CN112725020B - Method for producing low-carbon olefin - Google Patents
Method for producing low-carbon olefin Download PDFInfo
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- CN112725020B CN112725020B CN201911058759.4A CN201911058759A CN112725020B CN 112725020 B CN112725020 B CN 112725020B CN 201911058759 A CN201911058759 A CN 201911058759A CN 112725020 B CN112725020 B CN 112725020B
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003921 oil Substances 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 239000002699 waste material Substances 0.000 claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000010687 lubricating oil Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000005194 fractionation Methods 0.000 claims abstract description 22
- 230000008929 regeneration Effects 0.000 claims abstract description 5
- 238000011069 regeneration method Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000008162 cooking oil Substances 0.000 claims description 29
- 239000000571 coke Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims description 17
- 238000004939 coking Methods 0.000 claims description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010457 zeolite Substances 0.000 claims description 17
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 150000002739 metals Chemical class 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000008157 edible vegetable oil Substances 0.000 claims description 3
- 238000005374 membrane filtration Methods 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 claims description 2
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000010705 motor oil Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000006240 deamidation Effects 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 235000019198 oils Nutrition 0.000 description 86
- 239000007789 gas Substances 0.000 description 50
- 239000000047 product Substances 0.000 description 25
- 238000004523 catalytic cracking Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- 239000012263 liquid product Substances 0.000 description 12
- 239000002199 base oil Substances 0.000 description 11
- 239000002283 diesel fuel Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000003225 biodiesel Substances 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- -1 carbon olefins Chemical class 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
- 235000019864 coconut oil Nutrition 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000010806 kitchen waste Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003346 palm kernel oil Substances 0.000 description 2
- 235000019865 palm kernel oil Nutrition 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G55/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
- C10G55/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only
- C10G55/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process plural serial stages only including at least one catalytic cracking step
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G2300/40—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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for producing low-carbon olefin, which comprises the following steps: (1) Pretreating the waste lubricating oil and/or the waste oil to ensure that the total metal content in the treated material is not higher than 300ppm; (2) The treated material in the step (1) enters a riser reactor to contact with a catalyst for reaction, the generated oil gas and the carbon-containing catalyst are subjected to gas-solid separation, and the separated catalyst is subjected to steam stripping and regeneration for recycling; and the separated reaction oil gas enters a fractionation system for separation to obtain the low-carbon olefin. The method can be used for efficiently utilizing the waste lubricating oil and/or the waste oil to produce more light olefins.
Description
Technical Field
The invention relates to a method for producing low-carbon olefin, in particular to a method for producing low-carbon olefin by taking waste lubricating oil and/or illegal cooking oil as raw materials, and particularly relates to a method for increasing the yield of propylene.
Background
The used lubricating oil is mainly characterized in that the lubricating oil is gradually aged and deteriorated due to the oxidation of high temperature and air in the use process, and the physicochemical properties of the lubricating oil are changed by metal powder rubbed off from a friction part, moisture entering the oil due to respiration and other reasons, impurities invading from the environment and the like. The waste lubricating oil can be used for producing other products, such as products for cracking to produce light diesel oil, gasoline and the like, and can also be used for producing lubricating oil base oil.
CN 105505550B discloses a method for regenerating waste lubricating oil, which comprises the steps of solvent treatment, membrane separation, hydrogenation modification, adsorption supplementary refining and normal pressure fractionation. Most metals and polar additives are removed by a solvent treatment and membrane separation method, aromatic hydrocarbon, heteroatoms, insoluble substances, most residual carbon and residual metals are removed by fixed bed hydrogenation modification, and the residual polar additives are removed by adsorption, supplement and refining, so that the light stability and the heat stability of the product are improved, high-quality lubricating oil base oil is produced, and high-quality naphtha and diesel oil are byproducts.
CN 1268557A discloses a method for regenerating light diesel oil for vehicles by using waste lubricating oil as raw material, which uses waste lubricating oil as raw material, and carries out thermal cracking in a coking kettle capable of directly refluxing, and a reflux valve is arranged at the bottom of a matched product fractionating tower and connected with a reflux valve at the top of the coking kettle, so that heavy fraction in the fractionating tower can directly reflux into the coking kettle, the temperature of the coking kettle is controlled at 570 ℃, and the temperature of the tower is controlled at about 350 ℃, and the light diesel oil for vehicles is produced by the method.
CN 107699282A discloses an environment-friendly process for regenerating diesel oil from catalytic cracking waste lubricating oil, which comprises a waste lubricating oil dehydration and drying process, a catalytic hydrocracking process, a vacuum rectification process and a catalyst regeneration process. The process for treating the waste lubricating oil has no coking phenomenon, can ensure continuous production, has the oil yield of over 85 percent, light yellow and clear color, oil quality close to the national standard, tail oil which can be directly used as an asphalt additive, catalyst which can be recycled, high efficiency, environmental protection and energy saving.
CN 103484156B discloses a method for producing diesel oil from waste lubricating oil, which comprises heating waste lubricating oil and catalyst to 180-410 deg.C for reaction, condensing the fraction generated at this temperature to obtain oil phase as gas oil, refining the gas oil to obtain diesel oil product, using catalyst containing 1-10wt% of oxygenIron oxide 1-10wt% and magnesium oxide 20-40wt% gamma-Al 2 O 3 And/or eta-Al 2 O 3 3-20wt% of calcium oxide and 20-40wt% of silicon dioxide.
CN 104726130A discloses a method for producing diesel oil by using lubricating oil for distillation, but this process produces a large amount of acid-base waste liquid in the process of adding acid and alkali to the distillate for many times, and these waste liquids are easy to pollute the environment when being improperly treated.
CN104726133A provides a method for producing base oil from waste lubricating oil, which comprises distilling the waste lubricating oil to obtain a fraction below 500 ℃ and a fraction above 500 ℃, hydrorefining the fraction below 500 ℃, fractionating to obtain fuel oil and a base oil fraction, and hydrorefining the fraction above 500 ℃ after reactive distillation. The disadvantage of this process is that the spent lubricating oil can be coked during the distillation separation.
The illegal cooking oil is a general term for poor oil in life of people, such as recycled edible oil, repeatedly used frying oil and the like. On one hand, the production of a large amount of illegal cooking oil can cause pollution to the environment, such as blockage of illegal cooking oil and even stink; on the other hand, the problems that the illegal cooking oil flows back to a dining table and the like exist, and a large number of potential safety hazards of diet are caused. At present, the adopted technology is more to convert the illegal cooking oil into biodiesel, environment-friendly base oil, biomass-based surfactant and the like.
CN 103074155A discloses a process for treating illegal cooking oil, which comprises the process steps of cleaning and slag separation, primary filtration, secondary filtration, deep processing treatment and the like, wherein the illegal cooking oil is separated from solid waste by a cleaning and isolating device, filtered by a 20-mesh filter bag, and refined before deep processing of the illegal cooking oil by a nanometer ultra-frequency vibration membrane group.
CN 105273837A discloses a comprehensive utilization method of illegal cooking oil, which comprises the steps of obtaining an oil layer and precipitates through saponification reaction and centrifugal separation, preparing a heavy metal ion adsorbent from the oil layer, preparing the remaining precipitates into biodiesel, and comprehensively utilizing the illegal cooking oil. CN 107699370A discloses a method for preparing biodiesel by using recycled illegal cooking oil, which comprises the steps of precipitating illegal cooking oil, removing mechanical impurities, rough filtering, filtering by a nanometer ultra-frequency vibration membrane group to obtain raw oil, transferring the raw oil into a reaction kettle, filling oxygen into the reaction kettle, heating the reaction kettle to 60 to 85 ℃, keeping the temperature for 1 to 1.5 hours, stopping oxygenation, stirring, cooling, centrifugally filtering to obtain high-concentration illegal cooking oil, and emulsifying, blending and defoaming to obtain the biodiesel. CN 1078929958A and CN 107815352A disclose a method for producing biodiesel from illegal cooking oil in kitchen waste, which comprises filtering kitchen waste, precipitating, heating to obtain raw oil, feeding the raw oil into a stirrer, adding catalyst, heating, adding additive, and stirring for a period of time to obtain biodiesel. Although the process of the patent is simpler, the process is not beneficial to large-scale operation and industrialization.
CN 108559574A discloses a method for producing environment-friendly base oil by using swill-cooked dirty oil, which comprises the steps of firstly removing impurities, degumming and decoloring the swill-cooked dirty oil, then catalyzing esterification reaction by a two-step acid method to obtain crude base oil, and then washing and decoloring the crude base oil to obtain the environment-friendly base oil.
CN 108277118A discloses a biomass-based surfactant containing waste oil extract and a preparation method thereof, wherein palm kernel oil fatty acid obtained by hydrolyzing natural palm kernel oil, palm oil fatty acid obtained by hydrolyzing palm oil, coconut oil fatty acid obtained by hydrolyzing coconut oil, and waste oil fatty acid are mixed according to a certain proportion and then mixed with caustic soda to produce soap particles, but the processing procedure is complicated.
In the regeneration process of the waste lubricating oil, the prior art is mainly used for producing light diesel oil, fuel oil, lubricating oil base oil and the like, and although the technologies have certain effects, the technologies have the problems of complex process, low economic benefit and subsequent pollution to a certain extent. The production method and the process principle of the method are feasible at present for preparing the biodiesel and the environment-friendly base oil by utilizing the illegal cooking oil, but the preparation of high-purity products has higher cost and higher energy consumption, and the application of low-purity products is limited.
Low carbon olefins (generally C2-C4 olefins) are important foundations of petrochemical industry, at present, ethylene is mainly obtained by hydrocarbon thermal cracking, and butene is mainly obtained by catalytic cracking (catalytic cracking) technology. Propylene, in addition to the higher selectivity propane dehydrogenation technology, is typically a thermal cracking byproduct from the production of ethylene or a catalytic cracking (catalytic cracking) byproduct. That is to say, the propylene yield is generally only about 50% of the ethylene yield in the conventional ethylene production technology using naphtha as the important chemical raw material which is difficult to obtain in trienes (ethylene, propylene and butylene). The catalytic cracking (catalytic cracking) technology is another main source of propylene, wherein more solutions are specially used for improving the yield of the propylene, but the yield of the propylene is generally only about 20%, and meanwhile, the raw material restriction factor exists, most of the propylene yield increasing technologies are at the cost of low yield gasoline, which may be contradictory to the yield increasing gasoline.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a method for producing low-carbon olefins, which can efficiently use waste lubricating oil and/or waste oil for producing more low-carbon olefins, and particularly further improve the yield and selectivity of propylene on the premise of higher total yield of C2-C4 olefins.
The invention provides a method for producing low-carbon olefin, which comprises the following steps:
(1) Pretreating the waste lubricating oil and/or the illegal cooking oil to ensure that the total metal content in the treated material is not higher than 300ppm, preferably not higher than 150ppm, further preferably not higher than 45ppm, 30ppm, 25ppm, 20ppm, 15ppm, 10ppm, 5ppm, 3ppm and 1ppm, wherein the metal is at least one or more of IA metal, IIA metal, VIB metal, VIIB metal, VIIIB metal and IIB metal, and preferably at least one of Na, K, mg, ca, mo, mn, fe, co, ni, V and Zn;
(2) The material treated in the step (1) enters the bottom of a riser reactor to contact with a catalyst for reaction, preferably enters the bottom of the riser reactor to contact with the catalyst for reaction after heat exchange, the generated oil gas and the catalyst containing carbon are subjected to gas-solid separation, and the separated catalyst to be generated is subjected to steam stripping and regeneration for recycling; and the separated reaction oil gas enters a fractionation system for further separation to obtain the low-carbon olefin.
In the method, the waste lubricating oil in the step (1) is one or a mixture of waste engine oil and waste mineral oil, and the illegal cooking oil is one or a mixture of various poor oils existing in life, such as recovered edible oil, repeatedly used frying oil and the like.
In the method, the total content of one or more of alkali metals, alkaline earth metals or IIB metals in the treated material in the step (1) is preferably less than 200ppm, preferably less than 100ppm, further preferably less than 25ppm, 20ppm, 15ppm, 10ppm, 5ppm, 3ppm, 1ppm, 0.5ppm and 0.2ppm, further preferably the total content of one or more of alkali metals, alkaline earth metals or IIB metals is less than the total content of other metals, particularly preferably less than the total content of VIIIB metals in the material, and the total content of VIIIB metals in the material is 0.5-15ppm, preferably 1-10ppm, further preferably 1-5 ppm. Appropriate VIIIB metal is remained in the material fraction, the formation of an intermediate product of the dehydroaromatization reaction is appropriately promoted, and the selectivity of propylene is improved. The partial removal (partial retention) of metals also reduces the load and operating costs of the pretreatment unit.
In the method, materials with different components from the waste lubricating oil and/or the illegal cooking oil are introduced into the step (1) optionally before the pretreatment or before the pretreated materials enter the riser reactor, wherein the materials with different components from the waste lubricating oil and/or the illegal cooking oil comprise one or more of VGO, raffinate oil of recycle oil after aromatic hydrocarbon extraction, hydrotreated oil, FCC clarified oil, paraffin-based crude oil and the like, and the introduction amount is 1-60wt% of the mass of the materials before the pretreatment or after the pretreatment, preferably 55%, 50%, 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10% or 5% of the mass of the materials before the pretreatment or after the pretreatment. The proper amount of these materials is introduced, the product distribution is not changed basically, and the low-carbon olefin mainly containing propylene can be produced in large quantity, and is different from the results of the single catalytic cracking (catalytic cracking) of these materials.
The method comprises the step (1) of pretreating, wherein the pretreatment comprises one or more of filtration, fractional distillation, adsorption, centrifugal separation, flocculation separation and standing sedimentation, and filtration and/or fractional distillation are preferred.
The method comprises the following specific pretreatment method in the step (1): and (2) feeding the waste lubricating oil and/or the waste oil into a fractionating system, wherein the fractionating system comprises one or more of a distillation tower, a flash tank, a stripping tower, an oil-gas separator and a separation stabilizing tower, and after fractionation, the obtained light distillate oil is subjected to heat exchange and then enters the bottom of a riser reactor to contact with a catalyst for reaction, wherein the 90% distillation temperature of the light distillate oil is controlled to be 400-490 ℃, and preferably 430-450 ℃.
In the pretreatment method, heavy distillate oil obtained after fractionation enters a coking unit to coke a coke tower, oil gas generated by reaction escapes from the top of the coke tower and enters the fractionating tower for separation, and optionally, the separated material enters a riser reactor or all or part of the oil gas (for example, more than 10wt%, more than 20wt%, more than 30wt%, more than 40wt%, more than 50wt%, more than 60wt%, more than 70wt%, more than 80wt%, more than 90 wt%) is directly mixed with the pretreated raw material without separation and then enters the riser reactor or directly enters the riser reactor, and preferably, all or part of the oil gas directly enters the middle part of the riser reactor without separation. Research results show that the oil gas directly enters the bottom of the riser reactor without separation, so that the deep contact between the pretreated material and the catalyst can be improved, the reaction temperature is further increased, and the low-carbon olefin is favorably generated.
In the pretreatment method, before optional fractionation, the waste lubricating oil and/or the waste oil are filtered, or the heavy fraction after fractionation is filtered and then enters a coking unit.
The method of the invention, another specific pretreatment method in the step (1) is as follows: adopting a membrane filtration mode, preferably ceramic membrane filtration, wherein the maximum membrane pore diameter is 5 to 10 μm, the filtration pressure is 0.2 to 5.0Mpa, the filtration temperature is 40 to 350 ℃, and the filtered material enters the bottom of the riser reactor for reaction after heat exchange.
In the method, the heat exchange in the step (2) adopts a heating furnace heating mode, so that the temperature of the pretreated material is 300 to 380 ℃, preferably 320 to 360 ℃.
In the method, the catalyst in the step (2) can be an amorphous silicon-aluminum catalyst or a zeolite catalyst, the active component of the zeolite catalyst is selected from one or a mixture of more than one of Y-type zeolite, HY-type zeolite, ultrastable Y-type zeolite, ZSM-5 series zeolite or high-silicon zeolite with a five-membered ring structure and ferrierite in any proportion, and the zeolite can contain rare earth and/or phosphorus or does not contain rare earth and phosphorus.
In the method, the reaction condition in the step (2) is that the reaction temperature is 480 to 680 ℃, preferably 520 to 650 ℃; the weight ratio of the catalyst to the pretreated material (hereinafter referred to as agent-oil ratio) is (2-40): 1, preferably (10 to 30): 1; the weight ratio of the water vapor to the pretreated materials (hereinafter referred to as water-oil ratio) is (0.02-0.3): 1, the pressure is normal pressure to 450kPa.
According to the method, reaction oil gas separated in the step (2) enters a fractionating system to at least separate gas, and the gas after leaving a device is subjected to amine removal and alkali removal processes and enters a gas separation and refining device to obtain ethane, propane, propylene and isobutene.
According to the method, the reaction oil gas separated in the step (2) enters a fractionation system to separate gas and liquid, or the separated reaction oil gas enters the fractionation system to separate gas, gasoline fraction and liquid, all or part of (for example, more than 10wt%, more than 20wt%, more than 30wt%, more than 40wt%, more than 50wt%, more than 60wt%, more than 70wt%, more than 80wt%, more than 90 wt%) liquid is mixed with the pretreated materials and then enters a reaction tube to continue to react, and the liquid phase can remarkably reduce the viscosity of the pretreated materials, promote the catalytic cracking reaction and improve the yield of low-carbon olefins.
The yield of propylene (based on the total weight of the product) in the process of the invention is more than 25%, preferably more than 30%, more than 35%, more than 40%, generally not more than 55%, and usually not more than 50%. The proportion of the propylene in the total alkene rate of C2-C4 can reach about 50%, generally 40-60%, preferably 45-65%. The yield and selectivity exceed the effect of the same technology in the field.
Compared with the prior art, the lubricating oil/illegal cooking oil treatment method has the beneficial effects that:
(1) The method provided by the invention can be used for producing low-carbon olefin products with high added value to the maximum extent by using the waste lubricating oil/waste oil, avoids the complex process of conventional waste lubricating oil/waste oil treatment, and has great industrial popularization value;
(2) According to the method provided by the invention, metal powder, mechanical residues, impurities invading from the environment, food residues and the like in the raw materials can be concentrated in heavy components through pretreatment, and the raw materials are prevented from directly entering a catalytic cracking reactor to cause catalyst poisoning and inactivation;
(3) According to the method provided by the invention, the catalytic cracking reaction oil gas enters a fractionation system to separate gas and liquid, or the separated reaction oil gas enters the fractionation system to separate gas, gasoline fraction and liquid, the liquid is mixed with the pretreated material and then enters a reaction tube to continue to react, and the liquid phase can remarkably reduce the viscosity of the pretreated material, promote the catalytic cracking reaction and improve the yield of low-carbon olefins;
(4) According to the method provided by the invention, heavy fractions obtained by pretreating raw materials can enter the delayed coking unit, oil gas generated by coking can partially replace pre-lifting steam, and the energy consumption of the device is reduced; meanwhile, the feeding temperature can be increased, the catalytic cracking reaction is promoted, and the yield of the low-carbon olefin is increased.
Drawings
Fig. 1 is a process flow diagram of a method for producing low carbon olefins according to the present invention, wherein 1 is a waste lubricating oil/illegal cooking oil raw material, 2 is a pretreatment unit fractionating tower, 3 is a light fraction oil (light component), 4 is a heavy fraction oil (heavy component), 5 is a delayed coking unit (including a heating furnace and a coke tower), 6 is a coke product, 7 is a coking-generated oil gas, 8 is a riser reactor, 9 is a regenerator, 10 is a riser reactor reaction product, 11 is a fractionating tower, 12 is a catalytic cracking gas product, and 13 is a catalytic cracking liquid product.
Detailed Description
The method of the present invention will be described in further detail with reference to the accompanying drawings and examples, but the following examples are not intended to limit the method of the present invention.
As shown in fig. 1: the raw material 1 passes through a pretreatment unit 2 to obtain a light component 3 and a heavy component 4, the light component 3 is mixed with a liquid product 13 from the bottom of a catalytic cracking fractionating tower, the mixture is heated to a preset temperature by a heating furnace, and then enters a riser reactor 8, and is contacted with a high-temperature catalyst from a regenerator 9 in the mixture, and then is vaporized and reacted, a reaction product 10 is separated out of an entrained catalyst by a cyclone separator, and then leaves a settler to the bottom of a fractionating tower 11, an overhead gas 12 and a bottom liquid product 13 are separated, the overhead gas 12 is discharged from the device, the bottom liquid product 13 returns to the riser reactor 8 to continue reacting, and the process is repeated; heavy components 4 can be directly discharged from the device, or introduced into a regenerator 9 to be combusted, or enter a delayed coking unit 5 (heated to a preset temperature by a heating furnace and then enter a coke tower), oil gas 7 generated by coking escapes from the top of the coke tower, is not fractionated and directly enters the middle part of a riser reactor 8 to continue reacting, and when the coke tower finishes a coke charging process, steam purging and the coke charging process are carried out on the coke tower, so that a coke product 6 is obtained.
Example 1
The method comprises the following steps of taking waste lubricating oil provided by a certain refinery as a raw material, and subjecting the raw oil to a reduced pressure distillation device to obtain light distillate oil and heavy distillate oil, wherein the distillation temperature of 90% of the light distillate oil is controlled to be 450 ℃, the total content of alkali metals, alkaline earth metals or IIB metals in the light distillate oil is 0ppm, the total content of VIIIB metals is 5ppm, the light distillate oil in the light distillate oil is preheated to 320 ℃ by a heating furnace, enters a riser reactor to react, is contacted with a high-temperature catalyst of a regenerator, and is vaporized to react, and the reaction conditions are as follows: the reaction temperature is 560 ℃, the weight ratio of the catalyst to the pretreated material (hereinafter referred to as catalyst-oil ratio) is 10:1, the weight ratio of the water vapor to the pretreated material (hereinafter referred to as water-oil ratio) is 0.1:1, separating generated oil gas and a catalyst at the pressure of 200kPa, feeding the separated oil gas and the catalyst into the bottom of a fractionating tower, cutting the oil gas and the catalyst into tower top gas and tower bottom liquid products in the fractionating tower, discharging the tower top gas out of a device, and returning all the tower bottom liquid products to the bottom of a riser reactor for continuous reaction; and (3) feeding heavy distillate oil obtained by reduced pressure distillation into a delayed coking unit, heating to 460 ℃ by a heating furnace, feeding into a coke tower for coke charging, controlling the top pressure of the coke tower to be 0.5MPa, and directly feeding oil gas generated by coking into the middle part of a riser reactor for continuous reaction without fractionation, wherein the oil gas escapes from the top of the coke tower. The specific property analysis of the feedstock used in this example is shown in Table 1, the catalyst properties are shown in Table 2, and the product distribution is shown in Table 3.
Examples 1 to 1
The same raw materials and devices as those in example 1 are adopted, and only oil gas generated by coking does not enter the riser reactor, but enters the fractionating device, gas, gasoline, diesel oil and wax oil are separated out, and the oil is discharged out of the device. The product distribution is shown in Table 3.
Examples 1 to 2
The same raw materials and equipment as in example 1 were used except that the coker gas-oil was first separated into a gas phase by a fractionating column and the liquid was returned to the riser reactor for further reaction. The product distribution is shown in Table 3.
Examples 1 to 3
The same raw materials and equipment as in example 1 were used except that the catalytic cracking reaction product was separated into overhead gas, gasoline, diesel oil and recycle oil by a fractionating tower, the bottom product was returned to the riser reactor, and the remaining products were directly taken out of the equipment. The product distribution is shown in Table 3.
Examples 1 to 4
The same feed and apparatus as in example 1 were used except that VGO was introduced into the light distillate oil in an amount of 30% by weight, and the VGO properties are shown in Table 4. The product distribution is shown in Table 3.
TABLE 1 used lubricating oil feedstock Properties
TABLE 2 catalyst Properties
Example 2
The method comprises the following steps of adding raw oil and argil accounting for 5% of the mass of the raw oil into a mixer by using the same raw materials as in example 1, mixing the raw oil and the argil into slurry, heating the slurry to 100 ℃, keeping the temperature for 30min, filtering the slurry by using a Schler filter and a plate-and-frame filter to obtain refined oil, preheating the refined oil to 320 ℃ by using a heating furnace, allowing the refined oil to enter a riser reactor for reaction, contacting with a high-temperature catalyst of a regenerator, and evaporating the refined oil for reaction, wherein the reaction conditions are as follows: the reaction temperature is 560 ℃, the ratio of solvent to oil is 10:1, water-oil ratio of 0.1:1, the pressure is 200kPa, generated oil gas and a catalyst are separated and then enter the bottom of a fractionating tower, the oil gas and the catalyst are cut into tower top gas and tower bottom liquid products in the fractionating tower, the tower top gas is discharged from a device, and the tower bottom liquid products are all returned to the bottom of a riser reactor for continuous reaction. The specific property analysis of the feedstock used in this example is shown in Table 1, the catalyst properties are shown in Table 2, and the product distribution is shown in Table 3.
Example 3
Taking illegal cooking oil as a raw material, and passing the raw material oil through a ceramic membrane filter device to obtain filtrate and filter residue, wherein the maximum aperture of a ceramic membrane is 10 microns, the filtering pressure is 0.5Mpa, the filtering temperature is 100 ℃, the total content of alkali metal, alkaline earth metal or IIB metal in the filtrate is 1ppm, the total content of VIIIB metal is 6ppm, the filtrate is preheated to 320 ℃ by a heating furnace, and enters a riser reactor for reaction, and is contacted with a high-temperature catalyst of a regenerator, and then is vaporized for reaction, and the reaction conditions are as follows: the reaction temperature is 600 ℃, the ratio of the catalyst to the oil is 20:1, the water-oil ratio is 0.1:1, separating generated oil gas and a catalyst at the pressure of 100kPa, then feeding the separated oil gas and the catalyst into the bottom of a fractionating tower, cutting the oil gas and the catalyst into tower top gas and tower bottom liquid products in the fractionating tower, discharging the tower top gas out of a device, and returning all the tower bottom liquid products to the bottom of a riser reactor for continuous reaction; the filter residue can be directly discharged from the device or introduced into the regenerator. The specific property analysis of the feedstock used in this example is shown in Table 5, the catalyst properties are shown in Table 2, and the product distribution is shown in Table 3.
Example 4
The same raw materials as in example 3 were used, and degumming was carried out at 60 ℃ using a citric acid-silica gel combination method: adding citric acid with the mass of 0.1 percent of that of the illegal cooking oil into the illegal cooking oil for acidification treatment for 40min, then adding deionized water with the volume of 3 percent of that of the illegal cooking oil for hydration treatment for 30min, standing and settling for 12h, taking an upper oil phase, wherein the total content of alkali metal, alkaline earth metal or IIB metal and VIIIB metal in the oil phase are 3ppm and 7ppm respectively, preheating the oil phase to 320 ℃ by a heating furnace, entering a riser reactor for reaction, contacting with a high-temperature catalyst of a regenerator, and then vaporizing for reaction, wherein the generated oil gas is separated from the catalyst and then enters the bottom of a fractionating tower under the same reaction conditions as in the embodiment 3, and is cut into tower top gas and tower bottom liquid products in the fractionating tower, the tower top gas is discharged from a device, and the tower bottom liquid products are all returned to the bottom of the riser reactor for continuous reaction; the filter residue can be directly discharged from the device or introduced into a regenerator. The specific property analysis of the feedstock used in this example is shown in Table 5, the catalyst properties are shown in Table 2, and the product distribution is shown in Table 3.
TABLE 3 product distribution
* Based on the total product recovered.
TABLE 4 VGO Properties
TABLE 5 properties of the illegal cooking oil feedstock
Claims (19)
1. A method for producing low-carbon olefin is characterized by comprising the following steps: the method comprises the following steps:
(1) Pretreating the waste lubricating oil and/or the swill-cooked dirty oil to ensure that the total metal content in the treated material is not higher than 45ppm, wherein the metal is at least one or more of IA metal, IIA metal, VIB metal, VIIB metal, VIII metal and IIB metal;
the total content of one or more of alkali metals, alkaline earth metals or IIB metals in the treated material or the material before entering the riser reactor is less than the total content of VIII metals in the material, and the total content of the VIII metals in the material is 5-10ppm;
(2) The material after pretreatment in the step (1) enters a riser reactor after heat exchange to contact with a catalyst for reaction, the generated oil gas and the catalyst containing carbon are subjected to gas-solid separation, and the separated catalyst is subjected to steam stripping and regeneration and then is recycled; the separated reaction oil gas enters a fractionation system to be separated to obtain low-carbon olefin;
the heat exchange adopts a heating furnace heating mode, so that the temperature of the pretreated material is 300 to 380 ℃;
the catalyst is an amorphous silicon-aluminum catalyst or a zeolite catalyst, and the active component of the zeolite catalyst is selected from one or more of Y-type zeolite, ZSM-5 series zeolite or high-silicon zeolite with a five-membered ring structure and ferrierite;
the reaction conditions are as follows: the reaction temperature is 480 to 680 ℃; the weight ratio of the catalyst to the pretreated material is (2-40): 1; the weight ratio of the water vapor to the pretreated material is (0.02-0.3): 1, the pressure is normal pressure to 450kPa.
2. The method of claim 1, wherein: in the step (1), the waste lubricating oil is one or a mixture of waste engine oil and waste mineral oil, and the swill-cooked dirty oil is one or a mixture of recovered edible oil and repeatedly used frying oil.
3. The method of claim 1, wherein: in the step (1), the total metal in the treated material is at least one of Na, K, mg, ca, mo, mn, fe, co, ni and Zn.
4. The method of claim 1, wherein: in the step (1), materials different from the components of the waste lubricating oil and/or the illegal cooking oil are introduced before the pretreatment or before the pretreated materials enter the riser reactor, and the introduction amount is 1-60wt% of the mass of the materials before the pretreatment or after the pretreatment.
5. The method of claim 4, wherein: the materials with different components from the waste lubricating oil and/or the illegal cooking oil are one or more of VGO, raffinate oil obtained by extracting aromatic hydrocarbon from recycle oil, hydrotreated oil, FCC clarified oil and paraffin-based crude oil.
6. The method of claim 1, wherein: the pretreatment method in the step (1) comprises one or more of filtration, fractionation, adsorption, centrifugal separation, flocculation separation and standing sedimentation.
7. The method of claim 1, wherein: the pretreatment method in the step (1) is as follows: and the waste lubricating oil and/or the waste oil enter a fractionation system, and light distillate oil obtained after fractionation enters a riser reactor to contact with a catalyst for reaction after heat exchange.
8. The method of claim 7, wherein: the fractionation system comprises one or more of a distillation tower, a flash tank, a stripping tower, an oil-gas separator and a separation stabilizing tower, and the 90% distillation temperature of the light distillate oil is controlled to be 400 to 490 ℃.
9. The method of claim 8, wherein: the distillation temperature of 90 percent of the light distillate oil is controlled to be 430 to 450 ℃.
10. The method of claim 7, wherein: and (3) feeding heavy distillate oil obtained after fractionation into a coking unit to coke a coke tower, and allowing oil gas generated by reaction to escape from the top of the coke tower and enter a fractionating tower for separation.
11. The method of claim 7, wherein: and the light distillate oil which enters the fractionating tower for separation enters the riser reactor from the middle part of the riser reactor.
12. The method of claim 7, wherein: and before fractionation, filtering the waste lubricating oil and/or the waste oil or filtering the heavy fraction after fractionation and then entering a coking unit.
13. The method of claim 1, wherein: the pretreatment method in the step (1) is as follows: adopting a ceramic membrane filtration mode, wherein the diameter of a maximum membrane hole is 5 to 10 mu m, the filtration pressure is 0.2 to 5.0Mpa, the filtration temperature is 40 to 350 ℃, and the filtered material enters a riser reactor for reaction after heat exchange.
14. The method of claim 1, wherein: in the step (2), the temperature of the pretreated material is controlled to be 320-360 ℃.
15. The method of claim 1, wherein: the zeolite catalyst in the step (2) contains rare earth and/or phosphorus.
16. The method of claim 1, wherein: the reaction conditions in the step (2) are as follows: the reaction temperature is 520-650 ℃; the weight ratio of the catalyst to the pretreated material is (10 to 30): 1.
17. the method of claim 1, wherein: and (3) introducing the reaction oil gas separated in the step (2) into a fractionation system to at least separate gas, and introducing the gas after the gas is discharged from the device and is subjected to deamidation and dealkalization processes into a gas separation refining device to obtain ethane, propane, propylene and isobutene.
18. The method of claim 1, wherein: and (3) the reaction oil gas separated in the step (2) enters a fractionation system to separate gas and liquid.
19. The method of claim 1, wherein: the Y-type zeolite is HY type zeolite or ultrastable Y-type zeolite.
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| GB1556901A (en) * | 1976-04-29 | 1979-11-28 | Mobil Oil Corp | Catalytic eracking of metal-contaminated oils |
| CN101314718A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for improving productivity of low carbon olefin hydrocarbon in biological oil and fat catalytic conversion reaction |
| CN103059926A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing low carbon olefin by catalytic conversion of lightweight hydrocarbon oil |
| CN109096028A (en) * | 2018-08-29 | 2018-12-28 | 河南省君恒实业集团生物科技有限公司 | A method of alkene is prepared using waste lubricating oil |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1556901A (en) * | 1976-04-29 | 1979-11-28 | Mobil Oil Corp | Catalytic eracking of metal-contaminated oils |
| CN101314718A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for improving productivity of low carbon olefin hydrocarbon in biological oil and fat catalytic conversion reaction |
| CN103059926A (en) * | 2011-10-18 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing low carbon olefin by catalytic conversion of lightweight hydrocarbon oil |
| CN109096028A (en) * | 2018-08-29 | 2018-12-28 | 河南省君恒实业集团生物科技有限公司 | A method of alkene is prepared using waste lubricating oil |
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Effective date of registration: 20231116 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |