CN114105724B - Method and system for producing low-carbon olefin and aromatic hydrocarbon from waste plastic oil - Google Patents
Method and system for producing low-carbon olefin and aromatic hydrocarbon from waste plastic oil Download PDFInfo
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- CN114105724B CN114105724B CN202010904415.7A CN202010904415A CN114105724B CN 114105724 B CN114105724 B CN 114105724B CN 202010904415 A CN202010904415 A CN 202010904415A CN 114105724 B CN114105724 B CN 114105724B
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- 239000004033 plastic Substances 0.000 title claims abstract description 58
- 229920003023 plastic Polymers 0.000 title claims abstract description 58
- 239000002699 waste material Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 37
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- 238000003795 desorption Methods 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 16
- -1 carbon olefin Chemical class 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 134
- 230000003197 catalytic effect Effects 0.000 claims description 44
- 229910021536 Zeolite Inorganic materials 0.000 claims description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 30
- 239000010457 zeolite Substances 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 239000003463 adsorbent Substances 0.000 claims description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 15
- 230000000382 dechlorinating effect Effects 0.000 claims description 15
- 238000006298 dechlorination reaction Methods 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003502 gasoline Substances 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 8
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008041 oiling agent Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229940043430 calcium compound Drugs 0.000 claims description 5
- 150000001674 calcium compounds Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 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 claims description 4
- 229910052621 halloysite Inorganic materials 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 abstract description 22
- 239000000047 product Substances 0.000 abstract description 15
- 238000004891 communication Methods 0.000 description 12
- 239000012530 fluid Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 238000000197 pyrolysis Methods 0.000 description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 231100001261 hazardous Toxicity 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The method comprises the steps of carrying out adsorption and desorption separation on waste plastic oil to obtain adsorbed oil and desorbed oil, wherein the adsorbed oil enters a first catalytic cracking catalyst in a main riser reactor to contact, and carrying out a first catalytic cracking reaction; feeding the oil agent obtained by the reaction of the main riser reactor into a fluidized bed reactor for continuous second catalytic cracking reaction; and introducing the desorption oil into a secondary riser reactor to contact with a second catalytic cracking catalyst and perform a third catalytic cracking reaction, and separating reaction products to obtain products containing low-carbon olefin and aromatic hydrocarbon. The invention processes waste plastic oil, and has high and low carbon olefin and high arene yield.
Description
Technical Field
The invention relates to a method and a system for producing low-carbon olefin and aromatic hydrocarbon by using waste plastic oil.
Background
The plastic market demand of China is increased year by year, about 4000 ten thousand tons of waste plastic are produced annually, and the recycling rate is only about 30%. With the improvement of environmental awareness and the continuous increase of environmental pressure, the main treatment methods of plastics at present are landfill and incineration, but plastic products have low bulk density and are not easy to decompose, and the landfill is difficult to effectively realize reduction and harmlessness in a short period; the incineration can generate a large amount of greenhouse gases and release harmful gases such as dioxin, and the treatment mode can not effectively solve the problem of white pollution and is also a serious waste of petrochemical resources. Therefore, the waste plastic treatment means are gradually changed from landfill and incineration to recycling utilization mainly comprising physical recovery, chemical recovery and the like, wherein the chemical recovery pyrolysis technology has been applied. At present, most of domestic plastic pyrolysis technology adopts a rotary kiln reactor with an intermittent method, mainly produces oil products, and has an oil product yield of 30% -50%, and the balance of coke and pyrolysis gas. Because of the complex composition and sources of waste plastics, equipment corrosion is serious in the plastic pyrolysis process, and environmental pollution is large; and the plastic pyrolysis oil has large fluctuation of yield and unstable property, and the content of impurities such as micromolecular organic chlorine, organic silicon and the like in the oil product is up to thousands of times of that of petroleum products. Therefore, the plastic oil cannot be directly used as petrochemical product and needs to be further processed.
US2016/0264874A1 adopts an integrated technology to convert waste plastics into high added value products, the technology adopts the same hydrogenation reactor to realize waste plastics hydrofining, dechlorination and hydrocracking, so that the products can meet the requirements of steam cracking raw materials, and finally, low-carbon olefins are produced through steam cracking.
CN201510122785.4 discloses a method for producing high-quality gasoline and diesel oil by using chlorine-containing plastic oil, which 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, and the dechlorinated plastic oil is subjected to catalytic distillation and hydrofining to obtain high-quality gasoline and diesel oil.
CN201410225940.0 discloses a method for producing clean fuel oil from chlorine-containing plastic oil, which comprises the steps of reacting and rectifying chlorine-containing plastic oil in a catalytic distillation tower, and hydrodechlorinating the chlorine-containing plastic oil after catalytic conversion; the distillate oil after liquid phase hydrogenation enters a hydrofining tower again, so that gasoline and diesel oil mixed oil with no peculiar smell and high quality can be obtained, and then gasoline and diesel oil distillate oil can be obtained through distillation.
The annual processing capacity of the catalytic cracking of China is more than 2 hundred million tons, the annual production of the waste catalyst is more than 12 ten thousand tons, and the traditional treatment method of the catalytic cracking waste catalyst comprises landfill and magnetic separation. The landfill method is simple and convenient, but with the improvement of oil refining capability, the production of the waste catalyst rises year by year, and the waste catalyst generally contains Ni, V and other metal elements, so that the direct landfill tends to cause metal resource waste, pollute the environment and harm human health. In the national hazardous waste directory recently released in 2016, the catalytic cracking spent catalyst is characterized as HW50 hazardous waste, and the waste catalyst must be subjected to landfill treatment according to the hazardous solid waste disposal requirement, but the construction cost of a hazardous solid waste landfill is higher. The magnetic separation technology is to separate the waste catalyst with high metal content by utilizing the magnetism of the metal, and the catalyst with relatively good performance is reused in the catalytic cracking device. However, the magnetic separation technology has high cost, and how to make the best use of the catalytic cracking dead catalyst at low cost is the development direction of the utilization of the catalytic cracking dead catalyst.
From the prior art, the processing and utilizing technologies of plastic oil all take fuel oil as a main product, and the processing technologies of plastic oil for producing low-carbon olefin and aromatic hydrocarbon are rarely available. When the fuel oil is used as a target product, a hydrogenation technology is generally adopted as a main method to achieve the dechlorination effect, but the hydrogenation technology consumes hydrogen to complicate the process flow, has high requirements on equipment materials, and greatly increases the investment cost. Therefore, with the overmuch of oil refining yield and the gradual saturation of the fuel oil market, the development of the technology for converting the low-cost chlorine-containing plastic oil into the low-carbon olefin and the aromatic hydrocarbon with high added value can bring higher social benefit and economic benefit.
Disclosure of Invention
One of the purposes of the invention is to provide a method for producing low-carbon olefin and aromatic hydrocarbon by using waste plastic oil.
It is another object of the present invention to provide a system for producing light olefins and aromatics from waste plastic oil.
The invention provides a method for producing low-carbon olefin and aromatic hydrocarbon by using waste plastic oil, which comprises the following steps:
Introducing the waste plastic oil raw material into an adsorption and desorption reactor to contact with an n-alkane adsorbent and perform adsorption separation to obtain the residual oil and the adsorbent adsorbed with the n-alkane;
Carrying out desorption treatment on the obtained adsorbent adsorbed with normal alkane by adopting desorption gas to obtain desorption oil and the desorbed adsorbent;
Introducing the raffinate oil into a main riser reactor to contact with a first catalytic conversion catalyst and perform a first catalytic conversion reaction;
Introducing a dechlorination agent into the downstream of the main riser reactor to contact with the oiling agent in the reactor for dechlorination reaction;
Feeding the oiling agent obtained by the reaction of the main riser reactor into a fluidized bed reactor for continuously carrying out a second catalytic conversion reaction to obtain a first reaction product and a first spent catalyst;
Introducing desorption oil into a secondary riser reactor to contact with a second catalytic conversion catalyst and perform a third catalytic conversion reaction to obtain a second reaction product and a second spent catalyst;
separating the obtained first reaction product and the second reaction product to obtain at least ethylene, propylene, butylene and gasoline containing aromatic hydrocarbon;
And sending the obtained first spent catalyst and the second spent catalyst into a regenerator for burning regeneration, and returning at least part of the obtained regenerated catalyst to the main riser reactor and the auxiliary riser reactor to be used as the first catalytic conversion catalyst and the second catalytic conversion catalyst.
The invention provides a system for producing low-carbon olefin and aromatic hydrocarbon from waste plastic oil, which comprises an adsorption and desorption reactor, a main riser reactor, an auxiliary riser reactor, a fluidized bed reactor, a stripping section, a settler and a regenerator, wherein the settler, the fluidized bed reactor and the stripping section are arranged from top to bottom and are in fluid communication, and the main riser reactor passes through the stripping section from bottom to top and enters the fluidized bed reactor;
The adsorption and desorption reactor is provided with a waste plastic oil raw material inlet, a desorption gas inlet, an adsorption and desorption oil outlet and a main riser reactor, wherein the adsorption and desorption oil outlet is in fluid communication with the feed inlet of the main riser reactor, and the desorption oil outlet is in fluid communication with the feed inlet of the auxiliary riser reactor;
The main riser reactor is provided with a feed inlet, a catalyst inlet, a dechlorinating agent inlet and an oil agent outlet, the auxiliary riser reactor is provided with a desorption oil feed inlet, a catalyst inlet and an oil agent outlet, the stripping section is provided with a catalyst outlet, and the settler is provided with an oil gas outlet;
The oil outlet of the main riser reactor is positioned in the fluidized bed reactor, and the oil outlet of the auxiliary riser reactor is in fluid communication with the settler;
The regenerator is provided with a catalyst inlet in fluid communication with the catalyst outlet of the stripping section and a catalyst outlet in fluid communication with the catalyst inlets of the primary and secondary riser reactors.
The invention separates normal alkane component (i.e. desorption oil) which has lower reactivity and is ideal component for generating low-carbon olefin in waste plastic oil from non-normal alkane component (i.e. raffinate oil) which has higher reactivity and is ideal component for generating aromatic hydrocarbon, and the normal alkane component independently enters the reactor to contact and react with regenerated catalyst, thereby reducing the competition reaction of the non-normal alkane component to the active center of the catalyst, improving the catalytic cracking reaction performance of the normal alkane component to generate low-carbon olefin, and simultaneously improving the selectivity of the catalytic cracking of the non-normal alkane component to generate aromatic hydrocarbon.
The invention can partially remove the chlorine compounds in the waste plastic oil in the adsorption separation process, and reduce the equipment corrosion problem caused by the decomposition of the chlorine compounds into hydrogen chloride in the catalytic cracking process.
The invention not only solves the problems of reasonable and high-efficiency utilization of waste plastic oil, but also meets the continuous growing demands of the market on basic chemical raw materials such as low-carbon olefin, aromatic hydrocarbon and the like, and improves the economic benefit and the social benefit of petrochemical industry.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
FIG. 1 is a process flow diagram of a method and system for producing light olefins and aromatic hydrocarbons from waste plastic oil provided by the invention.
Detailed Description
One of the embodiments is:
a method for producing low-carbon olefin and aromatic hydrocarbon by using waste plastic oil, which comprises the following steps:
introducing the waste plastic oil raw material into an adsorption and desorption reactor to contact with an n-alkane adsorbent and perform adsorption and separation reaction to obtain the residual oil and the adsorbent adsorbed with the n-alkane;
Carrying out desorption treatment on the obtained adsorbent adsorbed with normal alkane by adopting desorption gas to obtain desorption oil and the desorbed adsorbent;
Introducing the raffinate oil into a main riser reactor to contact with a first catalytic conversion catalyst and perform a first catalytic conversion reaction;
Introducing a dechlorination agent into the downstream of the main riser reactor to contact with the oiling agent in the reactor for dechlorination reaction;
Feeding the oiling agent obtained by the reaction of the main riser reactor into a fluidized bed reactor for continuously carrying out a second catalytic conversion reaction to obtain a first reaction product and a first spent catalyst;
Introducing desorption oil into a secondary riser reactor to contact with a second catalytic conversion catalyst and perform a third catalytic conversion reaction to obtain a second reaction product and a second spent catalyst;
separating the obtained first reaction product and the second reaction product to obtain at least ethylene, propylene, butylene and gasoline containing aromatic hydrocarbon;
And sending the obtained first spent catalyst and the second spent catalyst into a regenerator for burning regeneration, and returning at least part of the obtained regenerated catalyst to the main riser reactor and the auxiliary riser reactor to be used as the first catalytic conversion catalyst and the second catalytic conversion catalyst.
The waste plastic oil raw material is processed by waste polyvinyl chloride or a mixture containing the polyvinyl chloride, wherein the normal alkane content is 6-30 wt%, the alkene content is 20-40 wt% and the chlorine content is 50-2000 mg/kg.
The chlorine content in the raffinate oil is 20-1000 mg/kg; the content of normal alkane in the desorption oil is 85-98 wt% and the content of chlorine is 0-100 mg/kg.
The adsorption and desorption reactor is selected from one or more of a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor or an expanded bed reactor.
The normal alkane adsorbent is one or more selected from activated carbon, activated carbon fiber, carbonized resin silica gel, natural zeolite, synthetic zeolite, molecular sieve and activated alumina.
The conditions of the adsorption separation reaction include: the temperature is 250-380 ℃, and the weight hourly space velocity of the waste plastic oil raw material is 0.1-20 hours-1; the conditions of the desorption treatment include: the temperature is 300-450 ℃, the desorption gas is nitrogen or hydrogen, and the weight hourly space velocity of the desorption gas is 100-200 hours -1.
The conditions of the first catalytic conversion reaction include: the reaction temperature is 500-700 ℃, preferably 530-650 ℃, the reaction time is 1-10 seconds, preferably 1-5 seconds, the weight ratio of the first catalytic conversion catalyst to the raffinate oil (abbreviated as the catalyst-oil weight ratio) is 1-50, preferably 5-30, and the weight ratio of the water vapor to the raffinate oil (abbreviated as the water-oil weight ratio) is 0.01-1.
The feeding weight ratio of the raffinate oil to the desorbed oil is 1-10.
The conditions of the second catalytic conversion reaction include: the reaction temperature is 490-680 ℃, preferably 510-630 ℃, and the weight hourly space velocity is 0.5-20 hours -1, preferably 2-10 hours -1.
The conditions for the third catalytic conversion reaction include: the reaction temperature is 560-750 ℃, preferably 580-730 ℃, the reaction time is 1-10 seconds, preferably 1-8 seconds, the weight ratio of the third catalytic conversion catalyst to the desorption oil (abbreviated as the catalyst-oil weight ratio) is 1-100, preferably 10-50, and the weight ratio of the water vapor to the desorption oil (abbreviated as the water-oil weight ratio) is 0.01-1, preferably 0.15-0.50.
The method further comprises the steps of: the pre-heated desorption oil and the pre-heated desorption oil are respectively introduced into the main riser reactor and the auxiliary riser reactor, and the temperature of the pre-heated desorption oil and the pre-heated desorption oil are respectively and independently 350-450 ℃.
The first and second catalytic conversion catalysts each independently comprise, on a dry basis and based on the total weight of the catalyst, from 1 to 60 wt% zeolite, from 5 to 99 wt% inorganic oxide, and from 0 to 70 wt% clay; the inorganic oxide is silicon dioxide and/or aluminum oxide; the clay is kaolin and/or halloysite.
The zeolite comprises 50-100 wt% of a medium pore zeolite and 0-50 wt% of a large pore zeolite on a dry basis and based on the total weight of the zeolite.
The zeolite comprises, on a dry basis and based on the total weight of the zeolite, from 70 to 100% by weight of a medium pore zeolite and from 0 to 30% by weight of a large pore zeolite.
The medium pore zeolite is ZSM series zeolite and/or ZRP zeolite, and the large pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silicon Y.
The dechlorinating agent comprises 5-80 wt% of calcium compound, 5-95 wt% of inorganic oxide and 0-50 wt% of clay on a dry basis and based on the total weight of the dechlorinating agent; the calcium compound is one or more of calcium hydroxide, calcium carbonate and calcium oxide; the inorganic oxide is silicon dioxide and/or aluminum oxide; the clay is kaolin and/or halloysite.
The dechlorinating agent is used in an amount of 50 to 5000 mg/kg, preferably 100 to 2000 mg/kg, based on the total weight of the waste plastic oil feed.
The dechlorinating agent is introduced into the main riser reactor at a position 1/3-3/4, preferably 1/2-2/3, from the bottom of the reactor.
A second embodiment is:
The system comprises an adsorption and desorption reactor, a main riser reactor, an auxiliary riser reactor, a fluidized bed reactor, a stripping section, a settler and a regenerator, wherein the settler, the fluidized bed reactor and the stripping section are arranged from top to bottom and are in fluid communication, and the main riser reactor passes through the stripping section from bottom to top and enters the fluidized bed reactor;
The adsorption and desorption reactor is provided with a waste plastic oil raw material inlet, a desorption gas inlet, an adsorption and desorption oil outlet and a main riser reactor, wherein the adsorption and desorption oil outlet is in fluid communication with the feed inlet of the main riser reactor, and the desorption oil outlet is in fluid communication with the feed inlet of the auxiliary riser reactor;
The main riser reactor is provided with a feed inlet, a catalyst inlet, a dechlorinating agent inlet and an oil agent outlet, the auxiliary riser reactor is provided with a desorption oil feed inlet, a catalyst inlet and an oil agent outlet, the stripping section is provided with a catalyst outlet, and the settler is provided with an oil gas outlet;
The oil outlet of the main riser reactor is positioned in the fluidized bed reactor, and the oil outlet of the auxiliary riser reactor is in fluid communication with the settler;
The regenerator is provided with a catalyst inlet in fluid communication with the catalyst outlet of the stripping section and a catalyst outlet in fluid communication with the catalyst inlets of the primary and secondary riser reactors.
The adsorption and desorption reactor is a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor or an expanded bed reactor; the system further comprises a preheating device for preheating the desorbed oil and/or the raffinate oil.
The invention will be further described with reference to the accompanying drawings, but the invention is not limited thereto.
As shown in fig. 1, waste plastic oil enters the top of an adsorption and desorption reactor 6 through a pipeline 21, and after adsorption and separation by an adsorbent, the residual oil enters a heating furnace 7 through a pipeline 24 for preheating; nitrogen is injected into the bottom of the adsorption-desorption reactor 6 through a pipeline 22, so that the molecular sieve desorbs the adsorbed normal alkane component, and the generated desorption oil enters the heating furnace 7 through a pipeline 23 for preheating.
The pre-lifting medium enters from the bottom of the main riser reactor 1 through a pipeline 19, the regenerated catalyst from the regeneration inclined tube 18 enters the main riser reactor 1 and moves upwards along the main riser reactor under the lifting action of the pre-lifting medium, preheated raffinate oil is injected into the main riser reactor 1 through a pipeline 9 together with atomized steam from a pipeline 8 and is mixed with the existing material flow of the main riser reactor 1, the raw material oil undergoes catalytic cracking reaction on the hot catalyst, and a dechlorinating agent enters the downstream of the main riser reactor through a pipeline 26, contacts with the existing material flow in the reactor to undergo dechlorination reaction and moves upwards and enters the fluidized bed reactor 2. The preheated desorption oil is injected into the bottom of the secondary riser reactor 3 through a line 11 together with atomized steam from a line 10, contacts the regenerated catalyst injected through a line 25, and undergoes catalytic cracking reaction. The generated reaction product and the spent catalyst enter a cyclone separator 14 in a settler 4 to realize the separation of the spent catalyst and the reaction product, the reaction product enters a gas collection chamber 15, and the catalyst fine powder returns to the settler. The spent catalyst in the settler flows to stripping section 12 and is contacted with steam from line 13. The reaction products stripped from the spent catalyst pass through the cyclone and enter the plenum 15. The stripped spent catalyst enters the regenerator 5 through a spent inclined pipe 17, coke on the spent catalyst is burned off, and flue gas enters a subsequent energy recovery system through a flue gas pipeline 20. Wherein the pre-lifting medium may be dry gas, water vapor or a mixture thereof.
The regenerated catalyst enters the bottom of the main riser reactor through a regeneration inclined tube 18 communicated with the catalyst outlet of the regenerator 5, and the reaction product oil gas in the gas collection chamber 7 enters a subsequent separation system through an atmosphere pipeline 16.
The following examples further illustrate the invention, but are not intended to limit it.
The chlorine-containing plastic oils used in the examples and comparative examples were processed from a mixture of at least one of waste plastic PVC and PE, PP, PS, PET, the pretreatment catalyst was an industrial catalytic cracker waste catalyst, the catalytic conversion catalyst was commercially available under the trade designation DMMC-2, and the properties are shown in Table 1. The low carbon olefin yield is the total yield of ethylene, propylene and butene.
The preparation method of the dechlorinating agent used in the examples is briefly described as follows:
Pulping the multi-water kaolin by using deionized water, adding pseudo-boehmite, regulating the PH of the multi-water kaolin to 2-4 by using hydrochloric acid, uniformly stirring, standing and aging for 1 hour at 60-70 ℃, keeping the PH to 2-4, cooling to below 60 ℃, adding aluminum sol, and stirring for 40 minutes to obtain mixed slurry. And adding the calcium compound into the obtained mixed slurry, uniformly stirring, spray-drying, forming and drying to obtain the dechlorination agent sample.
Comparative example 1
The test is carried out on a medium-sized device of the riser reactor, preheated waste plastic oil enters the bottom of the main riser reactor and the bottom of the auxiliary riser reactor respectively for catalytic cracking reaction, the outlet of the main riser reactor is communicated with the fluidized bed reactor, and the weight ratio of the waste plastic oil to the feed of the main riser reactor and the auxiliary riser reactor in unit time is 3:1. The reaction product and the spent catalyst enter a closed cyclone separator from the outlet of the reactor, the reaction product and the spent catalyst are rapidly separated, and the reaction product is cut and separated according to the distillation range in a separation system, so that fractions such as ethylene, propylene, butylene, pyrolysis gasoline rich in aromatic hydrocarbon and the like are obtained.
The spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped spent catalyst enters a regenerator to be in contact with air for regeneration; the regenerated catalyst enters a degassing tank to remove oxygen-containing gas adsorbed and carried by the regenerated catalyst; the degassed regenerated catalyst is returned to the riser reactor for recycling; the operating conditions and product distribution are listed in Table 2.
As can be seen from the results of Table 2, the yield of the light olefins was 28.71 wt% and the yield of the aromatic hydrocarbons was 14.93 wt%.
Example 1
The test was carried out according to the flow chart of fig. 1, the raw oil is waste plastic oil raw material, the adsorption separation reaction is carried out on a fixed bed adsorption and desorption reactor, the normal alkane adsorbent is 5A molecular sieve, and the adsorption separation reaction conditions are as follows: the temperature is 300 ℃, and the weight hourly space velocity of the waste plastic oil raw material is 1.0 hour -1; desorption treatment conditions: the desorption gas is nitrogen, the weight hourly space velocity of the desorption gas is 150 hours -1, and the temperature is 360 ℃. The chlorine content in the adsorbed oil was 310 mg/kg, the normal paraffin content in the desorbed oil was 95 wt.%, and the chlorine content was 15 mg/kg. And (3) the desorption oil and the residual oil generated by the adsorption separation of the waste plastic oil enter a heating furnace to be heated to 420 ℃.
The catalytic cracking reaction is carried out on a medium-sized device in the riser reactor, preheated residual absorbing oil enters the main riser reactor to carry out a first catalytic cracking reaction, contacts with a dechlorinating agent injected from the downstream in the main riser reactor and carries out a dechlorinating reaction, a reaction oil mixture enters the fluidized bed reactor from an outlet of the main riser reactor to carry out a second catalytic cracking reaction, and preheated desorption oil enters the bottom of the auxiliary riser reactor to carry out a third catalytic cracking reaction; the feeding weight ratio of the residual oil to the desorption oil in unit time is 3:1. Cutting the reaction product in a separation system according to the distillation range, thereby obtaining fractions such as ethylene, propylene, butylene, pyrolysis gasoline rich in aromatic hydrocarbon and the like; the spent catalyst enters a stripping section under the action of gravity, hydrocarbon products adsorbed on the spent catalyst are stripped by steam, and the stripped catalyst enters a regenerator; the regenerated catalyst returns to the riser reactor for recycling after regeneration; the operating conditions and product distribution are listed in Table 2.
As can be seen from the results in Table 2, the yield of the low-carbon olefin was 43.98 wt% and the yield of the aromatic hydrocarbon was 20.79 wt%.
As can be seen from the results of the examples, the method of the invention ensures that the yield of the low-carbon olefin generated by decomposing the waste plastic oil is high, especially the yield of propylene is high, and the chlorine content in the fuel oil is greatly reduced.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the present invention can be made, as long as it does not depart from the gist of the present invention, which is also regarded as the content of the present invention.
TABLE 1
| Chlorine-containing plastic oil | |
| Density in kg/m 3 | 800.11 |
| Sulfur content, mg/kg | 145 |
| Carbon residue, weight percent | 0.04 |
| Nitrogen content, mg/kg | 260 |
| Group composition, weight percent | |
| N-alkanes | 28.2 |
| Naphthenes/olefins | 18.1 |
| Aromatic hydrocarbons | 10.0 |
| Chlorine content, mg/kg | 1350 |
TABLE 2
| Comparative example | Examples | |
| Adsorption separation reaction and desorption treatment | ||
| Adsorption temperature, DEG C | / | 300 |
| Weight hourly space velocity of feed, hours -1 | / | 1.0 |
| Desorption temperature, DEG C | / | 360 |
| Desorbing gas weight hourly space velocity, hours -1 | / | 150 |
| Catalytic cracking unit | ||
| Main riser reactor | ||
| Outlet temperature, DEG C | 550 | 550 |
| Reaction time, seconds | 2 | 2 |
| Water-oil weight ratio | 0.1 | 0.1 |
| Weight ratio of agent to oil | 8 | 8 |
| Dechlorinating agent dosage, weight percent | / | 0.02 |
| Fluidized bed reactor | ||
| Temperature of reaction bed layer, DEG C | 535 | 535 |
| Weight hourly space velocity, hours -1 | 5 | 5 |
| Auxiliary riser reactor | ||
| Outlet temperature of auxiliary riser, DEG C | 650 | 650 |
| Reaction time, seconds | 1.8 | 1.8 |
| Water-oil weight ratio | 0.2 | 0.2 |
| Weight ratio of agent to oil | 25 | 25 |
| Distribution of the product, weight percent | ||
| Dry gas | 8.6 | 7.8 |
| LPG | 30.2 | 50.36 |
| Pyrolysis gasoline | 37.54 | 27.58 |
| Cracking diesel oil | 10.5 | 5.26 |
| Cracking heavy oil | 4.15 | 1.5 |
| Coke | 9.01 | 7.5 |
| Totalizing | 100.00 | 100.00 |
| Low-carbon olefin, wt% | 28.71 | 43.98 |
| Aromatic hydrocarbon yield, wt% | 14.93 | 20.79 |
Claims (20)
1. A method for producing low-carbon olefin and aromatic hydrocarbon by using waste plastic oil, which comprises the following steps:
Introducing a waste plastic oil raw material into an adsorption and desorption reactor to be contacted with an n-alkane adsorbent and perform adsorption separation to obtain an adsorbed residual oil and the adsorbent adsorbed with the n-alkane, wherein the waste plastic oil raw material is prepared by processing waste polyvinyl chloride or a mixture containing the polyvinyl chloride, the n-alkane content is 6-30 wt%, the olefin content is 20-40 wt% and the chlorine content is 50-2000 mg/kg;
Carrying out desorption treatment on the obtained adsorbent adsorbed with normal alkane by adopting desorption gas to obtain desorption oil and the desorbed adsorbent;
Introducing the raffinate oil into a main riser reactor to contact with a first catalytic conversion catalyst and perform a first catalytic conversion reaction;
Introducing a dechlorination agent into the main riser reactor, and contacting the downstream of the main riser reactor with an oiling agent in the reactor to perform dechlorination reaction, wherein the dechlorination agent comprises 5-80 wt% of calcium compound, 5-95 wt% of inorganic oxide and 0-50 wt% of clay on a dry basis and based on the total weight of the dechlorination agent; the calcium compound is one or more of calcium hydroxide, calcium carbonate and calcium oxide; the inorganic oxide is silicon dioxide and/or aluminum oxide; the clay is kaolin and/or halloysite, and the dosage of the dechlorinating agent is 50-5000 mg/kg based on the total weight of the feeding amount of the waste plastic oil;
Feeding the oiling agent obtained by the reaction of the main riser reactor into a fluidized bed reactor for continuously carrying out a second catalytic conversion reaction to obtain a first reaction product and a first spent catalyst;
Introducing desorption oil into a secondary riser reactor to contact with a second catalytic conversion catalyst and perform a third catalytic conversion reaction to obtain a second reaction product and a second spent catalyst;
separating the obtained first reaction product and the second reaction product to obtain at least ethylene, propylene, butylene and gasoline containing aromatic hydrocarbon;
And sending the obtained first spent catalyst and the second spent catalyst into a regenerator for burning regeneration, and returning at least part of the obtained regenerated catalyst to the main riser reactor and the auxiliary riser reactor to be used as the first catalytic conversion catalyst and the second catalytic conversion catalyst.
2. The method of claim 1, wherein the chlorine content of the raffinate oil is from 20 to 1000 mg/kg; the content of normal alkane in the desorption oil is 85-98 wt% and the content of chlorine is 0-100 mg/kg.
3. The method of claim 1, wherein the adsorption-desorption reactor is selected from one or more of a fixed bed reactor, a moving bed reactor, a simulated moving bed reactor, or an expanded bed reactor.
4. The method of claim 1, wherein the normal paraffin adsorbent is one or more selected from the group consisting of activated carbon, activated carbon fiber, carbonized resin silica gel, natural zeolite, synthetic zeolite, molecular sieve, and activated alumina.
5. The method of claim 1, wherein the conditions of the adsorptive separation reaction comprise: the temperature is 250-380 ℃, and the weight hourly space velocity of the waste plastic oil raw material is 0.1-20 hours -1; the conditions of the desorption treatment include: the temperature is 300-450 ℃, the desorption gas is nitrogen or hydrogen, and the weight hourly space velocity of the desorption gas is 100-200 hours -1.
6. The method of claim 1, wherein the conditions of the first catalytic conversion reaction comprise: the reaction temperature is 500-700 ℃, the reaction time is 1-10 seconds, and the weight ratio of the first catalytic conversion catalyst to the raffinate oil is 1-50.
7. The method of claim 1, wherein the conditions of the first catalytic conversion reaction comprise: the reaction temperature is 530-650 ℃, the reaction time is 1-5 seconds, and the weight ratio of the first catalytic conversion catalyst to the raffinate oil is 5-30.
8. The method of claim 1, wherein the feed weight ratio of the raffinate oil to the desorb oil is from 1 to 10.
9. The method of claim 1, wherein the conditions of the second catalytic conversion reaction comprise: the reaction temperature is 490-680 ℃, and the weight hourly space velocity is 0.5-20 hours -1.
10. The method of claim 1, wherein the conditions of the second catalytic conversion reaction comprise: the reaction temperature is 510-630 ℃, and the weight hourly space velocity is 2-10 hours -1.
11. The method of claim 1, wherein the conditions of the third catalytic conversion reaction comprise: the reaction temperature is 560-750 ℃, the reaction time is 1-10 seconds, and the weight ratio of the third catalytic conversion catalyst to the desorption oil is 1-100.
12. The method of claim 1, wherein the conditions of the third catalytic conversion reaction comprise: the reaction temperature is 580-730 ℃, the reaction time is 1-8 seconds, and the weight ratio of the third catalytic conversion catalyst to the desorption oil is 10-50.
13. The method according to claim 1, wherein the method further comprises: the pre-heated desorption oil and the pre-heated desorption oil are respectively introduced into the main riser reactor and the auxiliary riser reactor, and the temperature of the pre-heated desorption oil and the pre-heated desorption oil are respectively and independently 350-450 ℃.
14. The process of claim 1, wherein the first catalytic conversion catalyst and the second catalytic conversion catalyst each independently comprise, on a dry basis and based on the total weight of the catalyst, from 1 to 60 wt% zeolite, from 5 to 99 wt% inorganic oxide, and from 0 to 70 wt% clay; the inorganic oxide is silicon dioxide and/or aluminum oxide; the clay is kaolin and/or halloysite.
15. The process of claim 11 wherein the zeolite comprises 50-100 wt% medium pore zeolite and 0-50 wt% large pore zeolite on a dry basis and based on the total weight of the zeolite.
16. The method of claim 15 wherein the zeolite comprises 70-100 wt% medium pore zeolite and 0-30 wt% large pore zeolite on a dry basis and based on the total weight of the zeolite.
17. The method according to claim 15 or 16, wherein the medium pore zeolite is ZSM-series zeolite and/or ZRP zeolite, and the large pore zeolite is one or more selected from rare earth Y, rare earth hydrogen Y, ultrastable Y and high silicon Y.
18. The method of claim 1, wherein the dechlorinating agent is used in an amount of 100 to 2000 mg/kg based on the total weight of the waste plastic oil feed.
19. The process of claim 1 wherein the dechlorinating agent is introduced into the main riser reactor at a location 1/3 to 3/4 of the distance from the bottom of the reactor.
20. The process of claim 19 wherein the dechlorinating agent is introduced into the main riser reactor at a location 1/2-2/3 of the bottom of the reactor.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980938A (en) * | 2014-05-26 | 2014-08-13 | 大连理工大学 | Method for producing clean fuel by adopting chlorine-containing plastic oil |
| CN104726134A (en) * | 2015-03-18 | 2015-06-24 | 大连理工大学 | Method for producing high-quality gasoline/diesel from chlorine-containing plastic oil |
| CN205821248U (en) * | 2016-06-30 | 2016-12-21 | 中国石油化工股份有限公司 | A kind of catalytic conversion reactor |
| CN107557063A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of catalysis conversion method of inferior feedstock oil |
| CN107974284A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons |
| CN109158100A (en) * | 2018-09-28 | 2019-01-08 | 广东省环境科学研究院 | A kind of catalyst and preparation method thereof of catalytic cracking waste-plastic production fuel oil |
| CN109694722A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of catalysis conversion method for producing clean gasoline from inferior feedstock oil |
| CN109694726A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of catalysis conversion method of producing more propylene and light aromatic hydrocarbons |
| CN109705914A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of method and system carrying out catalytic cracking using double lifting leg |
| CN110857394A (en) * | 2018-08-24 | 2020-03-03 | 中国石油化工股份有限公司 | Method and system for processing coking gasoline and heavy raw oil |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2020
- 2020-09-01 CN CN202010904415.7A patent/CN114105724B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980938A (en) * | 2014-05-26 | 2014-08-13 | 大连理工大学 | Method for producing clean fuel by adopting chlorine-containing plastic oil |
| CN104726134A (en) * | 2015-03-18 | 2015-06-24 | 大连理工大学 | Method for producing high-quality gasoline/diesel from chlorine-containing plastic oil |
| CN205821248U (en) * | 2016-06-30 | 2016-12-21 | 中国石油化工股份有限公司 | A kind of catalytic conversion reactor |
| CN107557063A (en) * | 2016-06-30 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of catalysis conversion method of inferior feedstock oil |
| CN107974284A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of to produce low-carbon alkene and the catalytic cracking method of light aromatic hydrocarbons |
| CN109694722A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of catalysis conversion method for producing clean gasoline from inferior feedstock oil |
| CN109694726A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of catalysis conversion method of producing more propylene and light aromatic hydrocarbons |
| CN109705914A (en) * | 2017-10-25 | 2019-05-03 | 中国石油化工股份有限公司 | A kind of method and system carrying out catalytic cracking using double lifting leg |
| CN110857394A (en) * | 2018-08-24 | 2020-03-03 | 中国石油化工股份有限公司 | Method and system for processing coking gasoline and heavy raw oil |
| CN109158100A (en) * | 2018-09-28 | 2019-01-08 | 广东省环境科学研究院 | A kind of catalyst and preparation method thereof of catalytic cracking waste-plastic production fuel oil |
Non-Patent Citations (2)
| Title |
|---|
| 周华兰等.混合废塑料裂解液相产物的分析.《工业催化》.2017,第25卷(第11期),第49页左栏，第51页第2.3部分，第49页第1.1部分，第49页左栏第二段. * |
| 温宗国等.《水泥窑协同处置生活垃圾关键技术及城乡统筹一体化应用》.中国环境出版集团,2019,(第2019年10月第1版),第129-131页. * |
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