WO2021246589A1 - Procédé d'élimination du chlore d'une huile usée à haute teneur en chlore à l'aide de substances acides solides - Google Patents

Procédé d'élimination du chlore d'une huile usée à haute teneur en chlore à l'aide de substances acides solides Download PDF

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WO2021246589A1
WO2021246589A1 PCT/KR2020/015788 KR2020015788W WO2021246589A1 WO 2021246589 A1 WO2021246589 A1 WO 2021246589A1 KR 2020015788 W KR2020015788 W KR 2020015788W WO 2021246589 A1 WO2021246589 A1 WO 2021246589A1
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Prior art keywords
chlorine
oil
waste oil
solid acid
reaction
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PCT/KR2020/015788
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English (en)
Korean (ko)
Inventor
김도경
전희중
최재석
김가영
이호원
김태진
추대현
Original Assignee
에스케이이노베이션 주식회사
에스케이종합화학 주식회사
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Priority claimed from KR1020200115425A external-priority patent/KR20210150246A/ko
Application filed by 에스케이이노베이션 주식회사, 에스케이종합화학 주식회사 filed Critical 에스케이이노베이션 주식회사
Priority to CN202080073734.6A priority Critical patent/CN114616308A/zh
Priority to US17/912,773 priority patent/US20230130559A1/en
Priority to EP20938561.6A priority patent/EP4105298A4/fr
Publication of WO2021246589A1 publication Critical patent/WO2021246589A1/fr

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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
    • C10G1/002—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
    • 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
    • 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 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 removed in the form of organic Cl in which olefin and Cl are combined.
  • 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.
  • 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 high chlorine content waste oil provided in step a) may include waste plastic pyrolysis oil, biomass pyrolysis oil, regenerated lubricating oil, high chlorine content crude oil or a combination thereof.
  • the solid acid material of step a) has a Bronsted acid site or a Lewis acid site, zeolite, clay, SAPO (silica-alumina-phosphate), ALPO (aluminum phosphate), MOF (Metal Organic Framework), silica alumina, or a mixture thereof.
  • impurities can be selectively reduced without reducing the molecular weight distribution of the waste oil, and the impurities are sulfur, nitrogen, oxygen, and Na, Ca, Fe, Al in addition to chlorine.
  • the impurities are sulfur, nitrogen, oxygen, and Na, Ca, Fe, Al in addition to chlorine.
  • As may include a metal such as.
  • step b) may implement a method of performing the impurity reduction reaction using a batch reactor, a semi-batch reactor, a continuous stirred tank reactor (CSTR), and a fixed bed reactor.
  • CSTR continuous stirred tank reactor
  • a method of separating through filtering, centrifugation, decanting, or the like may be used.
  • 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.
  • impurities that cause air pollutants such as N and S and metal components that adversely affect the catalyst activity of the refinery process such as Fe, As, Na and Ca can be simultaneously removed.
  • 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
  • 5 to 6 are graphs showing the residual N content and the residual S content by reaction temperature
  • 10 to 11 are graphs showing the residual N content and the residual S content by reaction time
  • 13 is a graph showing an apparent reaction rate equation of a reaction according to an embodiment
  • 16 to 17 are graphs showing the residual N content and the residual S content 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 chlorine-free oil means that it is measured at normal 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) reacting the mixture to remove chlorine; and c) recovering the chlorine-removed fraction by separating the mixture of the chlorine-removed fraction and the solid acid material.
  • 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. 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 is minute can be a ratio (A 2 / A 1) is 1 to 19 parts by weight of (A 2) of bp more than 150 °C ingredient relative to the weight (A 1) of less than 150 bp °C component.
  • the weight ratio A 2 /A 1 of the waste oil component may be 1 to 16, preferably 3 to 15, more preferably 9 to 13.
  • the weight ratio of the component having a bp of 265°C or higher to the component having a bp of 265°C or higher is 1.1 to 2.5, preferably 1.1 to 2.3 or 1.1 to 2.1, more preferably 1.1 to 2.0, 1.1 to 1.8 or 1.1 to 1.7 can be
  • the weight ratio of the C9+ component to the C4 to C8 component in the waste oil may be 1 to 19, for example, 1 to 16, preferably 3 to 15, more preferably 9 to 13.
  • the weight ratio of the C18+ component to the C4 to C17 component in the waste oil may be 1.1 to 2.5, preferably 1.1 to 2.3 or 1.1 to 2.1, more preferably 1.1 to 2.0, 1.1 to 1.8, or 1.1 to 1.7.
  • the waste oil is, with respect to the total weight, of C4 to C7 L-Naph 0.1 to 80% by weight, C6 to C8 H-Naph 0.1 to 80% by weight, C9 to C17 Kero 0.1 to 70% by weight, C18 to C20 It may include 0.1 to 80% by weight of LGO, 0.1 to 80% by weight of VGO of C21 to C25, and 0.1 to 99% by weight of AR of C26+, but the present invention is not limited thereto.
  • 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, specifically, a Bronsted acid or a Lewis acid site.
  • 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. As a result, it is possible to reduce the high Cl content in the waste oil to a level of several ppm and at the same time minimize product abnormalities (eg cracking) and yield loss (when Cl is removed as organic Cl or oil is cracked and removed as gas). have.
  • 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 for converting resid to light/middle distillate.
  • E-Cat Equilibrium Catalyst
  • 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 solid acid material introduced increases within the above range, the Cl removal effect is improved, and when it is 10 wt% or less, cracking reaction in the oil can be suppressed, which is preferable.
  • 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 the reaction by the active site of the 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 easily removed in the form of organic-Cl due to cracking.
  • the Cl removal reaction of the present invention can avoid the above-mentioned problems.
  • 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 200 °C or more and less than 300 °C.
  • 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 200 to 300 ° C, 230 to 300 ° C, 240 to 300 ° C, preferably 250 to 290 ° C, or 255 to 285 ° C, most preferably 260 to 280 ° C.
  • the temperature increases in the above-mentioned temperature range, the Cl reduction effect increases.
  • the conversion catalytic reaction of converting chlorine (Cl) contained in waste oil into hydrochloric acid (HCl) is greatly reduced. Therefore, because of the low Cl reduction performance, it is necessary to increase the catalyst content and reaction temperature/time to compensate for this, which is disadvantageous in terms of economical efficiency, so it is not suitable for treating waste oil containing a high Cl content.
  • the removal rate of N and S may also increase.
  • the removal reaction of 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 fluidized bed reactor can be used to produce a regenerated fraction, but in order to remove Cl from the regenerated fraction, the contact time between the catalyst and the fraction must be long.
  • the efficiency of reducing impurities such as Cl is low compared to an infinite batch reactor.
  • it is possible to increase the impurity reduction efficiency by increasing the reaction temperature there is a problem that a cracking side reaction occurs at high temperature and causes a composition change, and it has disadvantages in that it is relatively disadvantageous to secure economic feasibility due to high investment and operation costs for fluidized bed equipment.
  • 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.
  • LHSV 0.1-10 hr -1 preferably 0.3-5 hr -1 , more preferably 1-3 hr -1 and/or GOR (Gas over Oil ratio) 50-2000, 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.
  • the step of repeating steps a), b), and c) at least once or more may be further performed.
  • the step of repeating steps a), b), and c) at least once or more may be further performed.
  • the strict Cl content (1wppm level) allowed in the subsequent refinery process and by slightly increasing the average molecular weight and/or viscosity of the waste oil composition, abnormal reaction, deterioration of product properties, and product loss are prevented.
  • 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% 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 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 of the oil from which the chlorine has been removed may be less than 10 ppm, specifically, may be 9 ppm or less, 8 ppm or less, or 7 ppm or less.
  • the ratio (B 2 /B 1 ) of the weight (B 2 ) of the component at bp 150° C. or higher to the weight (B 1 ) of the component less than 150° C. (B 2 /B 1 ) may be 1 to 20.
  • the weight ratio B 2 /B 1 of the waste oil component may be 1 to 17, preferably 3 to 16, more preferably 5 to 14.
  • the weight ratio of the component having a bp of 265°C or higher to the component having a bp of 265°C or higher may be 1.8 to 3.0, specifically 1.8 to 2.8, preferably 1.8 to 2.6 or 1.9 to 2.5. .
  • the weight ratio of the C9+ component to the C4 to C8 component in the chlorine-removed fraction may be 1 to 20, for example 1 to 17, preferably 3 to 16, more preferably 5 to 14.
  • the weight ratio of the C18+ component to the C4 to C17 component in the chlorine-removed fraction may be 1.8 to 3.0, for example, 1.8 to 2.8, preferably 1.8 to 2.6 or 1.9 to 2.5. Within the above range, the above-described effects can be further improved.
  • the weight ratio of chlorine of the fraction from which chlorine is removed to chlorine of the waste fraction may be 0.01 to 0.25, for example, 0.01 to 0.20, 0.01 to 0.10, preferably 0.01 to 0.08.
  • 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.
  • 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 component may be 0.1 to 0.7, for example 0.1 to 0.5, preferably 0.4 or less
  • the weight ratio of Ca of the dechlorinated oil to Ca of the waste oil is 0.1 to 0.7, for example 0.1 to 0.6, preferably 0.5 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 (waste 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.
  • the pyrolysis oil used as a raw material had a composition of Naphtha 18.96wt%, Kero/LGO 43.93wt%, and VGO/AR oil content 36.50wt%.
  • the pyrolysis oil which is the high Cl content fraction of Example 1, which is solid at room temperature, was maintained in an oven at 70° C. for 3 hours or more, and converted into a liquid phase.
  • Liquid Example 1 120 g of pyrolysis oil and 4.2 g of RFCC E-cat were sequentially introduced into an autoclave having a reactor internal volume of 300 cc. The physical properties of the RFCC E-cat used were confirmed as shown in Table 3 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 mesopore or more specific surface area
  • Z/M is the ratio of the zeolite specific surface area (ZSA) to the mesopore or more specific surface area (MSA)
  • PV is the pore volume
  • APD is the average pore size.
  • 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. After quantitatively introducing pyrolysis oil and E-cat into the reactor, the reactor was connected, N 2 purge was performed. After stirring at 500rpm under N 2 1bar conditions, the temperature of the reactor was increased to 180°C by increasing the temperature of the reactor at a rate of 1°C/min. After the reaction was maintained for 3 hours, the reaction was terminated.
  • Example 2-1 The experiment was conducted in the same manner as in Example 2-1, except that zeolite was used as a solid acid material.
  • the recovered pyrolysis oil treated oil was analyzed for composition change and impurity content change, and the results are shown in Tables 8 to 10 and FIG. 4 .
  • Example 2-1 The experiment was conducted in the same manner as in Example 2-1, except that Clay was used as the solid acid material.
  • the recovered pyrolysis oil treated oil was analyzed for composition change and impurity content change, and the results are shown in Tables 8 to 10 and FIG. 4 .
  • Table 8 shows the analysis results of samples recovered after Cl reduction treatment using the solid acid materials of Examples 2-1, 2-2, and 2-3.
  • the pyrolysis-induced solid phase was maintained in an oven at 70° C. for 3 hours or more, it 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 into an autoclave having an internal volume of 300 cc. The same materials as those used in Example 2-1 of the RFCC E-cat used were used.
  • the weight was measured.
  • the reactor was connected, and N 2 purge was performed. Thereafter, the temperature of the reactor was raised to the target temperature by stirring at 500 rpm under N 2 1 bar conditions and at a rate of 1° C./min. After maintaining the reaction for 3 hours, it was terminated.
  • the recovery rate was calculated by maintaining the reactor temperature at 80° C., releasing the autoclave bond, and measuring the weight of the reactor containing the pyrolysis oil treated oil and E-cat mixture.
  • the mixture of pyrolysis oil treated oil and E-cat in the reactor was separated through filter paper.
  • the recovered pyrolysis oil treated oil was analyzed for composition change and impurity content change, and the results are shown in Tables 13 to 15 and FIGS. 4 to 10 below.
  • the recovery rate was 96.2 ⁇ 97.7%, and the loss occurred during the experiment was very low at 2.3 ⁇ 2.8%.
  • the Cl reduction rate (the amount of Cl reduction per unit E-cat) increases, and it was confirmed that the Cl removal performance was improved as the reaction temperature increased in the experimental temperature range.
  • A is the wt% of the bp (boiling point) 150 ° C or higher component with respect to the total weight of the raw material (waste oil), and B is the fraction of each oil treated with RFCC E-Cat, Zeolite and Clay It is the wt% of the component at bp 150°C or higher relative to the total weight.
  • 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 280°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 3-1. And the analysis results are shown in Tables 16-17 and FIGS. 8-12 below.
  • the reaction order of the Cl reduction reaction was calculated through the Cl reduction performance analysis according to the reaction time.
  • the reaction time (t) and the reciprocal of Cl weight (1/C) are plotted, it can be confirmed that the Cl reduction rate is close to the second-order reaction rate equation with respect to the reaction time.
  • the slope of the Cl removal amount rapidly decreased within 3 h and the desired Cl content ⁇ 10 ppm was satisfied, so it was most preferable to perform the high-temperature stirring operation for 3 h.
  • N showed a tendency to be removed in proportion to the increase in the amount of catalyst introduced. Even in the case of S, the tendency to be removed in proportion to the increase in the amount of catalyst introduced was the same, but the slope of S reduction up to 10 wt% of the amount of catalyst introduced was very low.
  • Example 3-1 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 280 ° C. of Example 3-1 with no composition change and high Cl reduction efficiency Metal impurity analysis was carried out for Table 22 shows the results of comparing the metal impurity content of the raw material sample to the metal impurity content of the sample recovered under the 280°C operating condition of Example 3-1. It was confirmed that more than 60% of Fe, Na, Ca, and Al were simultaneously removed.
  • N 2 35 bar conditions in the operating conditions derived from Examples 3-1, 3-2, and 3-3, 280° C., 3 hr, E-cat 10wt% operating conditions Cl reduction characteristics were confirmed.
  • Other reaction parameters, such as stirring speed, and the analysis method were carried out under the same conditions as in Example 3-1. The analysis results are shown in Tables 23-24 below.
  • Example 3-5 Review of impact of low-speed agitation treatment
  • the raw material/catalyst ratio may vary by location. Such raw material/catalyst non-uniformity may reduce the Cl reduction reaction activity, and a low-speed stirring experiment was conducted to confirm the Cl reduction effect in this phenomenon.
  • pyrolysis oil having a Cl content of 67wppm level used in Example 3-1 was used as the pyrolysis oil used as a raw material.
  • the spent clay was used for olefin removal during the petrochemical process, and then the discarded clay catalyst was used.
  • the spent clay catalyst is a catalyst discarded from the petrochemical process, and was used after removing the oil contained in the surface and the inside through drying.
  • the physical properties of the spent clay catalyst are shown in Table 27 below.
  • the pyrolysis oil which is the high Cl content fraction of Example 1 in a solid phase at room temperature, was maintained in an oven at 70° C. for 3 hours or more to convert it to a liquid phase.
  • 8.1 g of the same material as the RFCC E-cat of Examples 2 and 3 was filled in a Fixed Bed reactor, dried through a 280° C. N 2 Purge, pressurized to 37 bar, and then the pyrolysis oil was supplied using a liquid pump did
  • the diameter of the reactor used was 7 mm, and the filling amount and feed rate were varied according to the experimental conditions. Samples discharged to the rear end of the reactor were collected at different space velocity per catalyst, and the residual Cl content was measured, and the results are shown in Table 29 below.
  • Example 3-1 No change in composition compared to the raw material, and a Cl reduction rate of 90% or more
  • the experiment was conducted under the same operating conditions as those of Example 3-1 280°C, and the oil fraction of Example 6-1 was recovered. Analysis of the recovered oil was also performed in the same manner as in Example 3, and the results are shown in Table 31 below.
  • Example 3 (280° C. treatment) recovered by treatment under the same operating conditions and the fraction of Example 6-1 were Cl content and S, N, O content, composition All of them confirmed similar results, confirming that there is reproducibility.
  • the same reaction temperature condition was repeated once again, and the fraction of Example 6-2 was recovered.
  • the impurity content and composition of the recovered oil of Example 6-2 was carried out in the same manner as in Example 3, and the analysis results are shown in Table 32 below.
  • Example 6-2 sample recovered by reprocessing the Example 6-1 sample had a Cl content of 1 wppm, N and S content of 19 wppm and 7.8 wppm, respectively, confirming a very large impurity reduction effect. .
  • Most of the Cl content allowed in the refinery process limits the Cl content in the raw material to 1wppm level to prevent device corrosion. It was confirmed that the low impurity standard process can also be applied as a technology for raw material manufacturing.
  • an effect of oligomerization was observed, such as a decrease in the proportion of Naphtha region and a slight increase in the proportion of heavy hydrocarbons such as VGO through reprocessing, but overall there was no significant difference.

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Abstract

La présente invention concerne une technique d'élimination d'au moins 90 % du chlore d'une huile à haute teneur en Cl par réalisation d'un traitement à haute température à l'aide de substances acides solides. L'huile dont le Cl a été éliminé peut être incorporée dans un procédé de raffinage et ainsi convertie en combustible ou en un produit chimique. Selon la présente invention, le chlore peut être éliminé par un traitement thermique à haute température après mélange d'une huile à haute teneur en Cl avec des substances acides solides. Dans le procédé d'élimination de Cl, des impuretés majeures, telles que S, N et O, ainsi que Na, Ca et Fe, qui peuvent agir comme poisons catalytiques dans une réaction catalytique pendant le procédé de raffinage, sont également éliminées en même temps. Dans le procédé d'élimination de Cl de l'huile à haute teneur en Cl grâce aux substances acides solides, des réactions anormales, une détérioration des propriétés du produit et une perte de rendement peuvent être empêchées par augmentation légère du poids moléculaire moyen de la composition d'huile par l'intermédiaire de réactions d'oligomérisation et d'alkylation. Ce procédé est respectueux de l'environnement en ce que les substances acides solides résiduaires (zéolite résiduelle, argile résiduaire, etc.), qui sont rejetées après utilisation dans des procédés pétrochimiques, peuvent être utilisées en tant que substances acides solides pour l'élimination de Cl après avoir été soumises à un traitement simple.
PCT/KR2020/015788 2020-06-03 2020-11-11 Procédé d'élimination du chlore d'une huile usée à haute teneur en chlore à l'aide de substances acides solides WO2021246589A1 (fr)

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CN202080073734.6A CN114616308A (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
US17/912,773 US20230130559A1 (en) 2020-06-03 2020-11-11 Method for Removing Chlorine from High Chlorine Content Waste Oil Using Solid Acid Substances
EP20938561.6A EP4105298A4 (fr) 2020-06-03 2020-11-11 Procédé d'élimination du chlore d'une huile usée à haute teneur en chlore à l'aide de substances acides solides

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WO2023177148A1 (fr) * 2022-03-17 2023-09-21 Sk Innovation Co., Ltd. Procédé et dispositif de production d'huile de pyrolyse de déchets plastiques à teneur en chlore réduite

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JP2019527758A (ja) * 2016-08-01 2019-10-03 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ 混合プラスチックの熱分解と熱分解油の脱塩素と同時に行う触媒プロセス
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WO2023177148A1 (fr) * 2022-03-17 2023-09-21 Sk Innovation Co., Ltd. Procédé et dispositif de production d'huile de pyrolyse de déchets plastiques à teneur en chlore réduite

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