and various different shapes such as strip clover, butterfly, raschig ring, honeycomb shape and the like.
In one embodiment of the invention, the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 0-50% by weight of hydrogenation active metal oxide, 0-50% by weight of carbon and 0-40% by weight of sulfur, wherein the hydrogenation active metal is selected from one or more of VIII group metals and VIB group metals.
In one embodiment of the invention, the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 0-50 wt% of molybdenum oxide and/or tungsten oxide, 0-40 wt% of nickel oxide and/or cobalt oxide, 0-30 wt% of carbon and 0-30 wt% of sulfur.
In one embodiment of the invention, the waste hydrogenation catalyst comprises 1-40 wt% of hydrogenation active metal oxide and 20 wt% or less of carbon based on the total weight of the waste hydrogenation catalyst, wherein the hydrogenation active metal is selected from one or more of VIII group metal and VIB group metal.
In one embodiment of the invention, a plurality of waste hydrogenation catalysts are filled in layers, the equivalent diameter of the waste hydrogenation catalysts is gradually reduced along the material flow direction, the pore diameter is gradually reduced, and the active metal content is gradually increased.
In one embodiment of the invention, the impurity removal reactor is also filled with a dechlorinating agent, and the filling volume ratio of the dechlorinating agent to the waste catalyst is 1-80: 20 to 99. The waste hydrogenation catalyst and the dechlorinating agent are uniformly mixed and filled or layered filled.
In one embodiment of the invention, the waste hydrogenation catalyst and the dechlorinating agent are filled in layers, and the dechlorinating agent is filled 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 a plurality of dechlorinating agents, the dechlorinating agents can be packed in a graded combination or a mixed packing.
In one embodiment of the invention, the hydrogenation reactor is at least one moving bed hydrogenation reactor, and the waste hydrogenation catalyst and the dechlorinating agent are filled in the moving bed hydrogenation reactor. The waste hydrogenation catalyst and the dechlorinating agent are mechanically mixed according to a certain proportion.
In one embodiment of the invention, the dechlorinating 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 carrier and/or binder;
the carrier and/or the binder is selected from one or more of silicon oxide, aluminum oxide, silicon oxide-aluminum oxide, zirconium oxide and clay. The clay is one or more selected from 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 refer to one or more metal oxides selected from Cu, fe and Zn as optional components of the dechlorinating agent.
In the present invention, the dechlorinating agent is preferably a high-temperature dechlorinating agent and/or a medium-temperature dechlorinating agent. The invention has no limitation to high-temperature dechlorinating agent and medium-temperature dechlorinating agent, and the invention can be realized by conventional high-temperature dechlorinating agent and medium-temperature dechlorinating agent. Further preferred are high temperature dechlorinating agents and/or medium temperature dechlorinating agents having a large chlorine capacity.
In one embodiment of the invention, the chlorine content of the liquid phase material in the reaction effluent of step (1) is less than 0.5 μg/g.
In one embodiment of the invention, the stripping 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 Hydrogen oil volume ratio of 5-1000 Nm 3 /m 3 。
The preferred conditions for the stripping reaction are: hydrogen partial pressure of 1-12 MPa, reaction temperature of 100-400 ℃ and volume space velocity of 0.2-20 h -1 Hydrogen oil volume ratio of 10-800 Nm 3 /m 3 。
In the hydrofining unit of the step (2), the reaction effluent obtained in the impurity removal unit of the step (1) directly enters a hydrofining reactor, and is contacted with a hydrofining catalyst for reaction under the condition of hydrofining reaction, so that impurities such as sulfur, nitrogen and the like are removed, and olefin is hydrogenated and saturated.
In one embodiment of the invention, the hydrogenationThe refining reaction conditions are as follows: hydrogen partial pressure of 1.0-20.0 MPa, reaction temperature of 150-420 ℃ and volume space velocity of 0.5-20 h -1 Hydrogen oil volume ratio of 10-1000 Nm 3 /m 3 ；
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 -1 Hydrogen oil volume ratio of 50-800 Nm 3 /m 3 。
In one embodiment of the invention, the hydrofining catalyst comprises a hydrogenation metal active component and a carrier, wherein the content of the hydrogenation metal active component is 5-50 wt% based on the total weight of the hydrofining catalyst and calculated as oxide.
In a preferred case, the hydrogenation metal active component is at least one metal element selected from the group consisting of group VIB metal elements and at least one metal element selected from the group consisting of group VIII metal elements, wherein the group VIB metal elements are molybdenum and/or tungsten, and the group VIII metal elements are cobalt and/or nickel; the content of the group VIB metal element is 4 to 40 wt%, preferably 8 to 35 wt%, and the content of the group VIII metal element is 1 to 10 wt%, preferably 2 to 5 wt%, based on the total weight of the hydrofining catalyst, calculated as oxide.
And separating the reaction effluent obtained by the hydrofining reactor to obtain a gas-phase material and a liquid-phase material. The obtained liquid phase material is fractionated 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 present invention, the obtained naphtha fraction has a sulfur content of < 0.5. Mu.g/g, a nitrogen content of < 0.5. Mu.g/g, a bromine number of less than 0.5gBr/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, and an aromatic potential of > 35 mass%, and is a high-quality catalytic reforming raw material.
In another aspect, the invention provides a system for use in any of the above methods, comprising an optional prefractionation unit, a depuration unit, a hydrofinishing unit, a fractionation unit;
the prefractionation unit is provided with at least one waste plastic oil and/or waste tire oil inlet and at least one light fraction outlet;
the impurity removal unit is provided with an impurity removal reactor filled with waste hydrogenation catalyst, the impurity removal 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 catalyst is one or more selected from a protective agent and a catalyst from the end of any fixed bed hydrogenation process device in the hydrocarbon oil processing field to the end, and a regenerated protective agent and a regenerated catalyst;
the reaction effluent outlet of the impurity removal unit is communicated with the feed 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, 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 de-hybridization 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 removal reactor is more than two fixed bed hydrogenation reactors connected in parallel, each fixed bed hydrogenation reactor is filled with waste hydrogenation catalyst, and each fixed bed hydrogenation reactor is provided with at least one feed inlet and at least one reaction effluent outlet.
Drawings
FIG. 1 is a schematic diagram of one embodiment of a process for preparing a catalytic reforming feedstock from waste plastic oil and/or scrap tire oil provided by the present invention.
FIG. 2 is a schematic diagram of one embodiment of a process for preparing a catalytic reforming feedstock from waste plastic oil and/or scrap tire oil provided by the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings, without thereby limiting the invention.
FIG. 1 is a schematic diagram of one embodiment of the method for preparing a catalytic reforming raw material from waste plastic oil and/or waste tire oil according to the present invention, wherein as shown in FIG. 1, the waste plastic oil and/or waste tire oil raw material from the pipeline 1 is cut in the prefractionator 22 to obtain a light fraction and a heavy fraction, which are respectively extracted through the pipeline 23 and the pipeline 24.
After the light fraction from the pipeline 23 is boosted by the feed pump 2, the light fraction enters the heating furnace 4 from the pipeline 3 together with new hydrogen from the pipeline 17 and circulating hydrogen from the pipeline 16 for heating, the heated hydrogen-mixed material enters the impurity removing unit through the pipeline 5, the impurity removing unit is provided with two parallel fixed bed hydrogenation reactors 8 and 9, the fixed bed hydrogenation reactor 8 is internally provided with a catalyst bed layer A, the waste hydrogenation catalyst is filled in a grading manner, the fixed bed hydrogenation reactor 9 is internally provided with a catalyst bed layer B, and the waste hydrogenation catalyst is filled in a grading manner. In one embodiment, the hydrogen mixed material enters a fixed bed hydrogenation reactor 8 through a pipeline 6, contacts with the waste hydrogenation catalyst filled in a grading way, and carries out the impurity removal reaction under the impurity removal reaction condition, and the fixed bed hydrogenation reactor 9 is used for standby. After 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 a pipeline 7 to react, the fixed bed hydrogenation reactor 8 is cut out of the reaction system, and then the waste hydrogenation catalyst in the catalyst bed A is replaced.
The reaction effluent obtained from the impurity removal unit enters a hydrofining reactor 12 through pipelines 10 and 11 to be contacted with hydrofining catalyst for reaction, the reaction effluent enters a high-pressure separator 14 through a pipeline 13 to be subjected to gas-liquid separation, the obtained liquid phase material is extracted through a pipeline 18, and the obtained gas phase material is returned to the inlet of a heating furnace 4 through a pipeline 16 after being boosted by a circulating hydrogen compressor 15.
FIG. 2 is a schematic diagram of one embodiment of a method for preparing a catalytic reforming raw material from waste plastic oil and/or waste tire oil, wherein as shown in FIG. 2, after the waste plastic oil and/or waste tire oil from a pipeline 1 is boosted by a feed pump 2, the waste plastic oil and/or waste tire oil enters a heating furnace 4 from a pipeline 3 together with new hydrogen from a pipeline 17 and circulating hydrogen from a pipeline 16 to be heated, the heated hydrogen-mixed material enters a impurity removing unit through a pipeline 5, the impurity removing unit is provided with two parallel fixed bed hydrogenation reactors 8 and 9, a catalyst bed layer A is arranged in the fixed bed hydrogenation reactor 8, waste hydrogenation catalyst is filled in a grading manner, a catalyst bed layer B is arranged in the fixed bed hydrogenation reactor 9, and waste hydrogenation catalyst is filled in a grading manner. In one embodiment, the hydrogen mixed material enters a fixed bed hydrogenation reactor 8 through a pipeline 6, contacts with the waste hydrogenation catalyst filled in a grading way, and carries out the impurity removal reaction under the impurity removal reaction condition, and the fixed bed hydrogenation reactor 9 is used for standby. After 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 a pipeline 7 to react, the fixed bed hydrogenation reactor 8 is cut out of the reaction system, and then the waste hydrogenation catalyst in the catalyst bed A is replaced.
The reaction effluent obtained from the impurity removal unit enters a hydrofining reactor 12 through pipelines 10 and 11 to be contacted with hydrofining catalyst for reaction, the reaction effluent enters a high-pressure separator 14 through a pipeline 13 to be subjected to gas-liquid separation, the obtained liquid phase material is extracted through a pipeline 18, and the obtained gas phase material is returned to the inlet of a heating furnace 4 through a pipeline 16 after being boosted by a circulating hydrogen compressor 15.
The liquid phase material from line 18 is fed to fractionation column 19, and the resulting naphtha fraction is withdrawn via line 20 and the resulting heavy fraction is withdrawn via line 21.
The invention is further illustrated by the following examples, which are not intended to limit the invention in any way.
In the examples, the silicon content in the hydrocarbon material was measured by the method of measuring single wavelength dispersive X-ray fluorescence (SH/T0993-2019) 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 "measuring the total chlorine content in crude oil by coulometry" (RIPP 64-90) in "petrochemical analysis method" (RIPP test method). The instrument used was a microcoulomb analyzer and the sample was a liquid material.
The dechlorinating agent used in the examples was an industrially practiced dechlorinating agent RDY-100, manufactured by Jinan Ruidong Utility Co.
The reforming prehydrogenation end catalyst D used in the examples, the support was alumina, butterfly-shaped, equivalent diameter 1.6mm, composition comprising: 18% by weight of tungsten oxide, 2% by weight of nickel oxide, 0.04% by weight of cobalt oxide, 5.0% by weight of carbon and 6% by weight of sulfur;
the end catalyst E carrier of the gasoline hydrogenation used in the examples is alumina, butterfly-shaped, with equivalent diameter of 1.6mm, and the composition comprises: 10% by weight of molybdenum oxide, 3.5% by weight of cobalt oxide, 8.0% by weight of carbon and 7.0% by weight of sulfur;
the end catalyst F for diesel hydrofining used in the examples has a carrier of alumina, butterfly shape and equivalent diameter of 1.6mm, and comprises the following components: 26% of molybdenum oxide, 4.0% of nickel oxide, 20% of carbon and 15% of sulfur.
The hydrofining catalyst G used in the examples has a carrier of alumina, clover and an equivalent diameter of 1.6mm, and comprises the following components: tungsten oxide to 19 weight percent, nickel oxide to 2.0 weight percent and cobalt oxide to 0.4 weight percent.
The properties of the 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, raw material J is waste tire oil.
Examples 1 to 3
Cutting the waste plastic oil and/or the waste tire oil raw materials in a prefractionation 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 impurity removal reaction conditions, the obtained reaction effluent enters a hydrofining reactor to contact with a hydrofining catalyst, hydrofining reaction is carried out under hydrofining reaction conditions, 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 fractions are obtained after fractionation, and specific reaction conditions and product properties are shown in Table 2.
As shown in Table 2, the obtained 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 raw material,
examples 4 to 7
Waste plastic oil and/or waste tire oil raw materials enter a impurity removal reactor to contact with a waste hydrogenation catalyst in the presence of hydrogen, impurity removal reaction is carried out under impurity removal reaction conditions, obtained reaction effluent enters a hydrofining reactor to contact with a hydrofining catalyst, hydrofining reaction is carried out under hydrofining reaction conditions, 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, and specific reaction conditions and product properties are shown in Table 3.
As shown in Table 3, the obtained 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 Table 3
Example 8
In this example, two parallel fixed bed hydrogenation reactors 1 and 2 were set up, and the feedstock I was used as feed, and the catalyst loading conditions, the impurity removal reaction conditions and the reaction results were as shown in Table 4.
When the reactor 1 was operated for 800 hours, the metal content of the liquid phase material in the reaction effluent was more than 5. Mu.g/g, and at this time, the reactor was switched to the reactor 2, and the metal content of the liquid phase material was reduced to less than 1. Mu.g/g. The catalyst is replaced for the reactor 1, and thus the cycle achieves a long period of operation.
TABLE 4 Table 4
Example 9
In this example, two parallel fixed bed hydrogenation reactors 1 and 2 were set up, and the raw material H was used as a feed, and the catalyst loading conditions, the impurity removal reaction conditions and the reaction results were as 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 mug/g, and 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 mug/g. The catalyst is replaced for the reactor 1, and thus the cycle achieves a long period of operation.
TABLE 5
Example 10
The moving bed reactor of the stripping unit in this example, which uses the raw material H as the feed, the catalyst loading condition, the stripping reaction conditions and the reaction results are shown in Table 6.
As can be seen from Table 6, by adopting the method of the present invention, the raw material H with higher impurity content is treated by adopting a moving bed in the impurity removal unit, the silicon content of the obtained liquid phase reaction effluent is less than 1 mug/g, the chlorine content is less than 0.5 mug/g, the metal content is less than 5 mug/g, and the dosage consumption is 10.3 kg/ton of oil.
TABLE 6
| Impurity removing unit | Moving bed reactor |
| Catalyst | D |
| Raw oil | Raw material H |
| Reaction pressure, mpa | 1.6 |
| Reaction temperature, DEG C | 380 |
| Hydrogen to oil ratio, nm 3 /m 3 | 300 |
| Consumption of agent, kg/ton oil | 10.3 |
| Liquid phase reaction effluent | |
| Silicon content, μg/g | <1 |
| Chlorine content, μg/g | <0.5 |
| Metal content, μg/g | <5 |
It should be noted that the above-mentioned embodiments of the present invention are merely examples, and are not intended to limit the present invention, and various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (22)
1. A method for preparing catalytic reforming raw materials from waste plastic oil and/or junked tire oil, comprising the following steps:
(1') an optional prefractionation unit, and cutting the waste plastic oil and/or waste tire oil raw materials in the prefractionation unit to obtain light fraction with the final distillation point less than 180 ℃;
(1) The method comprises the steps that a impurity removal unit, waste plastic oil and/or waste tire oil raw materials or light fractions obtained in the step (1') enter an impurity removal reactor to be contacted with a waste hydrogenation catalyst in the presence of hydrogen, impurity removal reaction is carried out under impurity removal reaction conditions, the silicon content of liquid phase materials in obtained reaction effluent is less than 1 mug/g, the metal content is less than 5 mug/g, the waste hydrogenation catalyst is a protective agent and a catalyst which are selected from any fixed bed hydrogenation process device used to the end in the hydrocarbon oil processing field, the catalyst comprises, based on the total weight of the waste hydrogenation catalyst, the content of hydrogenation active metal oxide is 0-50 wt%, the carbon content is 5-50 wt%, the sulfur content is 6-40 wt%, and the hydrogenation active metal is selected from one or more of group VIII metals and group VIB metals; the impurity removal 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 Hydrogen oil volume ratio of 5-1000 Nm 3 /m 3 ；
(2) A hydrofining unit, wherein the reaction effluent obtained in the step (1) enters a hydrofining reactor to be contacted with a hydrofining catalyst, and hydrofining reaction is carried out under the condition of hydrofining reaction, 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 sulfur content in the naphtha fraction is less than 0.5 mug/g, the nitrogen content is less than 0.5 mug/g, and the bromine valence is less than 0.5gBr/100g, and the naphtha fraction is a catalytic reforming raw material.
2. The method according to claim 1, wherein the waste plastic oil is a hydrocarbon material obtained by one or more conversion methods of thermal cracking, catalytic cracking, and dissolution liquefaction of waste plastic; 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 are one or more of fresh household garbage, industrial and agricultural production and aged garbage, and the waste plastics are one or more selected from PE, PP, PS, PVC.
4. The method according to claim 1, wherein the junked tire oil is a hydrocarbon material obtained by one or more conversion methods of thermal cracking, catalytic cracking, and dissolution liquefaction of junked 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 scrap tires are various scrap tires made of natural rubber and/or synthetic rubber.
6. The process according to claim 1, wherein in the optional prefractionation unit of step (1'), the waste plastic oil and/or junked tire oil feedstock is cut to obtain a light fraction having a final boiling point of < 160 ℃.
7. The process according to claim 1, characterized in that the de-hybridization 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 removal reactor is more than two fixed bed hydrogenation reactors connected in parallel, each reactor is filled with a waste hydrogenation catalyst, the feed is subjected to impurity removal reaction through at least one fixed bed hydrogenation reactor, and when the waste hydrogenation catalyst in the fixed bed hydrogenation reactor is saturated with silicon or saturated with metal, the feed is switched to other fixed bed hydrogenation reactors.
9. The process of claim 8, wherein the waste hydrogenation catalyst in the dehazing reactor is considered to be saturated with silicon or metal when the silicon content of the liquid phase material in the reaction effluent is 1 μg/g or greater or when the metal content is 5 μg/g or greater.
10. The method according to claim 1, wherein the equivalent diameter of the spent hydrogenation catalyst is 0.5-16 mm.
11. The method according to claim 1, wherein the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, 0-50 wt% of molybdenum oxide and/or tungsten oxide, 0-40 wt% of nickel oxide and/or cobalt oxide, 5-30 wt% of carbon, and 6-30 wt% of sulfur.
12. The method according to claim 11, wherein the waste hydrogenation catalyst comprises 1-40 wt% of hydrogenation active metal oxide and 5-20 wt% of carbon based on the total weight of the waste hydrogenation catalyst, and the hydrogenation active metal is selected from one or more of group VIII metal and group VIB metal.
13. The method according to claim 1, wherein the impurity removal reactor is further filled with a dechlorinating agent, and the filling volume ratio of the dechlorinating agent to the waste catalyst is 1-80: 20 to 99.
14. The method according to claim 13, wherein the dechlorinating 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 is selected from one or more of silicon oxide, aluminum oxide, silicon oxide-aluminum oxide, zirconium oxide and clay.
15. The process according to claim 1 or 13, wherein the chlorine content of the liquid phase material in the reaction effluent of step (1) is less than 0.5 μg/g.
16. The method according to claim 1, wherein the stripping reaction conditions are: hydrogen partial pressure of 1-12 MPa, reaction temperature of 100-400 ℃ and volume space velocity of 0.2-20 h -1 Hydrogen oil volume ratio of 10-800 Nm 3 /m 3 。
17. The process of claim 1, wherein the hydrofinishing catalyst of step (2) comprises a hydrofinishing metal active component and a support, the hydrofinishing metal active component being present in an amount of from 5 to 50 wt% on an oxide basis based on the total weight of the hydrofinishing catalyst.
18. The process according to claim 17, characterized in that the hydrogenating metal active component is at least one metal element selected from the group consisting of group VIB metal elements and at least one metal element selected from the group VIII metal elements, the group VIB metal elements being molybdenum and/or tungsten and the group VIII metal elements being cobalt and/or nickel; the total weight of the hydrofining catalyst is taken as a reference, the content of the metal element of the VIB group is 4-40 wt% and the content of the metal element of the VIII group is 1-10 wt% based on oxide.
19. The process of claim 18 wherein the group VIB metal element is present in an amount of 8 to 35 wt.% and the group VIII metal element is present in an amount of 2 to 5 wt.% on an oxide basis based on the total weight of the hydrofinishing catalyst.
20. The process 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 -1 Hydrogen oil volume ratio of 10-1000 Nm 3 /m 3 。
21. The process of claim 1, wherein the hydrofinishing 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 -1 Hydrogen oil volume ratio of 50-800 Nm 3 /m 3 。
22. The method according to claim 1, wherein the chlorine content of the naphtha fraction obtained in the step (3) is < 0.5. Mu.g/g and the metal content is < 1. Mu.g/g.
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| WO2016142809A1 (en) * | 2015-03-10 | 2016-09-15 | Sabic Global Technologies, B.V. | A robust integrated process for conversion of waste plastics to final petrochemical products |
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