US20230130559A1 - Method for Removing Chlorine from High Chlorine Content Waste Oil Using Solid Acid Substances - Google Patents

Method for Removing Chlorine from High Chlorine Content Waste Oil Using Solid Acid Substances Download PDF

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US20230130559A1
US20230130559A1 US17/912,773 US202017912773A US2023130559A1 US 20230130559 A1 US20230130559 A1 US 20230130559A1 US 202017912773 A US202017912773 A US 202017912773A US 2023130559 A1 US2023130559 A1 US 2023130559A1
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oil
waste oil
chlorine
reaction
waste
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Dokyoung Kim
Heejung JEON
Jaesuk CHOI
Kayoung Kim
Howon Lee
TaeJin KIM
Daehyun Choo
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SK Innovation Co Ltd
SK Geo Centric Co Ltd
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SK Innovation Co Ltd
SK Geo Centric Co Ltd
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Priority claimed from KR1020200115425A external-priority patent/KR20210150246A/ko
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Assigned to SK INNOVATION CO., LTD., SK GEO CENTRIC CO., LTD. reassignment SK INNOVATION CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIM, KAYOUNG, KIM, TAEJIN, CHOO, Daehyun, CHOI, Jaesuk, JEON, Heejung, LEE, HOWON, KIM, Dokyoung
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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
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G7/00—Distillation of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—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
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials
    • C10G2300/1007—Used oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • 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

Definitions

  • the present invention relates to a method for removing chlorine from a waste oil having a high chlorine content using a solid acid material.
  • waste oil produced by a cracking or pyrolysis reaction of the waste material such as a waste plastic pyrolysis oil
  • air pollutants such as SO x and NO x may be released, and in particular, a Cl component may be converted into HCl which may cause device corrosion in a high-temperature treatment process and released.
  • Japanese Patent Laid-Open Publication No. 1999-504672 A relates to a method of producing gasoline, diesel engine oil, and carbon black from waste rubber and/or waste plastic materials. Specifically, it includes: removing Cl, N, S, and the like by bonds using a base material such as KOH or NaOH by a primary impurity removal process from a pyrolysis oil obtained from pyrolysis of waste rubber and waste plastic, and removing Cl, N, and S simultaneously with cracking of the pyrolysis oil in a secondary catalytic cracking process, wherein a cracked oil is then separated to produce a final product.
  • a base material such as KOH or NaOH
  • Related Art Document 2 Japanese Patent Registration No. 4218857 B2 relates to a chlorine compound remover. Specifically, it removes Cl from a fluid including a chlorine compound by adsorption using a clay chlorine remover such as zinc oxide and talc, and the adsorption removal is Cl removal by bonding and it is characterized in that Cl bonded to a Cl remover is not released.
  • Related Art Document 2 uses a low-Cl content oil having a Cl content of less than 10 ppm as a raw material, as described in the evaluation test of a chlorine compound removal performance in a liquid hydrocarbon, and the Cl removal technology using an adsorbent as such is generally appropriate for adsorbing a trace amount of Cl for a long time. Therefore, applying the adsorption technology to the waste oil having a high Cl content is not effective.
  • Japanese Patent Laid-Open Publication No. 2019-532118 A relates to a dechlorination method of a mixed plastic pyrolysis oil using devolatilization extrusion and a chloride scavenger. Specifically, it is characterized by converting plastic or a plastic pyrolysis oil into a mild oil having bp ⁇ 370° C. by a pyrolysis reaction using a fluidized bed catalyst to remove Cl.
  • Cl is removed simultaneously with a pyrolysis reaction, it is removed in the form of organic Cl in which an olefin and Cl are bonded, and moisture simultaneously occurs to cause problems of equipment corrosion, reaction abnormality, deterioration of product properties, and product loss.
  • An object of the present invention is to provide a technology of reducing Cl in a waste oil having a high Cl content by using a solid acid material, for high value added (fuel, chemical conversion) of a waste oil having a high Cl content by application of a refinery process.
  • an object of the present invention is to provide a technology of conversion into a Cl oil at a level to allow introduction to a refinery process, by removing 90 wt % or more of Cl from a pyrolysis oil having a high Cl content recovered by waste plastic pyrolysis by a Cl catalytic conversion reaction using a solid acid material.
  • a method for removing chlorine from a waste oil includes: a) preparing a mixture of a chlorine-containing waste oil and a solid acid material; b) reacting the mixture to remove chlorine; and c) separating a dechlorinated oil fraction and the solid acid material from the mixture to recover the dechlorinated oil fraction, wherein the following Relation 1 is satisfied:
  • A is a wt % of components having a boiling point (bp) of 150° C. or higher with respect to a total weight of the waste oil
  • B is a wt % of components having bp of 150° C. or higher with respect to a total weight of the dechlorinated oil fraction.
  • the waste oil having a high chlorine content provided in step a) may include a waste plastic pyrolysis oil, a biomass pyrolysis oil, a regenerated lubricant, a crude oil having a high chlorine content, or a combination thereof.
  • the solid acid material in step a) has a Bronsted acid point or a Lewis acid point, and may include zeolite, clay, silica-alumina-phosphate (SAPO), aluminum phosphate (ALPO), metal organic framework (MOF), silica alumina, or a mixture thereof.
  • SAPO silica-alumina-phosphate
  • APO aluminum phosphate
  • MOF metal organic framework
  • impurities may be selectively reduced without a decrease in a molecular weight distribution of the waste oil, and the impurities may include sulfur, nitrogen, oxygen, and metals such as Na, Ca, Fe, Al, and As in addition to chlorine.
  • a method of carrying out an impurity reduction reaction may be implemented using a batch reactor, a semi-batch reactor, a continuous stirred-tank reactor (CSTR), and a fixed bed reactor.
  • CSTR continuous stirred-tank reactor
  • separating the oil from which impurities have been removed and the solid acid material in step c) may use a separation method using filtering, centrifugation, decanting, and the like.
  • the dechlorinated oil fraction having a chlorine content of less than 10 ppm may be prepared by steps a) to c).
  • the average molecular weight of the pyrolysis oil composition is slightly increased by an oligomerization reaction of an olefin and an alkylation reaction between the olefin and a branched paraffin in the pyrolysis oil, thereby preventing reaction abnormality, deterioration of product properties, and product loss.
  • waste solid acid material (waste zeolite, waste clay, and the like) which is discarded after use in a petrochemical process may be used as a solid acid material for Cl removal as it is or after being simply treated, it is preferred from an environmental point of view.
  • FIGS. 1 and 2 are schematic diagrams of a method for removing chlorine according to an exemplary embodiment of the present invention.
  • FIG. 3 is a graph showing a composition of a waste oil having a high Cl content.
  • FIG. 4 is a graph showing a composition change of an oil recovered after a CI reduction reaction.
  • FIGS. 5 and 6 are graphs showing a residual N content and a residual S content by reaction temperature.
  • FIG. 7 is a graph showing an oil composition change by reaction temperature.
  • FIGS. 8 and 9 are graphs showing a residual Cl content and a Cl reduction rate by reaction time.
  • FIGS. 10 and 11 are graphs showing a residual N content and a residual S content by reaction time.
  • FIG. 12 is a graph showing an oil composition change by reaction time.
  • FIG. 13 is a graph showing an apparent reaction rate equation of a reaction according to an exemplary embodiment.
  • FIGS. 14 and 15 are graphs showing a residual Cl content and a Cl reduction rate by catalytic amount.
  • FIGS. 16 and 17 are graphs showing a residual N content and a residual S content by catalytic amount.
  • FIG. 18 is a graph showing an oil composition change by catalytic amount.
  • a to B refers to “A or more and B or less”, unless otherwise particularly defined.
  • a and/or B refers to at least one selected from the group consisting of A and B, unless otherwise particularly defined.
  • a boiling point (bp) of a waste oil and a dechlorinated oil fraction refers to that measured at a normal pressure (1 atm), unless otherwise defined.
  • a method for removing chlorine from a waste oil includes: a) preparing a mixture of a chlorine-containing waste oil and a solid acid material; b) reacting the mixture to remove chlorine; and c) separating a dechlorinated oil fraction and the solid acid material from the mixture to recover the dechlorinated oil fraction, wherein the following Relation 1 is satisfied:
  • A is a wt % of components having a boiling point (bp) of 150° C. or higher with respect to a total weight of the waste oil
  • B is a wt % of components having bp of 150° C. or higher with respect to a total weight of the dechlorinated oil fraction.
  • a technology of reducing Cl in a waste oil having a high Cl content by using a solid acid material, for high value added (fuel, chemical conversion) of a waste oil having a high Cl content by application of a refinery process may be provided.
  • a) a mixture of a chlorine-containing waste oil and a solid acid material is prepared.
  • the waste oil may include a waste plastic pyrolysis oil, a biomass pyrolysis oil, a regenerated lubricant, a crude oil having a high chlorine content, or a mixture thereof. Since a large amount of impurities produced from a waste material are included in the waste oil produced by a cracking or pyrolysis reaction of the waste material such as a waste plastic pyrolysis oil, when the waste oil is used, air pollutants may be released, and in particular, a Cl component may be converted into HCl and released in a high temperature treatment process, and thus, it is necessary to pretreat the waste oil to remove impurities.
  • Chlorine in the waste oil may be inorganic Cl, organic Cl, or a combination thereof, and a chlorine content in the waste oil may be 10 ppm or more or 20 ppm or more. Meanwhile, the upper limit of the content of chlorine in the waste oil is not particularly limited, but may be 600 ppm or less, preferably 500 ppm or less.
  • a treatment technology of reducing Cl in a waste oil in which a Cl content (several ppm of Cl) is reduced to a level to allow introduction of the refinery process by treating the waste oil having a high CI content is required.
  • impurities in the waste oil may include N, S, and O which may be released as air pollutants such as SO x and NO x , and Fe, Na, Ca, Al, and the like as a metal component which adversely affects a refinery process catalytic activity.
  • N, S, and O may be included at a N content of 100 wppm or more or 500 to 8,000 wppm, a S content of 10 wppm or more or 20 to 1,000 wppm, and an O content of 2,000 wppm or more or 3,000 wppm to 3 wt % with respect to the total weight of the waste oil
  • Fe, Na, Ca, and Al may be included at a Fe content of 1 wppm or more or 1 to 10 wppm, a Na content of 1 wppm or more or 1 to 10 wppm, a Ca content of 0.1 wppm or more or 0.1 to 5 wppm, and an Al content of 0.1 wppm or more or 0.1 to 5 wppm with respect to the total weight of the waste oil.
  • the waste oil may have a ratio (A 2 /A 1 ) of 1 to 19, the ratio being a weight (A 2 ) of components having bp of 150° C. or higher to a weight (A 1 ) of components having bp of lower than 150° C.
  • the weight ratio (A 2 /A 1 ) of the waste oil components may be 1 to 16, preferably 3 to 15, and more preferably 9 to 13.
  • a weight ratio of components having bp of 265° C. or higher to components having bp of lower than 265° C. may be 1.1 to 2.5, preferably 1.1 to 2.3 or 1.1 to 2.1, and more preferably 1.1 to 2.0, 1.1 to 1.8, or 1.1 to 1.7.
  • a weight ratio of a C9+ component to a C4-C9 component may be 1 to 19, for example, 1 to 16, preferably 3 to 15, and more preferably 9 to 13.
  • a weight ratio of a C18+ component to a C4-C17 component may be 1.1 to 2.5, preferably 1.1 to 2.3 or 1.1 to 2.1, and more preferably 1.1 to 2.0, 1.1 to 1.8, or 1.1 to 1.7.
  • the waste oil may include 0.1 to 80 wt % of C4-C7 L-Naph, 0.1 to 80 wt % of C6-C8 H-Naph, 0.1 to 70 wt % of C9-C17 Kero, 0.1 to 80 wt % of C18-C20 LGO, 0.1 to 80 wt % of C21-C25 VGO, and 0.1 to 99 wt % of C26+AR, but the present invention is not limited thereto.
  • the waste oil may include 30 to 70 wt %, preferably 40 to 60 wt % of an olefin with respect to the total weight.
  • the waste oil may include 30 to 70 wt %, preferably 40 to 60 wt % of an olefin with respect to the total weight.
  • the solid acid material includes a Bronsted acid, a Lewis acid, or a mixture thereof, and specifically, a solid material in which a Bronsted acid or a Lewis acid site is present, and the solid acid material may be zeolite, clay, silica-alumina-phosphate (SAPO), aluminum phosphate (ALPO), metal organic framework (MOF), silica alumina, or a mixture thereof.
  • SAPO silica-alumina-phosphate
  • APO aluminum phosphate
  • MOF metal organic framework
  • the solid acid material is a solid material having a site capable of donating H + (Bronsted acid) or accepting a lone pair of electrons (Lewis acid), and allows derivation of various reactions such as cracking, alkylation, and neutralization depending on energy at an acid site.
  • the solid acid material is activated in specific process conditions, thereby carrying out a catalytic conversion reaction to convert Cl into HCl.
  • a high Cl content in the waste oil may be reduced to a several ppm level, and product abnormality (for example, cracking) and a yield loss (in the case in which Cl is removed as organic Cl, the case in which the oil is cracked and removed as gas, and the like) may be minimized.
  • waste zeolite, waste clay, and the like which are discarded after use in a petrochemical process are used as they are or used after a simple treatment for further activity improvement.
  • a fluidized bed catalyst is used in a RFCC process in which a residual oil is converted into a light/middle distillate, and in order to maintain the entire activity of the RFCC process constant, a certain amount of catalyst in operation is exchanged with a fresh catalyst every day, and the exchanged catalyst herein is named RFCC equilibrium catalyst (E-Cat) and discarded entirely.
  • RFCC E-Cat may be used as the solid acid material of the present invention, and RFCC E-Cat may be formed of 30 to 50 wt % of zeolite, 40 to 60 wt % of clay, and 0 to 30 wt % of other materials (alumina gel, silica gel, functional material, and the like).
  • a simple treatment may be needed in order to use the waste zeolite, the waste clay, and the like as the solid acid material of the process of the present invention, and when a material such as coke or oil physically blocks the active site of the solid acid material, the material may be removed.
  • a material such as coke or oil physically blocks the active site of the solid acid material
  • air burning may be performed or a treatment with a solvent may be performed for oil removal.
  • a DeMet process in which a weak acid or dilute hydrogen peroxide is treated at a medium temperature to remove the metal component may be applied.
  • the solid acid material may further include a carrier or a binder including carbon, alkali earth metal oxides, alkali metal oxides, alumina, silica, silica-alumina, zirconia, titania, silicon carbide, niobia, aluminum phosphate, or a mixture thereof.
  • a carrier or a binder including carbon, alkali earth metal oxides, alkali metal oxides, alumina, silica, silica-alumina, zirconia, titania, silicon carbide, niobia, aluminum phosphate, or a mixture thereof.
  • the solid acid material may be included at 5 to 10 wt %, preferably 7 to 10 wt %, and more preferably 8 to 10 wt % with respect to the total weight of the mixture.
  • the amount of the solid acid material introduced is increased, a CI removal effect is improved, and when the amount is 10 wt % or less, a cracking reaction in the oil may be suppressed, which is thus preferred.
  • the reaction of removing chlorine from an oil having a high chlorine content is largely expected as the following two types: one in which chlorine in a hydrocarbon structure is converted into HCl by a reaction by an active site of a solid acid catalyst and then is released as HCl or partially converted into organic Cl and then released, and the other one in which Cl is removed by a reaction of a direct bond to the active site of the solid acid material.
  • a conventional technology of removing Cl by H 2 feeding in a hydrotreating (HDT) process the waste oil is cracked, so that Cl is likely to be removed in the form of organic-Cl.
  • product loss is large and an olefin component content in the waste oil may be increased, which is thus not preferred.
  • the Cl removal reaction of the present invention may prevent the problems described above.
  • the reaction conditions may be a pressure of 1 bar or more and 100 bar or less under an inert gas atmosphere and a temperature of 200° C. or higher and lower than 300° C.
  • the process conditions may be performed under pressure conditions of 1 to 100 bar of N 2 , 1 to 60 bar of N 2 , or 1 to 40 bar of N 2 .
  • a catalytic pyrolysis reaction occurs to decrease the viscosity and the molecular weight of the pyrolysis oil and change the composition of the oil product.
  • Cl is bonded to an olefin to form organic Cl to be removed, thereby causing product loss.
  • reactor operation is difficult and process costs are increased, which is thus not preferred.
  • the process conditions may be performed at a temperature of, specifically 200 to 300° C., 230 to 300° C., 240 to 300° C., preferably 250 to 290° C. or 255 to 285° C., and most preferably 260-280° C.
  • a temperature of lower than 200° C. is applied, a conversion catalytic reaction in which chlorine (CI) contained in the waste oil is converted into a hydrochloric acid (HCl) is greatly decreased. Due to the low Cl reduction performance, it is necessary to increase a catalyst content, reaction temperature/time, and the like for complementing the performance, which is disadvantageous from an economic point of view, and thus, is inappropriate for treating the waste oil having a high Cl content.
  • a removal rate of N and S may be increased, and in particular, when the reaction proceeds at a temperature of 260° C. or higher, a reaction of removing N and S may proceed separately.
  • 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 regenerated oil may be prepared using a fluidized bed reactor
  • a contact time between the catalyst and the oil should be long for removing Cl in the regenerated oil, but the reduction efficiency of impurities such as Cl is low in the fluidized bed reactor having a very short contact time of several seconds or less as compared with the batch reactor having an infinite contact time between the catalyst and the oil.
  • impurity reduction efficiency may be increased by raising the reaction temperature, a cracking side reaction occurs at a high temperature to cause a composition change, and fluidized bed equipment investments and operation costs are high, and thus, it is relatively disadvantageous to secure economic feasibility.
  • the fixed bed reactor and a continuous reactor are also advantageous in terms of a catalyst contact time as compared with the fluidized bed reactor and in terms of easy operation and securing safety as compared with the batch reactor, but have low long-term stability and low Cl reduction efficiency for the Cl removal reaction.
  • a stirring operation may be performed at 30 to 2000 rpm, preferably 200 to 1000 rpm, and more preferably 300 to 700 rpm, and/or for a reaction time of 0.1 to 48 hrs or 0.5 to 24 hrs, preferably 1 to 12 hrs or 2 to 12 hrs, and more preferably 3 to 5 hrs.
  • the operation is performed at LHSV of 0.1 to 10 hr ⁇ 1 , preferably 0.3 to 5 hr ⁇ 1 , more preferably 1 to 3 hr ⁇ 1 , and/or gas over oil ratio (GOR) of 50 to 2000, preferably 200 to 1000, and more preferably 350 to 700.
  • LHSV 0.1 to 10 hr ⁇ 1 , preferably 0.3 to 5 hr ⁇ 1 , more preferably 1 to 3 hr ⁇ 1
  • GOR gas over oil ratio
  • the separation of the mixture may be performed by applying any known filtering or filtration method, but the present invention is not limited thereto.
  • the step of regenerating the separated waste solid acid material may be further performed, and for example, the used solid acid material may be placed in a calcination furnace and heat-treated at a temperature of 400 to 700° C., preferably 500 to 600° C. under an air atmosphere for 2 to 4 hrs, but the present invention is not limited thereto.
  • a step of repeating steps a), b), and c) at least once may be further performed.
  • the Cl content of strict standards (at a level of 1 wppm) accepted in a subsequent refinery process may be met, and the average molecular weight and/or the viscosity of the waste oil composition may be slightly increased, thereby preventing reaction abnormality, deterioration of product properties, and product loss.
  • the dechlorinated oil fraction according to an exemplary embodiment of the present invention is characterized by satisfying the following Relation 1:
  • A is a wt % of components having a boiling point (bp) of 150° C. or higher with respect to a total weight of the waste oil
  • B is a wt % of components having bp of 150° C. or higher with respect to a total weight of the dechlorinated oil fraction.
  • B/A may be 1 to 2, preferably 1 to 1.8, more preferably 1 to 1.5, and most preferably 1 to 1.3 or 1 to 1.2.
  • the chlorine content in the dechlorinated oil fraction may be less than 10 ppm, specifically 9 ppm or less, 8 ppm or less, or 1 to 7 ppm.
  • Cl When Cl is removed from the waste oil, the average molecular weight and/or the viscosity of the waste oil composition is slightly increased by an oligomerization reaction of an olefin and an alkylation reaction between the olefin and a branched paraffin in the waste oil, thereby preventing reaction abnormality, deterioration of product properties, and product loss.
  • the dechlorinated oil fraction may have a ratio (B 2 /B 1 ) of 1 to 20, the ratio being a weight (B 2 ) of components having bp of 150° C. or higher to a weight (B 1 ) of components having bp of lower than 150° C.
  • the weight ratio (B 2 /B 1 ) of the waste oil components may be 1 to 17, preferably 3 to 16, and more preferably 5 to 14.
  • a weight ratio of components having bp of 265° C. or higher to components having bp of lower than 265° C. may be 1.8 to 3.0, specifically 1.8 to 2.8, and preferably 1.8 to 2.6 or 1.9 to 2.5.
  • a weight ratio of a C9+ component to a C4-C8 component may be 1 to 20, for example, 1 to 17, preferably 3 to 16, and more preferably 5 to 14.
  • a weight ratio of a C18+ component to a C4-C17 component may be 1.8 to 3.0, for example, 1.8 to 2.8, and preferably 1.8 to 2.6 or 1.9 to 2.5.
  • the effects described above may be further improved within the above range.
  • a weight ratio of chlorine in the dechlorinated oil fraction to chlorine in the waste oil may be 0.01 to 0.25, for example, 0.01 to 0.20, 0.01 to 0.10, and preferably 0.01 to 0.08.
  • a Fe content may be less than 10 ppm, preferably 7 ppm or less or 5 ppm or less, and more preferably 3 ppm or less
  • a Na content may be less than 10 ppm, preferably 7 ppm or less or 5 ppm or less, and more preferably 3 ppm or less
  • a Ca content may be less than 5 ppm, preferably 3 ppm or less or 1 ppm or less, and more preferably 0.5 ppm or less or 0.3 ppm or less, with respect to the total weight of the dechlorinated oil fraction.
  • a weight ratio of Fe in the dechlorinated oil fraction to Fe in the waste oil may be 0.1 to 0.7, for example, 0.1 to 0.6, and preferably 0.5 or less
  • a weight ratio of Na in the dechlorinated oil fraction to Na in the waste oil may be 0.1 to 0.7, for example, 0.1 to 0.5, and preferably 0.4 or less
  • a weight ratio of Ca in the dechlorinated oil fraction to Ca in the waste oil may be 0.1 to 0.7, for example, 0.1 to 0.6, and preferably 0.5 or less
  • a weight ratio of Al in the dechlorinated oil fraction to Al in the waste oil may be 0.1 to 0.7, for example, 0.1 to 0.5, and preferably 0.4 or less.
  • a N content may be less than 300 ppm, preferably 250 ppm or less or 200 ppm or less, and more preferably 170 ppm or less
  • a S content may be less than 20 ppm, preferably 19 ppm or less or 18 ppm or less, and more preferably 17 ppm or less
  • an O content may be less than 0.2 wt %, preferably 0.15 wt % or less or 0.1 wt % or less, and more preferably less than 0.1 wt %, with respect to the total weight of the dechlorinated oil fraction.
  • a weight ratio of N in the dechlorinated oil fraction to N in the waste oil may be 0.1 to 0.7, for example, 0.1 to 0.6, and preferably 0.5 or less
  • a weight ratio of S in the dechlorinated oil fraction to S in the waste oil may be less than 1, for example, 0.1 to 0.9, and preferably 0.8 or less
  • a weight ratio of 0 in the dechlorinated oil fraction to O in the waste oil may be 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.
  • a waste oil (waste plastic pyrolysis oil) converted by pyrolysis of a plastic waste was recovered and used as a raw material of a Cl removal reaction.
  • the following analysis was performed.
  • GC-Simdis analysis HT-750
  • Analysis for impurities such as Cl, S, N, O, Fe, Ca, Na, Al, Si, and P was performed, and ICP, TNS, EA-O, and XRF analyses were performed for this.
  • GC-MSD analysis was performed for olefin content analysis. Compositions and impurity properties of the pyrolysis oils used as the raw material are shown in the following Tables 1 and 2 and FIG. 3 by the analysis results.
  • the pyrolysis oil used as a raw material had a composition of 18.96 wt % of naphtha, 43.93 wt % of Kero/LGO, and a VGO/AR oil content of 36.50 wt %.
  • TSA is a total specific surface area
  • ZSA is a zeolite specific surface area
  • MSA is a specific surface area of mesopores or larger pores
  • Z/M is a ratio of the zeolite specific surface area (ZSA) to the specific surface area of mesopores or larger pores (MSA)
  • PV is a pore volume
  • APD is an average pore size.
  • the RFCC E-cat used was 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.
  • Example 2-1 The experiment was carried out in the same manner as in Example 2-1, except that zeolite was used as the solid acid material.
  • the treated pyrolysis oil recovered was analyzed for a composition change and an impurity content change, and the results are shown in the following Tables 8 to 10 and FIG. 4 .
  • Example 2-1 The experiment was carried out in the same manner as in Example 2-1, except that clay was used as the solid acid material.
  • the treated pyrolysis oil recovered was analyzed for a composition change and an impurity content change, and the results are shown in Tables 8 to 10 and FIG. 4 .
  • Pyrolysis oil B used as the raw material was waste plastic pyrolysis oil having a CI content level of 67 wppm.
  • the molecular weight distribution and the impurity content were analyzed by the same analysis as Example 1, and the results are shown in the following Tables 11 and 12.
  • the pyrolysis oil was also solid, it was maintained in an oven at 70° C. for 3 hours or more, and then was converted into a liquid phase and used. 120 g of the liquid pyrolysis oil and 12 g of RFCC E-cat were sequentially introduced to an autoclave having a reactor internal volume of 300 cc. The same materials as those used in Example 2-1 of RFCC E-cat used were used.
  • the reactor temperature was maintained at 80° C., autoclave coupling was released, and the weight of the reactor including the mixture of the treated pyrolysis oil and E-cat was measured to calculate a recovery rate.
  • the treated pyrolysis oil and E-cat in the mixture in the reactor were separated by a filter paper.
  • the treated pyrolysis oil recovered was analyzed for a composition change and an impurity content change, and the results are shown in the following Tables 13 to 15 and FIGS. 4 to 10 .
  • the recovery rate was 96.2 to 97.7%, and the loss occurring during the experiment was 2.3 to 2.8% which was very low. It was confirmed that as the reaction temperature was raised, the Cl reduction rate (Cl reduction amount per unit E-cat) was increased, and as the reaction temperature was raised in the experimental temperature range, CI removal performance was improved.
  • A is wt % of components having a boiling point (bp) of 150° C. or higher with respect to the total weight of the raw material (waste oil), and B is wt % of components having bp of 150° C. or higher with respect to the total weight of each oil treated with RFCC E-Cat, Zeolite, and clay.
  • the composition was hardly changed at a reaction temperature of 170 to 240° C., and at 260° C. or higher, an oligomerization phenomenon in which the contents of naphtha and kerosene were slightly decreased and the contents of LGO and VGO were slightly increased was confirmed.
  • high temperature stirring operation was performed at a reaction temperature of 275 to 295° C., product abnormality and yield loss were minimized, and the Cl content to be desired of ⁇ 10 ppm was satisfied.
  • Example 3-1 In order to confirm the Cl reduction characteristics of the solid acid catalyst, the CI reduction tendency over time under the operating conditions at 280° C. in which a difference in composition derived in Example 3-1 was small and the Cl reduction efficiency was high was confirmed.
  • Other reaction variables such as a catalytic amount and a stirring speed and the analysis method were performed under the same conditions as Example 3-1. Further, the analysis results are shown in the following Tables 16 and 17 and FIGS. 8 to 12 .
  • a reaction order of the Cl reduction reaction was calculated by interpreting the Cl reduction performance over a reaction time.
  • a reciprocal (1/C) of the reaction time (t) and the Cl weight was shown, it was confirmed that the Cl reduction rate approximated the second-order reaction rate equation to the reaction time.
  • the slope of the Cl removal amount was rapidly decreased in more or less than 3 hours and the Cl content to be desired of ⁇ 10 ppm was satisfied, it was found that it is most preferred that the stirring operation at a high temperature is performed for 3 hours.
  • N showed a tendency of being removed in proportion to the increase in the catalytic amount introduced.
  • S had the same tendency of being removed in proportion to the increase in the catalytic amount introduced, but the slope of S reduction to the catalytic amount introduced of 10 wt % was very low.
  • metal impurities such as Fe, Na, and Ca may be removed in addition to impurities such as Cl, N, S, and O
  • analysis of metal impurities for the sample recovered under the operating conditions of 280° C. of Example 3-1 in which no composition was changed and Cl reduction efficiency was high was performed.
  • the Results of comparing the contents of metal impurities for the samples recovered under the operating conditions of 280° C. of Example 3-1 with the contents of metal impurities of the raw material sample are shown in Table 22. It was confirmed that 60% or more of Fe, Na, Ca, and Al was all removed at the same time.
  • the raw material/catalyst ratio by position may vary, unless the stirring speed was not maintained to a certain level or higher.
  • the raw material/catalyst non-uniformity as such may decrease the Cl reduction reaction activity, and in order to confirm the Cl reduction efficacy in the phenomenon, a low-speed stirring experiment was carried out.
  • the pyrolysis oil used as the raw material was a pyrolysis oil at a level of a CI content of 67 wppm used in Example 3-1.
  • the waste clay was a clay catalyst discarded after being used for removing an olefin during the petrochemical process.
  • the waste clay catalyst was a catalyst discarded in the petrochemical process, and was used after removing the oil included on the surface and in the inside by drying.
  • the physical properties of the waste clay catalyst are shown in the following Table 27.
  • the Cl reduction performance was superior to that of RFCC E-cat in the conditions of a temperature of 200° C., but in a high temperature/long term treatment, the Cl reduction performance was inferior to that of RFCC E-cat.
  • the oligomerization reactivity was higher than that of RFCC E-cat in the conditions of high temperature/long term treatment, and thus, a LGO/VGO composition increase phenomenon was higher.
  • Pyrolysis oil which was solid at room temperature and an oil having a high CI content of Example 1 was allowed to stand in an oven at 70° C. for 3 hours, and was converted into a liquid phase.
  • the fixed bed reactor was filled with 8.1 g of the same material as RFCC E-cat of Examples 2 and 3, dried by N 2 purge at 280° C., and pressed at 37 bar, and then the pyrolysis oil was supplied using a liquid pump.
  • the diameter of the reactor used was 7 mm, and the filling amount and the feed supply rate were varied depending on the experimental conditions.
  • the sample discharged to the rear end of the reactor with varied space velocity per catalyst was collected and a residual Cl content was measured, and the results are shown in the following Table 29.
  • Example 3 The raw material and the catalyst were the same as the pyrolysis oil and E-cat which were used in Example 3.
  • the experiment was performed under the same operating conditions as the treatment conditions at 280° C. of Example 3-1 having a CI reduction rate of 90% or more, with little change in the composition as compared with the raw material, thereby recovering the oil of Example 6-1.
  • the analysis of the recovered oil was performed in the same manner as in Example 3, and the results are shown in the following Table 31.
  • Example 6-1 The treatment was repeated once again under the same reaction temperature conditions, using the recovered oil of Example 6-1 as the raw material, and the oil of Example 6-2 was recovered.
  • the impurity content and the composition of the recovered oil of Example 6-2 were obtained in the same manner as in Example 3, and the analysis results are shown in the following Table 32.
  • Example 6-2 obtained by retreating and recovering the sample of Example 6-1 had a Cl content of 1 wppm and N and S contents of 19 wppm and 7.8 wppm, respectively, and thus, a very large impurity reduction effect was confirmed.
  • the Cl content acceptable in the most refinery processes is limited to a level of 1 wppm in the raw material for preventing device corrosion, and it was confirmed that the oil of Example 6-2 satisfied the standard of the impurity content.
  • a very low impurity standard process may be also applied as a technology for manufacturing a raw material by the repeated treatment.
  • the impurities may be selectively removed with little change in the composition of the oil, by treating the waste oil with the solid acid material, according to the present invention.
  • the impurities may be extremely decreased with little change in the composition of the oil by repeatedly applying the solid acid material.

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