WO2021246588A1 - 고체산 물질을 이용한 고함량 염소 함유 폐유분의 염소 제거방법 - Google Patents

고체산 물질을 이용한 고함량 염소 함유 폐유분의 염소 제거방법 Download PDF

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WO2021246588A1
WO2021246588A1 PCT/KR2020/015786 KR2020015786W WO2021246588A1 WO 2021246588 A1 WO2021246588 A1 WO 2021246588A1 KR 2020015786 W KR2020015786 W KR 2020015786W WO 2021246588 A1 WO2021246588 A1 WO 2021246588A1
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WIPO (PCT)
Prior art keywords
chlorine
oil
waste oil
weight
solid acid
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Application number
PCT/KR2020/015786
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English (en)
French (fr)
Korean (ko)
Inventor
김도경
전희중
최재석
김가영
이호원
김태진
추대현
Original Assignee
에스케이이노베이션 주식회사
에스케이종합화학 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from KR1020200124533A external-priority patent/KR20210150249A/ko
Application filed by 에스케이이노베이션 주식회사, 에스케이종합화학 주식회사 filed Critical 에스케이이노베이션 주식회사
Priority to EP20939068.1A priority Critical patent/EP4105299A4/en
Priority to CN202080073772.1A priority patent/CN114616309A/zh
Priority to US17/912,705 priority patent/US20230174872A1/en
Publication of WO2021246588A1 publication Critical patent/WO2021246588A1/ko

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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
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/095—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with "solid acids", e.g. phosphoric acid deposited on a carrier
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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

Definitions

  • the present invention relates to a method for removing chlorine from waste oil containing high chlorine content using a solid acid material.
  • waste oil generated through the cracking and pyrolysis reaction of waste materials such as waste plastic pyrolysis oil contains a large amount of impurities from waste materials.
  • the Cl component is converted into HCl that may cause corrosion of the device during high-temperature treatment and is discharged.
  • Prior art 1 Japanese Laid-Open Patent Publication No. 1999-504672 A
  • a method for producing gasoline, diesel engine oil and carbon black from waste rubber and/or waste plastic materials relates to a method for producing gasoline, diesel engine oil and carbon black from waste rubber and/or waste plastic materials.
  • Cl, N, and S are removed by using basic substances such as KOH and NaOH
  • Catalytic Cracking It includes removing Cl, N, and S at the same time as cracking of the pyrolysis oil, and then separating the cracked oil to prepare a final product.
  • Cl is reduced by neutralization (using a base material such as KOH or NaOH).
  • This neutralization debonding reaction does not have a high Cl removal efficiency per unit weight of the base material, so the content is low enough to be introduced into the refinery process. It is difficult to prepare a Cl fraction (Cl number ppm). In addition, since the use cycle of the catalyst is short and the process of regenerating the used (neutralization catalyst) material is complicated, it is not preferable in terms of process simplification.
  • Prior Art 2 Japanese Patent No. 4218857 B2
  • a chlorine compound remover Specifically, Cl is adsorbed and removed from a fluid containing chlorine compounds by using a clay chlorine remover such as zinc oxide or talc. characterized in that
  • a clay chlorine remover such as zinc oxide or talc.
  • a low Cl-containing oil having a chlorine compound content of less than 10 ppm is used as a raw material. It is suitable for adsorbing Cl for a long time. Therefore, it is not effective to apply the adsorption technique to the waste stream containing a high Cl content.
  • Prior Art 3 Japanese Patent Application Laid-Open No. 2019-532118 A
  • a plastic or plastic pyrolysis fraction is converted into a mild fraction of bp ⁇ 370° C. and Cl is removed.
  • Cl is removed at the same time as the pyrolysis reaction, it is mainly converted to organic Cl in which olefin and Cl are combined and then combined with a solid acid point or removed through gas release. , there is a product loss problem.
  • An object of the present invention is to provide a Cl reduction technology of high Cl-containing waste oil using a solid acid material for high addition (fuel, chemical conversion) by applying a refinery process to high Cl-containing waste oil.
  • One embodiment of the present invention comprises the steps of: a) preparing a mixture of a chlorine-containing waste oil and a solid acid material; b) removing chlorine by reacting the mixture at a pressure of 1 bar or more and 100 bar or less in an inert gas atmosphere; And c) recovering the chlorine-removed fraction by separating the mixture of the chlorine-removed fraction and the solid acid material; It contains 50 wt% or less, and provides a method for removing chlorine from waste oil, characterized in that it satisfies the following relation (1).
  • A is the weight% of the component at a boiling point of 150°C or higher with respect to the total weight of the waste oil component
  • B is the weight% of the component at a bp level of 150°C or higher with respect to the total weight of the oil from which the chlorine has been removed.
  • the waste oil may include waste plastic pyrolysis oil, biomass pyrolysis oil, regenerated lubricating oil, high chlorine content crude oil, or a mixture thereof.
  • the chlorine content of the waste oil may be 10 ppm or more.
  • the solid acid material may be zeolite, clay, SAPO (silica-alumina-phosphate), ALPO (aluminum phosphate), MOF (Metal Organic Framework), silica alumina, or a mixture thereof.
  • the solid acid material may be included in an amount of 5 to 10% by weight based on the total weight of the mixture.
  • the reaction of step b) may be a catalytic conversion reaction in which chlorine contained in the waste oil is removed from direct bonding to and/or converted to hydrochloric acid (HCl) at the active point of the solid acid material.
  • HCl hydrochloric acid
  • step b) may be carried out at a temperature of more than 280 °C and less than 380 °C.
  • the chlorine removal method of the waste oil may further include d) repeating steps a), b), and c) at least once or more.
  • the chlorine content of the chlorine-removed oil may be less than 10 ppm.
  • a weight ratio of chlorine in the chlorine-removed fraction to chlorine in the waste fraction may be 0.01 to 0.1.
  • the high Cl-containing fraction 90 wt% or more of Cl can be removed to convert the fraction to a Cl fraction that can be introduced into the refinery process.
  • waste solid acid material (waste zeolite, waste clay, etc.) that is discarded after use in the petrochemical process can be used as it is or simply treated as a solid acid material for Cl removal.
  • 1-2 is a schematic diagram of a chlorine removal method according to an embodiment
  • 3 to 4 are graphs showing the residual N content and the residual S content by reaction temperature
  • 6 to 7 are graphs showing the residual Cl content and Cl reduction rate by reaction time
  • 11 to 12 are graphs showing the residual Cl content and Cl reduction rate by catalyst amount
  • 13 to 14 are graphs showing the residual N content and the residual S content by catalyst amount
  • 15 is a graph showing changes in oil composition by catalyst amount.
  • a to B means “A or more and B or less” unless otherwise defined.
  • a and/or B means at least one selected from the group consisting of A and B, unless otherwise defined.
  • the bp (boiling point) of the waste oil and the chlorine-removed oil means measured at atmospheric pressure (1 atm).
  • a method for removing chlorine from waste oil comprises the steps of: a) preparing a mixture of a chlorine-containing waste oil and a solid acid material; b) removing chlorine by reacting the mixture at a pressure of 1 bar or more and 100 bar or less in an inert gas atmosphere; and c) recovering the chlorine-removed fraction by separating the mixture of the chlorine-removed fraction and the solid acid material; It contains 5 to 50% by weight, and it is characterized in that the following relation 1 is satisfied.
  • A is the weight% of the component at a boiling point of 150°C or higher with respect to the total weight of the waste oil component
  • B is the weight% of the component at a bp level of 150°C or higher with respect to the total weight of the oil from which the chlorine has been removed.
  • the waste oil may include waste plastic pyrolysis oil, biomass pyrolysis oil, regenerated lubricating oil, high chlorine content crude oil, or a mixture thereof.
  • waste oil generated through cracking and pyrolysis of waste materials such as waste plastic pyrolysis oil contains a large amount of impurities derived from waste materials, so there is a risk of air pollutant emission when using it. Since there is a problem of being converted to HCl and discharged during the process, it is necessary to pre-treat waste oil to remove impurities.
  • the chlorine in the waste oil may be organic Cl, organic Cl, or a combination thereof, and the chlorine content in the waste oil may be 10 ppm or more and 20 ppm or more.
  • the upper limit of the content of chlorine in the waste oil is not particularly limited, but may be, for example, 600 ppm or less, preferably 500 ppm or less.
  • impurities in the waste oil include N, S and O, which may emit exhaust pollutants such as SOx and NOx, and metal components that adversely affect the catalyst activity of the refinery process when using fuel, such as Fe, Na, Ca and Al. can do.
  • N, S and O may be 100 ppm or more, or 500 to 8,000 ppm, S content of 10 ppm or more, or 20 to 1,000 ppm, and O content of 2,000 ppm or more, or 3,000 ppm to 3 wt%, based on the total weight of the waste oil, , Fe, Na, Ca and Al are Fe content of 1 ppm or more, or 1 to 10 ppm, Na content 1 ppm or more, or 1 to 10 ppm, Ca content 0.1 ppm or more, or 0.1 to 5 ppm and Al content with respect to the total weight of the waste oil 0.1 ppm or more, or 0.1 to 5 ppm.
  • the waste oil contains 5 to 50% by weight of components below 150° C. bp based on the total weight, for example, 5 to 45% by weight, 5 to 40% by weight, 5 to 35% by weight, 5 to 30% by weight, 5 to 25% by weight, 5 to 20% by weight or 5 to 15% by weight may be included. In addition, 10 to 50% by weight, 15 to 50% by weight, 20 to 50% by weight, 25 to 50% by weight, 30 to 50% by weight, 35 to 50% by weight or 40 to 50% by weight may be included.
  • the waste oil of the present invention can prevent deterioration of product properties due to oligomerization and product loss due to excessive cracking by removing chlorine without substantially changing oil properties even when the content of light oil is high.
  • the waste oil contains 10 to 35% by weight, for example, 10 to 30% by weight, 10 to 29% by weight, 11 to 28% by weight, 12 to 27% by weight of the bp 150°C to 265°C component based on the total weight. , 13 to 26% by weight, 14 to 26% by weight or 15 to 25% by weight may be included.
  • the waste oil contains 10 to 35% by weight, for example, 10 to 30% by weight, 10 to 29% by weight, 11 to 28% by weight, 12 to 27% by weight of the bp component at 265°C to 340°C with respect to the total weight. , 13 to 26% by weight, 14 to 26% by weight or 15 to 25% by weight may be included.
  • the waste oil contains 20 to 65% by weight, for example, 25 to 60% by weight, 25 to 55% by weight, 25 to 50% by weight, 30 to 50% by weight, 32 To 48% by weight, 35 to 45% by weight may be included.
  • the waste oil may include 30 to 70% by weight of an olefin, preferably 40 to 60% by weight, based on the total weight.
  • an olefin preferably 40 to 60% by weight, based on the total weight.
  • the solid acid material includes a Bronsted acid, a Lewis acid, or a mixture thereof, and specifically, a Bronsted acid or a Lewis acid site is a solid material in which the solid acid is present.
  • the material may be zeolite, clay, silica-alumina-phosphate (SAPO), aluminum phosphate (ALPO), Metal Organic Framework (MOF), silica alumina, or a mixture thereof.
  • the solid acid material is a solid material having a site that can give H + (Bronsted acid) or receive a lone pair of electrons (Lewis acid), and it is possible to induce various reactions such as cracking, alkylation and neutralization depending on the energy at the acid site .
  • a catalytic conversion reaction for converting Cl to HCl may be performed by activating the solid acid material under specific process conditions.
  • waste zeolite, waste clay, etc. which are being discarded after use in a petrochemical process can be utilized as it is or through simple treatment for further improvement of activity.
  • a fluidized bed catalyst is used in the RFCC process of converting resid to light/middle distillate.
  • E-Cat Equilibrium Cat.
  • RFCC E-Cat can be used as the solid acid material of the present invention, and the RFCC E-Cat is zeolite 30-50 wt%, clay 40-60 wt% and other materials (Alumina Gel, Silica Gel, Functional material, etc.) 0 It may consist of ⁇ 30 wt%.
  • a simple treatment may be required to use the waste zeolite, waste clay, etc. as a solid acid material in the process of the present invention. If a material such as coke or oil physically blocks the active point of the solid acid material, it may be removed and used. have. To remove coke, air burning can be carried out, or solvent can be used to remove oil. If necessary, if the metal component affects the active point of the solid acid material and is deactivated, the DeMet Process can be applied to remove the metal component by medium temperature treatment with a weak acid or diluted hydrogen peroxide.
  • the solid acid material may further include a carrier or binder comprising carbon, alkaline earth metal oxide, alkali metal oxide, alumina, silica, silica-alumina, zirconia, titania, silicon carbide, niobia, aluminum phosphate or a mixture thereof.
  • a carrier or binder comprising carbon, alkaline earth metal oxide, alkali metal oxide, alumina, silica, silica-alumina, zirconia, titania, silicon carbide, niobia, aluminum phosphate or a mixture thereof.
  • the solid acid material may be included in an amount of 5 to 10 wt%, preferably 7 to 10 wt%, more preferably 8 to 10 wt%, based on the total weight of the mixture.
  • the amount of the solid acid material introduced increases within the above range, the Cl removal effect is improved, and when it is 10 wt% or less, it is preferable to suppress the cracking reaction in the oil.
  • the mixture is reacted at a pressure of 1 bar or more and 100 bar or less in an inert gas atmosphere to remove chlorine.
  • the chlorine removal reaction in the fraction containing high chlorine content is expected in two directions.
  • One is that chlorine in the hydrocarbon structure is converted to HCl by a reaction by the active site of a solid acid catalyst, and then HCl or some organic Cl It is expected to be converted to and discharged, and the other reaction is expected to be removed by bonding directly to the active point of the solid acid material.
  • the waste oil is cracked and easily removed in the form of organic-Cl.
  • the product loss is large and the content of the olefin component contained in the waste oil may increase due to the increase in gas generation.
  • Cracking reaction can also be induced in the Cl removal reaction of the present invention.
  • the reaction proceeds at a low temperature of greater than 280°C and less than 380°C compared to general cracking conditions of 530°C or higher, and dealuminated zeolite is a main component, and E-cat., a weak acid material, is applied.
  • E-cat. a weak acid material
  • the reaction conditions may be a pressure of 1 bar or more and 100 bar or less in an inert gas atmosphere, and a temperature condition of 280° C. or more and 380° C. or less.
  • the process conditions may be performed under a pressure of N 2 1 to 100 bar, N 2 1 to 60 bar, or N 2 1 to 40 bar.
  • a catalytic pyrolysis reaction occurs, reducing the viscosity and molecular weight of the pyrolysis oil, and changing the composition of the oily product.
  • product loss occurs as Cl combines with olefin to form organic Cl that is removed.
  • the pressure exceeds 100 bar, it is not preferable because the operation of the reactor is difficult and the process cost is increased.
  • the process conditions may specifically be a temperature of more than 280 °C and less than 380 °C, a temperature of 290 ⁇ 360 °C, preferably a temperature of 290 ⁇ 340 °C, most preferably, it may be carried out at a temperature condition of 295 ⁇ 335 °C.
  • the temperature increases in the above temperature range, the Cl reduction effect increases, but in order to minimize the problem of liquid yield reduction due to the gas conversion of waste oil due to the increase of cracking reaction, it is necessary to adjust the catalyst content and reaction temperature/time do.
  • it is an appropriate treatment method for rapidly treating waste oil containing a high Cl content.
  • the removal rate of N, S and metal impurities also increases, so that a sweetening effect for introducing the refinery process can be expected.
  • step b) may be carried out in a fixed bed catalytic reactor or a batch reactor, but the present invention is not limited thereto.
  • a fluidized bed reactor can be used to produce a regenerated fraction, but in order to remove Cl from the waste fraction, the contact time between the catalyst and the fraction must be long. There is a disadvantage in that the efficiency of reducing impurities such as Cl is low compared to an infinite batch reactor.
  • Fixed bed reactors and continuous reactors are also advantageous in terms of catalyst contact time compared to fluidized bed reactors and have advantages in terms of ease of operation and securing safety compared to batch reactors.
  • a stirring operation when carrying out the Cl reduction reaction in a batch reactor (batch) 30-2000 rpm, preferably 200-1000 rpm, more preferably 300-7000 rpm and/or reaction time 0.1-48 h or 0.5-24 h, preferably is 1 to 12 h or 2 to 12 h, more preferably 3 to 5 h may be a stirring operation.
  • LHSV 0.1 to 10 hr -1 preferably 0.3 to 5 hr -1 , more preferably 1-3 hr -1 and/or GOR (Gas over Oil ratio) 50 to 2000, good may be driving at 200 to 1000, better still at 350 to 700.
  • the chlorine-free fraction is recovered by separating a mixture of the chlorine-removed fraction and the solid acid material.
  • the step of regenerating the separated waste solid acid material may be further performed, for example, the used solid acid material is put in a kiln, and the air atmosphere is 400 to 700 ° C., preferably 500 to 600 ° C. for 2 to 4 hours. It may be heat-treated during, but the present invention is not limited thereto.
  • step of repeating steps a), b), and c) at least once or more may be further performed.
  • repeated treatment it is possible to limit the strict Cl content (1wppm level) allowed in the subsequent refinery process. It can prevent deterioration and product loss.
  • the chlorine-removed oil according to an embodiment of the present invention is characterized in that the following relational expression 1 is satisfied.
  • A is the weight % of the component at a boiling point of 150° C. or higher with respect to the total weight of the waste oil component
  • B is the weight percent of the component at bp 150° C. or higher with respect to the total weight of the oil from which the chlorine is removed.
  • the B/A may be, for example, 0.9 to 1.1 or 0.95 to 1.05. Also, for example, it may be 0.85 to 1.15, 0.85 to 1.1, or 0.85 to 1.0.5. Also, for example, it may be 0.90 to 1.15 or 0.95 to 1.15.
  • the chlorine content of the chlorine-removed oil may be less than 10 ppm, specifically 8 ppm or less, 6 ppm or less, preferably 1 to 5 ppm or 1 to 4 ppm.
  • organic Cl generated through the combination of Cl generated by the breakdown of the olefin and C-Cl bond with the generated olefin by suppressing the cracking reaction and inducing a mild cracking reaction rather than an excessive cracking reaction is a solid acid. It can be debonded to the acid sites of the material, or it can be released as a gas. In addition, it may be externally discharged in the form of HCl through HCl conversion.
  • the chlorine-removed oil contains 5 to 60% by weight of components less than 150° C. bp based on the total weight, for example, 5 to 55% by weight, 5 to 50% by weight, 5 to 45% by weight, 5 to 40 Weight %, 5 to 35% by weight, 5 to 30% by weight, 5 to 25% by weight, 5 to 20% by weight or 5 to 15% by weight may be included. Also for example 10 to 60% by weight, 15 to 60% by weight, 20 to 60% by weight, 25 to 60% by weight, 30 to 60% by weight, 35 to 60% by weight, 40 to 60% by weight, 45 to 60% by weight % or 50 to 60% by weight.
  • the chlorine-removed oil may include a bp 150°C to 265°C component in an amount of 10 to 45% by weight, for example, 10 to 40% by weight or 10 to 35% by weight, based on the total weight.
  • the chlorine-removed oil contains 10 to 35% by weight, for example, 10 to 30% by weight, 10 to 29% by weight, 11 to 28% by weight, 12 to bp 265°C to 340°C component based on the total weight. 27% by weight, 13 to 26% by weight, 14 to 26% by weight or 15 to 25% by weight may be included.
  • the dechlorinated oil contains 20 to 60% by weight, for example, 20 to 55% by weight, 20 to 50% by weight, 20 to 45% by weight, or 25 to 40% by weight of components having a bp higher than 340°C with respect to the total weight. % can be included.
  • the weight ratio of chlorine of the chlorine-removed fraction to the chlorine of the waste fraction is 0.01 to 0.5, for example, 0.01 to 0.4, 0.01 to 0.3, or 0.01 to 0.2. preferably 0.01 to 0.1, more preferably 0.01 to 0.09, 0.01 to 0.08, 0.01 to 0.07, 0.01 to 0.06 or 0.01 to 0.05.
  • the Fe content may be less than 10 ppm, preferably 7 ppm or less, or 5 ppm or less, more preferably 3 ppm or less, and the Na content less than 10 ppm, preferably 7 ppm or less, based on the total weight of the oil from which the chlorine has been removed, or 5 ppm or less, more preferably 3 ppm or less, Ca content less than 5 ppm, preferably 3 ppm or less or 1 ppm or less, more preferably 0.5 ppm or less or 0.3 ppm or less, Al content less than 3 ppm, preferably 1 ppm or less or 0.5 ppm or less, more preferably 0.3 ppm or less or 0.1 ppm or less.
  • the weight ratio of Fe of the chlorine-removed fraction to Fe of the waste oil may be 0.1 to 0.7, for example, 0.1 to 0.6, preferably 0.5 or less, and the chlorine to Na of the waste oil is removed.
  • the weight ratio of Na in the oil may be 0.1 to 0.7, for example, 0.1 to 0.5, preferably 0.45 or less
  • the weight ratio of Ca of the dechlorinated oil to Ca of the waste oil is 0.1 to 0.8, for example 0.2 to 0.7, preferably 0.6 or less
  • a weight ratio of Al of the chlorine-removed fraction to Al of the waste fraction may be 0.1 to 0.7, for example 0.1 to 0.5, preferably 0.4 or less.
  • the N content may be less than 300 ppm, preferably 250 ppm or less, or 200 ppm or less, more preferably 170 ppm or less, S content less than 20 ppm, preferably 19 ppm or less, or It may be 18 ppm or less, more preferably 17 ppm or less, and the O content may be less than 0.2 wt%, preferably 0.15 wt% or less or 0.1 wt% or less, even more preferably less than 0.1 wt%.
  • the weight ratio of N of the chlorine-removed oil to N of the waste oil may be 0.1 to 0.7, for example, 0.1 to 0.6, preferably 0.5 or less, and the chlorine-removed S to S of the waste oil.
  • the weight ratio of S of the oil component may be less than 1, for example, 0.1 to 0.9, preferably 0.8 or less, and the weight ratio of O of the dechlorinated oil to O of the waste oil is less than 1, for example, 0.1 to 0.9. , preferably 0.8 or less, 0.7 or less, 0.6 or less, or 0.5 or less.
  • Waste oil (plastic pyrolysis oil) converted through pyrolysis of plastic waste was recovered and used as a raw material for Cl removal reaction.
  • GC-Simdis analysis HT 750
  • Impurities were analyzed for Cl, S, N, O, Fe, Ca, Na, Al, Si, P, etc., and for this purpose, ICP, TNS, EA-O, and XRF analysis were performed.
  • GC-MSD analysis was performed to analyze the olefin content.
  • Example 1 Since the pyrolysis-induced solid phase of Example 1 was maintained in an oven at 70° C. for 3 hours or more, it was converted into a liquid phase and used.
  • RFCC E-cat. was used for the solid acid material used to reduce impurities including Cl.
  • the physical properties of the RFCC E-cat. used were confirmed as shown in Tables 3 and 4 below.
  • Type TSA (m 2 /g) ZSA (m 2 /g) MSA (m 2 /g) Z/M Ratio PV (cc/g) APD ( ⁇ ) RFCC E-cat. 122 36 86 0.42 0.20 67
  • TSA is the total specific surface area
  • ZSA is the zeolite specific surface area
  • MSA is the mesoporous specific surface area
  • Z/M is the ratio of the zeolite specific surface area (ZSA) to the mesoporous specific surface area (MSA)
  • PV is the pore Volume
  • APD is the mean pore size.
  • RFCC E-cat. a catalyst having a total specific surface area of 112 m 2 /g, a pore volume of 0.20 cc/g, and an average particle size of 79 ⁇ m was used.
  • Example 3-1 In order to confirm the Cl reduction characteristics of the solid acid catalyst, the Cl reduction tendency with time was confirmed under the operating conditions of 330°C, where the composition difference derived in Example 3-1 was small and the Cl reduction efficiency was high.
  • Other reaction parameters such as catalyst amount and stirring speed, and the analysis method were carried out under the same conditions as in Example 2-1. And the analysis results are shown in Tables 8 to 10 and FIGS. 6 to 10 below.
  • Example 2-1 In order to check whether it is possible to remove metal impurities such as Fe, Na, Ca in addition to impurities such as Cl, N, S, O, etc., the sample recovered under the operating conditions of 330 ° C. of Example 2-1 with no composition change and high Cl reduction efficiency Metal impurity analysis was carried out for It was confirmed that more than 60% of Fe, Na, Ca, and Al were simultaneously removed.

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PCT/KR2020/015786 2020-06-03 2020-11-11 고체산 물질을 이용한 고함량 염소 함유 폐유분의 염소 제거방법 WO2021246588A1 (ko)

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EP20939068.1A EP4105299A4 (en) 2020-06-03 2020-11-11 METHOD FOR REMOVAL OF CHLORINE FROM HIGH CHLORINE WASTE OIL FRACTIONS USING SOLID ACID MATERIAL
CN202080073772.1A CN114616309A (zh) 2020-06-03 2020-11-11 利用固体酸物质去除含有高含量氯的废油馏分中的氯的方法
US17/912,705 US20230174872A1 (en) 2020-06-03 2020-11-11 Method for Removing Chlorine from Waste Oil Fractions Containing High Content of Chlorine Using Solid Acid Material

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WO2023195710A1 (en) * 2022-04-04 2023-10-12 Sk Innovation Co., Ltd. Method and device for producing waste plastic pyrolysis oil with reduced chlorine

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