MANUFACTURING METHOD AND MANUFACTURING SYSTEM OF BLENDED HYDROCARBON COMPOSITION

Abstract

Provided are a method for manufacturing a blended hydrocarbon composition including operation S1) applying voltage to a first blended solution in which waste plastic pyrolysis oil, washing water, and a demulsifier are blended to dehydrate the first blended solution; operation S2) hydrotreating a second blended solution in which the first blended solution dehydrated in operation S1) and a sulfur source are blended to produce refined pyrolysis oil from which impurities have been removed; and operation S3) blending the refined pyrolysis oil from which impurities have been removed in operation S2) with a petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition, and a manufacturing system of the blended hydrocarbon composition.

Claims

1. A method for manufacturing a blended hydrocarbon composition, the method comprising: operation S1) applying voltage to a first blended solution in which waste plastic pyrolysis oil, washing water, and a demulsifier are blended to dehydrate the first blended solution; operation S2) hydrotreating a second blended solution in which the first blended solution dehydrated in operation S1) and a sulfur source are blended to produce refined pyrolysis oil from which impurities have been removed; and operation S3) blending the refined pyrolysis oil from which impurities have been removed in operation S2) with a petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition.

2. The method for manufacturing the blended hydrocarbon composition of claim 1, wherein the petroleum-based hydrocarbon includes at least one selected from the group consisting of gasoline, kerosene, aviation fuel, diesel, lube base oil, marine fuel oil, asphalt, and wax.

3. The method for manufacturing the blended hydrocarbon composition of claim 1, further comprising: before operation S1), adding waste plastics to a pyrolysis reactor to manufacture pyrolysis gas; and adding the pyrolysis gas to a hot filter to manufacture the waste plastic pyrolysis oil.

4. The method for manufacturing the blended hydrocarbon composition of claim 3, wherein a liquid condensed in the hot filter is reintroduced to the pyrolysis reactor.

5. The method for manufacturing the blended hydrocarbon composition of claim 3, wherein the hot filter is filled with beads.

6. The method for manufacturing the blended hydrocarbon composition of claim 5, wherein the beads include at least one selected from the group consisting of silica sand (SiO.sub.2) and aluminum oxide (Al.sub.2O.sub.3).

7. The method for manufacturing the blended hydrocarbon composition of claim 3, wherein a temperature gradient is formed in the hot filter.

8. The method for manufacturing the blended hydrocarbon composition of claim 7, wherein the temperature gradient is formed by providing at least two heaters outside the hot filter.

9. The method for manufacturing the blended hydrocarbon composition of claim 1, wherein in operation S1), the waste plastic pyrolysis oil is blended at a larger volume than the washing water.

10. The method for manufacturing the blended hydrocarbon composition of claim 1, wherein the voltage is applied by alternating current or a combination of alternating current and direct current.

11. The method for manufacturing the blended hydrocarbon composition of claim 1, wherein the voltage is applied through a vertical electrode.

12. The method for manufacturing the blended hydrocarbon composition of claim 1, further comprising in operation S1), after applying the voltage, removing a rag layer from the first blended solution.

13. The method for manufacturing the blended hydrocarbon composition of claim 1, wherein operation S1) includes dehydrating the dehydrated first blended solution by moisture coalescence.

14. The method for manufacturing the blended hydrocarbon composition of claim 1, wherein the sulfur source includes one or two or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds.

15. The method for manufacturing the blended hydrocarbon composition of claim 1, further comprising: before operation S3), a distillation process of distilling the refined pyrolysis oil to produce a refined hydrocarbon derived from the refined pyrolysis oil, wherein in operation S3), the refined hydrocarbon is blended with the petroleum-based hydrocarbon to manufacture the blended hydrocarbon composition.

16. A manufacturing system of a blended hydrocarbon composition comprising: a dehydrator which applies voltage to a first blended solution in which waste plastic pyrolysis oil is blended with washing water and a demulsifier to dehydrate the first blended solution; a hydrotreating device which hydrotreats a second blended solution in which the dehydrated first blended solution and a sulfur source are blended to manufacture refined pyrolysis oil from which impurities have been removed; and a blending device which blends the refined pyrolysis oil with a petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition.

17. The manufacturing system of the blended hydrocarbon composition of claim 16, further comprising: a pyrolysis reactor which manufactures pyrolysis gas by adding waste plastics; and a hot filter which manufactures waste plastic pyrolysis oil by adding the pyrolysis gas.

18. The manufacturing system of the blended hydrocarbon composition of claim 17, further comprising: a connection pipe which connects the hot filter and the pyrolysis reactor so that a liquid condensed in the hot filter is reintroduced to the pyrolysis reactor.

19. The manufacturing system of the blended hydrocarbon composition of claim 16, further comprising: a distillation device which distills the refined pyrolysis oil to produce a refined hydrocarbon derived from the refined pyrolysis oil, wherein the blending device blends the refined hydrocarbon with the petroleum-based hydrocarbon to manufacture thee blended hydrocarbon composition.

20. A method for manufacturing a blended hydrocarbon composition, the method comprising: forming a first blended solution including a waste plastic pyrolysis oil, washing water, and a demulsifier; applying voltage to the first blended solution to form a dehydrated first blended solution; adding a sulfur source to the dehydrated first blended solution to form a second blended solution; hydrotreating the second blended solution to produce a refined pyrolysis oil; and blending the refined pyrolysis oil with a petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition, wherein the petroleum-based hydrocarbon includes at least one selected from the group consisting of gasoline, kerosene, aviation fuel, diesel, lube base oil, marine fuel oil, asphalt, and wax.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0038] FIG. 1 is a flow diagram showing a method for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure.

[0039] FIG. 2 is a process diagram for manufacturing waste plastic pyrolysis oil according to an embodiment of the present disclosure.

[0040] FIG. 3 is a simplified schematic of a hot filter according to an embodiment of the present disclosure.

[0041] FIG. 4 is a process diagram for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure.

[0042] FIG. 5 is a process diagram for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure.

CROSS REFERENCE OF MAIN ELEMENTS

[0043] 11: Supply raw material [0044] 12: Supply raw material injection part [0045] 13: Pretreatment reactor [0046] 14: Pyrolysis reactor [0047] 15: Hot filter [0048] 16: Condenser [0049] 17: Heater [0050] 18: Pyrolysis oil recovery part [0051] 19: Connection pipe [0052] 21: Feed tank [0053] 22: Dehydration device [0054] 23: Hydrotreating device [0055] 24-1: First separator [0056] 24-2: Second separator [0057] 24-3: Third separator [0058] 24-4: Fourth separator [0059] 25: Blending device [0060] 26: Distillation device

DETAILED DESCRIPTION

[0061] Advantages and features of the embodiments of the present disclosure and methods of achieving them will become apparent from the following detailed description. However, the embodiments of the present disclosure are not limited to the embodiments disclosed below, but may be implemented in various other forms. The embodiments of the present disclosure are provided so that those with ordinary skill in the art can easily understand the scope of the present disclosure.

[0062] Unless otherwise defined herein, all terms used in the present disclosure (including technical and scientific terms) may have a meaning that is commonly understood by those skilled in the art.

[0063] The singular form of the term used herein may also include a plural form, unless otherwise indicated.

[0064] The numerical range used in the present disclosure includes all values within the range including the lower limit and the upper limit, increments logically derived from the form and breadth of a defined range, all double limited values, and all possible combinations of the upper limit and the lower limit in the numerical range defined in different forms. Unless otherwise defined in the present disclosure, values which may be outside a numerical range due to experimental error or rounding off of a value are also included in the defined numerical range.

[0065] The term comprise mentioned in the present disclosure is an open-ended description having a meaning equivalent to the term such as is/are provided, contain, have, or is/are characterized, and does not exclude elements, materials, or processes which are not further listed.

[0066] The term reactor used in the present disclosure may refer to an instrument which may be used in processes such as production, refinement, separation, and blending of waste plastic pyrolysis oil. For example, the reactor may be interpreted as referring to an instrument such as a dehydrator, a coalescer, a hydrotreating reactor, and a separator, which are used in the refining process of waste plastic pyrolysis oil.

[0067] In the present disclosure, a pyrolysis oil yield refers to a weight ratio of an oil fraction to the total weight of oil fraction, water-based by-product, pyrolysis char, and by-product gas.

[0068] The term vertical electrode used in the present disclosure may refer to an electrode standing vertically on the ground, and the term horizontal electrode may refer to an electrode laying horizontally on the ground.

[0069] The term gasoline used in the present disclosure may refer to a composition containing a C.sub.5-C.sub.12 hydrocarbon, unless otherwise stated. In an embodiment, the gasoline may refer to a composition which contains a C.sub.5-C.sub.12 hydrocarbon and meets the ASTM standard D439.

[0070] The term kerosene used in the present disclosure may refer to a composition meeting the ASTM standard D3699.

[0071] The term aviation fuel used in the present disclosure may refer to a composition meeting the ASTM standard D1655 or D910.

[0072] The term diesel used in the present disclosure may refer to a middle distillate fuel containing a C.sub.10-C.sub.25 hydrocarbon. In an embodiment, the diesel may refer to a composition which contains a C.sub.10-C.sub.25 hydrocarbon and meets ASTM standard D975 or D396.

[0073] The term marine fuel oil used in the present disclosure may refer to a composition meeting ASTM D396 or D2069.

[0074] The term olefin used in the present disclosure may refer to a compound having a structure of a double bond between carbons (C). For example, olefin may refer to at least one selected from the group consisting of ethylene, propylene and butylene, but is not limited thereto.

[0075] The manufacturing method and the manufacturing system of a blended hydrocarbon composition according to the present disclosure may include a dehydration operation going through water washing, demulsifying, voltage application, and the like, in order to decrease problems such as catalyst deactivation by moisture dispersed in an emulsion form in a waste plastic pyrolysis oil and corrosion of a reactor by chlorine included in moisture and low pH of moisture. In addition, the embodiments include a hydrotreating operation capable of minimizing production of an ammonium salt which causes various problems in the process of refining waste plastic pyrolysis oil and the manufacturing process of the blended hydrocarbon composition including refined pyrolysis oil. The method for manufacturing a blended hydrocarbon composition according to the present disclosure may stably produce a high-quality blended hydrocarbon composition, since the series of operations are organically combined.

[0076] Hereinafter, the manufacturing method and the manufacturing system of a blended hydrocarbon composition will be described in detail. However, it is only illustrative, and the present disclosure is not limited to the specific embodiments which are illustratively described in the present disclosure.

[0077] Referring to FIG. 1, the present disclosure provides a method for manufacturing a blended hydrocarbon composition including operation S1) applying voltage to a first blended solution in which waste plastic pyrolysis oil, washing water, and a demulsifier are blended to dehydrate the first blended solution; operation S2) hydrotreating a second blended solution in which the first blended solution dehydrated in operation S1) and a sulfur source are blended to produce refined pyrolysis oil from which impurities have been removed; and operation S3) blending the refined pyrolysis oil from which impurities have been removed in operation S2) with a petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition.

[0078] First, operation S1) is an operation applying voltage to a first blended solution in which waste plastic pyrolysis oil, washing water, and a demulsifier are blended, and dehydrating the first blended solution.

[0079] The waste plastic pyrolysis oil includes moisture and may cause problems such as deactivation of a hydrotreating catalyst and corrosion of a reactor due to the moisture in the pyrolysis oil, and since the moisture includes water-soluble impurities, the moisture needs to be removed. The moisture present in an emulsion form in the waste plastic pyrolysis oil may be easily removed by going through operation S1).

[0080] The waste plastic pyrolysis oil according to an embodiment of the present disclosure may be a hydrocarbon oil fraction blend produced by pyrolyzing waste plastics, and the waste plastics may include solid or liquid wastes related to synthetic polymer compounds such as waste synthetic resin, waste synthetic fiber, waste synthetic rubber, and waste vinyl.

[0081] The hydrocarbon oil fraction blend according to an embodiment of the present disclosure may include impurities such as a chlorine compound, a nitrogen compound, an oxygen compound, a metal compound, and char-derived particles, in addition to the hydrocarbon oil fraction, may include impurities in the form a compound to which chlorine, nitrogen, oxygen, or metal is bonded in the hydrocarbon, and may include hydrocarbons in the form of paraffin, olefin, naphthene, or aromatics.

[0082] The washing water according to an embodiment of the present disclosure may serve to increase a probability of contact between moistures in the form of emulsion present in the waste plastic pyrolysis oil. In addition, a basic compound may be added to the washing water to remove a water-soluble acidic material included in moisture, and the basic compound may be sodium hydroxide (NaOH), but is not particularly limited thereto. The waste plastic pyrolysis oil according to an embodiment may be blended in a larger volume than the washing water, and specifically, the first blended solution may be blended at a volume ratio of 1:0.001 to 0.5, more specifically 1:0.005 to 0.4, and most specifically 1:0.01 to 0.3 between the waste plastic pyrolysis oil and the washing water. When the range is satisfied, washing is sufficiently performed to significantly decrease impurities in the pyrolysis oil, and the cost of removing the washing water may be minimized.

[0083] The demulsifier according to an embodiment of the present disclosure may be one or a mixture of two or more selected from the group consisting of polyethylene glycol, tert-butanol, acetone, alkyl naphthalene sulfonate, alkylbenzene sulfonate, non-ionic alkoxylated alkyl phenol resin, polyalkylene oxide, and polyoxyethylene sorbitan ester, but is not limited thereto.

[0084] The first blended solution according to an embodiment of the present disclosure may be a blend in which the waste plastic pyrolysis oil and the demulsifier are blended in a volume ratio of 1:0.000001 to 0.001, specifically 1:0.000002 to 0.0005, and more specifically 1:0.000003 to 0.0001. When the range is satisfied, an emulsion may be decomposed while minimizing the impact on quality of the pyrolysis oil.

[0085] The demulsifier according to an embodiment of the present disclosure may have a weight average molecular weight in a range of 200 to 2,000, specifically 300 to 1,000, and more specifically 400 to 800. When the range is satisfied, blending of the waste plastic pyrolysis oil and the washing water is easily performed under the conditions in which a dehydration process is carried out, and the decomposition efficiency of moisture emulsion may be increased.

[0086] Since the moisture in the form of emulsion included in the first blended solution in which the waste plastic pyrolysis oil, the washing water, and the demulsifier are blended is stable, it is still difficult to remove it. Therefore, application of voltage to the first blended solution may make it easy to remove moisture.

[0087] The voltage according to an embodiment of the present disclosure may be applied by an alternating current or a combination of an alternating current and a direct current. Some impurity particles included in the waste plastic pyrolysis oil exhibits polarity, and when direct current voltage is applied, polar impurity particles accumulate in a specific electrode, and when the process proceeds for a long time, fixation of impurities on the electrode may occur. However, when alternating current voltage is applied, polarity of the electrode changes periodically, and thus, fixation of impurity particles may be prevented. In addition, the frequency of the alternating current according to an embodiment of the present disclosure may be a single frequency or a combination of two or more frequencies, and as a specific embodiment, in the case of a single frequency, an alternating current of a frequency of 60 Hz may be applied, and in the case of a combination of two or more frequencies, an alternating current of frequencies of 50 Hz and 60 Hz may be alternately applied, but the embodiments are not limited thereto.

[0088] The voltage according to an embodiment of the present disclosure may be applied through a vertical electrode. When impurity particles accumulate on an electrode in the method for manufacturing the blended solution or in the voltage application process, unless the impurity particles are artificially washed, they may be fixed on the electrode after a long period of time. However, when the vertical electrode is used, even in the case of not performing a separate washing operation, the impurity particles fall to the bottom of the reactor by gravity without accumulating on the electrode, and thus, fixation of the impurity particles may be prevented in advance.

[0089] The size of the voltage according to an embodiment of the present disclosure may be 0.1 to 50 kV, specifically 1 to 30 kV, and more specifically 5 to 20 kV, but is not limited thereto.

[0090] The dehydration according to an embodiment of the present disclosure may be performed by any method known in the art. As a non-limiting example, water may be removed by pouring a water layer separated from oil-water after voltage application. Water may also be removed in a gas-liquid separator.

[0091] Metal impurities in the waste plastic pyrolysis oil stabilize an emulsion to prevent oil-water separation and help formation of a stable emulsion layer which is referred to as a rag layer. The rag layer may be formed between a desalted oil layer in the upper portion and a water layer in the lower portion of the first blended solution and may be gradually thickened in a continuous dehydration process. An excessively thickened rag layer may be discharged to a hydrotreatment stage facility with a desalted oil. This reduces a desalination effect of the desalted oil to reduce process efficiency. In addition, the rag layer discharged together with water causes a problem in the waste water treatment process. Therefore, it is preferred to remove the rag layer formed between the desalted oil layer and the water layer.

[0092] Thus, the method for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure may further include after applying voltage in operation S1), removing a rag layer from the first blended solution. The removal of the rag layer may be performed through a pipe which penetrates the wall surface of a dehydrator and is connected to the outside, after grasping the formed position and thickness of the rag layer by measuring a density change of the blended solution through a density meter in the dehydrator, but the embodiment is not necessarily limited thereto.

[0093] Operation S1) according to an embodiment of the present disclosure may be dehydrating the first blended solution and then further dehydrating the dehydrated first blended solution by moisture coalescence.

[0094] The additional dehydration according to an embodiment of the present disclosure may be performed by supplying the dehydrated first blended solution to a coalescer. Specifically, a residual amount of moisture included in the dehydrated first blended solution may be coalesced by a capture filter in the coalescer and removed, but this is only a specific embodiment, and the embodiments of the present disclosure are not necessarily limited thereto. Since the moisture content in the waste plastic pyrolysis oil is further decreased by the additional dehydration, deactivation of a catalyst by moisture is prevented, and process stability and quality of the blended hydrocarbon composition may be improved.

[0095] A ratio between the moisture content of the waste plastic pyrolysis oil and the moisture content of the dehydrated first blended solution according to an embodiment of the present disclosure may be 1:0.0001 to 0.9, specifically 1:0.0005 to 0.5, and more specifically 1:0.001 to 0.1. When the range is satisfied, the risk of trouble occurring is significantly decreased in the subsequent processes including the hydrotreatment, and high-quality refined pyrolysis oil at a level which satisfies the standard as the raw material of a distillation process described later may be produced, but the embodiments are is not necessarily limited thereto.

[0096] Operation S1) according to an embodiment of the present disclosure may be performed at a pressure of 50 bar or less. When it is performed at a pressure of 50 bar or less, moisture removal in the pyrolysis oil is easily performed, and process stability may be secured. Specifically, it may be performed at a pressure of 30 bar or less, more specifically 20 bar or less, and unlimitedly, 5 bar or more.

[0097] Operation S1) according to an embodiment of the present disclosure may be performed at a temperature of 20 C. to 300 C. When the range is satisfied, emulsion decomposition and moisture coalescence occur easily to improve dehydration efficiency. It may be performed at a temperature of specifically 50 C. to 250 C., more specifically 80 C. to 200 C. In operation S1) according to an embodiment of the present disclosure, one or more additional processes selected from the group consisting of centrifugation and distillation before dehydration, after dehydration, or both before and after dehydration may be performed improve dehydration efficiency. The additional process described above may be performed by a method known in the art, but the embodiments is not particularly limited thereto.

[0098] Next, operation S2) is an operation treating a second blended solution in which the first blended solution dehydrated in S1 and a sulfur source are blended to produce refined pyrolysis oil from which impurities have been removed.

[0099] The second blended solution according to an embodiment of the present disclosure may have a chlorine (Cl) concentration of 10 ppm or more, specifically 100 ppm or more, and more specifically 200 ppm or more and as the upper limit, unlimitedly 3000 ppm or less, but is not limited thereto.

[0100] The second blended solution according to an embodiment of the present disclosure may have a weight ratio of nitrogen to chlorine of 1:0.1 to 10, specifically 1:0.5 to 5, and more specifically 1:1 to 2, but the weight ratio is only a specific embodiment which may be included in the waste plastic pyrolysis oil, and the composition of the waste plastic pyrolysis oil is not limited thereto.

[0101] The hydrotreatment according to an embodiment of the present disclosure may be performed under the conditions of a ratio of hydrogen to the second blended solution of 100 Nm.sup.3/Sm.sup.3 to 5000 Nm.sup.3/Sm.sup.3, specifically 500 Nm.sup.3/Sm.sup.3 to 3000 Nm.sup.3/Sm.sup.3, and more specifically 1000 Nm.sup.3/Sm.sup.3 to 1500 Nm.sup.3/Sm.sup.3. When the range is satisfied, impurities may be effectively removed, the high activity of the hydrotreating catalyst may be maintained, and process efficiency may be improved.

[0102] The sulfur source refers to a sulfur source which may continuously supply a sulfur component during a refining process.

[0103] Operation S2) may suppress deactivation of a molybdenum-based hydrogenation catalyst due to lack of the sulfur source and operation at a high temperature in the catalytic activity, by refining process and maintain manufacturing the second blended solution including the sulfur source.

[0104] The sulfur source according to an embodiment of the present disclosure may include a sulfur-containing oil fraction. The sulfur-containing oil fraction refers to an oil fraction formed of a hydrocarbon containing sulfur obtained using crude oil as a raw material. The sulfur-containing oil fraction is not particularly limited as long as it is an oil fraction containing sulfur, and may be, for example, light gas oil, straight-run naphtha, decompression naphtha, pyrolysis naphtha, straight-run kerosene, decompression kerosene, pyrolysis straight-run diesel, decompression diesel, pyrolysis diesel, a sulfur-containing waste tire oil fraction, and the like, or any mixture thereof.

[0105] Since the waste tire oil fraction is included as the sulfur-containing oil fraction according to an embodiment of the present disclosure, a high content of sulfur included in waste tire is converted into an oil fraction with hydrocarbon and may preferably act as the sulfur source of the waste plastic pyrolysis oil. In addition, it is favorable to divert the waste tire oil fraction to the sulfur source of the waste plastic pyrolysis oil, in terms of a decrease in an environmental load due to waste tire recycling and the long-term maintenance of the catalytic activity.

[0106] Specifically, the sulfur-containing oil fraction may be a light gas oil (LGO) having a specific gravity of 0.7 to 1. When used, the sulfur-containing oil fraction may be uniformly blended with the dehydrated first blended solution and has high hydrotreating efficiency. Specifically, the specific gravity may be 0.75 to 0.95, and more specifically, 0.8 to 0.9. The sulfur-containing oil fraction may include 100 ppm or more of sulfur. When the sulfur component is included at 100 ppm or less, the content of the sulfur component supplied is small, so that the effect of preventing the deactivation of the molybdenum-based hydrogenation catalyst may be insignificant. Specifically, the sulfur component may be included at 800 ppm or more, more specifically 8,000 or more, and unlimitedly 200,000 ppm or less.

[0107] The second blended solution according to an embodiment of the present disclosure may include 100 ppm or more of sulfur. As in the case of the sulfur-containing oil fraction, when the sulfur component in the second blended solution is included at 100 ppm or less, the content of the sulfur component supplied is small, so that the effect of preventing the deactivation of the molybdenum-based hydrogenation catalyst may be insignificant. Specifically, the sulfur component may be included at 800 ppm or more or more, more specifically 8,000 ppm or more or more, and unlimitedly 200,000 wt % or less.

[0108] The sulfur-containing oil fraction according to an embodiment of the present disclosure may be included at less than 0.5 parts by weight based on 100 parts by weight of the dehydrated first blended solution in operation S1). Specifically, the sulfur-containing oil fraction may be included at less than 0.1 parts by weight, more specifically less than 0.05 parts by weight, and unlimitedly, at more than 0.01 parts by weight. Since the sulfur-containing oil fraction is included at less than 0.5 parts by weight, the concentration of chlorine (Cl) or nitrogen (N) included in the waste plastic pyrolysis oil may be lowered to control the production rate of an ammonium salt (NH.sub.4Cl) and process stability may be improved.

[0109] The sulfur source according to an embodiment of the present disclosure may include one or two or more sulfur-containing organic compounds selected from disulfide-based compounds, sulfide-based compounds, sulfonate-based compounds, and sulfate-based compounds. Specifically, the sulfur source may include one or a mixture of two or more selected from dimethyl disulfide, dimethyl sulfide, polysulfide, dimethyl sulfoxide (DMSO), methyl methanesulfonate, ethyl methanesulfonate, propylsulfonate, propenyl propenesulfonate, propenyl cyanoethansulfonate, ethylene sulfate, bicycloglyoxal sulfate, and methyl sulfate, which are only presented as an example, and the present disclosure is not limited thereto.

[0110] The sulfur-containing organic compound according to an embodiment of the present disclosure may be included at 0.01 to 0.1 parts by weight based on 100 parts by weight of the dehydrated first blended solution in operation S1). Specifically, it may be included at 0.02 to 0.08 parts by weight, and more specifically, 0.03 to 0.06 parts by weight. When it is included at less than 0.01 part by weight, the content of the sulfur component supplied is small, so that the effect of preventing the deactivation of the molybdenum-based hydrogenation catalyst may be insignificant.

[0111] The hydrotreatment may refer to a hydrogenation reaction occurring by adding a reaction gas including hydrogen gas (H.sub.2) to the second blended solution in which the first blended solution dehydrated in operation S1) and the sulfur source are blended in the presence of the molybdenum-based hydrogenation catalyst. Specifically, the hydrotreatment may refer to a conventionally known hydrotreatment including a hydrodesulfurization reaction, a hydrocracking reaction, a hydrodechlorination reaction, a hydrodenitrification reaction, a hydrodeoxygenation reaction, and a hydrodemetallation reaction. Impurities including chlorine (Cl), nitrogen (N), and oxygen (O) and some olefins are removed and other metal impurities may be removed by the hydrotreatment, and by-products including the impurities are produced.

[0112] The by-products are produced by a reaction between chlorine (Cl), nitrogen (N), sulfur(S), or oxygen (O) which is an impurity included in the waste plastic pyrolysis oil and hydrogen gas (H.sub.2), and specifically, may include hydrogen sulfide gas (H.sub.2S), hydrogen chloride (HCl), ammonia (NH.sub.3), water vapor (H.sub.2O), and the like, and additionally, may include unreacted hydrogen gas (H.sub.2), a trace amount of methane (CH.sub.4), ethane (C.sub.2H.sub.5), propane (C.sub.3H.sub.8), butane (C.sub.4H.sub.10), or the like.

[0113] The molybdenum-based hydrogenation catalyst according to an embodiment of the present disclosure may be a catalyst in which a molybdenum-based metal, or a metal including one or two or more selected from nickel, cobalt, and tungsten and a molybdenum-based metal are supported on a support. The molybdenum-based hydrogenation catalyst has high catalytic activity in the hydrotreating and may be used alone or in the form of a binary catalyst combined with a metal such as nickel, cobalt, and tungsten, if necessary.

[0114] As the support according to an embodiment of the present disclosure, alumina, silica, silica-alumina, titanium oxide, a molecular sieve, zirconia, aluminum phosphate, carbon, niobia, or a mixture thereof may be used, but is not limited thereto.

[0115] The molybdenum-based hydrogenation catalyst according to an embodiment of the present disclosure may include a molybdenum-based sulfide hydrogenation catalyst. For example, it may include molybdenum sulfide (MOS) or molybdenum disulfide (MOS.sub.2), but is not limited thereto, and may include a known molybdenum-based sulfide hydrogenation catalyst.

[0116] The reaction gas according to an embodiment of the present disclosure may further include hydrogen sulfide gas (H.sub.2S). The hydrogen sulfide gas (H.sub.2S) included in the reaction gas may act as a sulfur source and regenerate the activity of the molybdenum-based hydrogenation catalyst which is deactivated in the refining process with the sulfur source blended with the waste plastic pyrolysis oil.

[0117] The hydrotreatment according to an embodiment may be performed at a pressure of 150 bar or less. Specifically, it may be performed at a pressure of 120 bar or less, more specifically 100 bar or less, and unlimitedly, 50 bar or more. When the hydrotreatment is performed under the pressure conditions or more than 150 bar, ammonia and hydrogen chloride are produced in an excessive amount during hydrotreatment, and thus, an ammonium salt formation temperature rises to easily cause differential pressure in the process such as a reactor and significantly reduce process stability. The rise in the ammonium salt formation temperature may be partly suppressed even under the pressure conditions of more than 150 bar by adjusting the contents of nitrogen and chlorine in the waste plastic pyrolysis oil, but in this case, the waste plastic pyrolysis oil subjected to the refining process according to the present disclosure may be extremely limited, which is inappropriate.

[0118] The hydrotreatment according to an embodiment of the present disclosure may be performed at a temperature of 150 C. to 500 C. When the range is satisfied, hydrotreating efficiency may be improved. Specifically, it may be performed at a temperature of 200 C. to 400 C.

[0119] The hydrotreatment according to an embodiment of the present disclosure may be performed in multiple step operations (or multiple operations), and as a specific embodiment, may be performed in two operations. When the hydrotreatment is performed in two-step operation, the first step operation (or the first operation) may be performed at a lower temperature than the second operation. Herein, the first operation may be performed at 150 C. to 300 C., specifically 200 C. to 250 C., and the second step operation (or the second operation) may be performed at 300 C. to 500 C., specifically 350 C. to 400 C., but is not limited thereto.

[0120] The refining method of waste plastic pyrolysis oil according to an embodiment of the present disclosure may further include performing gas-liquid separation of a stream including refined pyrolysis oil from which the impurities have been removed and washing.

[0121] The stream including the refined pyrolysis oil from which the impurities have been removed according to an embodiment of the present disclosure may include hydrogen chloride, ammonia, and unreacted hydrogen gas, and the like, including the refined pyrolysis oil from which the impurities have been removed, discharged from the subsequent stage of the reactor in which operation S2) is performed.

[0122] The refined pyrolysis oil preferably has a chlorine content of less than about 50 ppm, less than about 20 ppm, less than about 10 ppm, less than about 5 ppm, or less than about 1 ppm.

[0123] Ammonia and hydrogen chloride produced by the hydrotreatment are removed from a stream including the refined pyrolysis oil from which impurities have been removed by the gas-liquid separation, and unreacted hydrogen gas may be recovered.

[0124] The gas-liquid separation according to an embodiment of the present disclosure may be performed by a method known in the art through a separator and is not particularly limited.

[0125] The gas-liquid separation according to an embodiment of the present disclosure may be performed 2 to 4 times, specifically 3 or 4 times, and more specifically 4 times. When the range is satisfied, since the refined pyrolysis oil contains a trace amount of NH.sub.3 and HCl, production of the ammonium salt may be minimized even in low temperature conditions for oil-water separation. In addition, an oil refining process using refined pyrolysis oil as a raw material may be stably performed without adding a separate salt remover to the refined pyrolysis oil later.

[0126] The gas stream produced as a result of the gas-liquid separation according to an embodiment of the present disclosure may include off-gas including light hydrocarbon, hydrogen sulfide, ammonia, hydrogen chloride, or the like, and unreacted hydrogen gas. The off-gas and the unreacted hydrogen gas are separated according to the method known in the art, the unreacted hydrogen gas may be recirculated in the process, and the off-gas may be treated through the operation described later and may be used as a fuel and discharged into the atmosphere.

[0127] The salt included in the gas stream may be removed by being dissolved by the washing according to an embodiment of the present disclosure, or salt formation may be suppressed by dissolving gas capable of forming a salt. The washing may be performed by a method known in the art and is not particularly limited.

[0128] The washing according to an embodiment of the present disclosure may be performed 2 to 4 times, specifically 2 or 3 times. When the range is satisfied, the effect of salt removal and salt formation suppression may be sufficiently exhibited to obtain high-quality refined pyrolysis oil, and process stability may be secured.

[0129] The method for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure may further include after performing gas-liquid separation of the stream including the refined pyrolysis oil from which the impurities have been removed and then washing the stream, burning the separated off-gas; and treating unburned off-gas.

[0130] The off-gas according to an embodiment of the present disclosure may include C.sub.1-C.sub.4 light hydrocarbon, hydrogen sulfide (H.sub.2S), ammonia (NH.sub.3), and the like. Therefore, to use the off-gas as a fuel, the off-gas needs to be burned to remove hydrogen sulfide (H.sub.2S), ammonia (NH.sub.3), and the like. Exhaust gas including sulfur dioxide (SO.sub.2), nitrogen dioxide (NO.sub.2), and the like may be subjected to caustic scrubbing to meet emission standards, and then discharged to the atmosphere.

[0131] In addition, unburned gas after the operation of burning the off-gas may be subjected to sour water stripping, adsorption, biological treatment, oxidation, amine scrubbing, or caustic scrubbing and be discharged as waste water.

[0132] Next, operation S3) is an operation blending the refined pyrolysis oil from which impurities have been removed in operation S2) with a petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition.

[0133] The petroleum-based hydrocarbon is a general term for a mixture of naturally occurring hydrocarbons, a compound separated from the mixture, or a refined petroleum product, and as a specific example, may include at least one selected from the group consisting of Kuwait (KWT) crude oil, Arabian heavy (ARH), Arabian medium (ARM), and Arabian light (ARL) crude oils, gasoline, kerosene, aviation fuel, diesel, lube base oil, marine fuel oil, asphalt, and wax, but is not limited thereto. More specifically, the petroleum-based hydrocarbon may include at least one selected from the group consisting of gasoline, kerosene, aviation fuel, diesel, lube base oil, marine fuel oil, asphalt, and wax.

[0134] In an embodiment according to the present disclosure, the refined pyrolysis oil and the petroleum-based hydrocarbon may be blended at a blending ratio of 0.00001:1 to 2:1, 0.00001:1 to 1:1, 0.00001:1 to 0.5:1, 0.00001:1 to 0.3:1, 0.0001:1 to 0.1:1, or 0.001:1 to 0.1:1.

[0135] In an embodiment according to the present disclosure, the refined oil and pyrolysis the petroleum-based hydrocarbon may be blended by a common blending method, and specifically, may be blended by a blender, but is not limited thereto.

[0136] The blended hydrocarbon composition according to an embodiment of the present disclosure may include 5 wt % or more, 10 wt % or more, 20 wt % or more, 40 wt % or more, or 50 wt % or more and as the upper limit, 95 wt % or less of the refined pyrolysis oil from which impurities have been removed in operation S2) with respect to the total weight of the blended hydrocarbon composition. Though the embodiments of the present disclosure are not necessarily limited to the above range, generally, as the content of impurities in the refined pyrolysis oil is lower, the refined pyrolysis oil may be included in the blended hydrocarbon composition at a higher ratio.

[0137] In an embodiment according to the present disclosure, the method for manufacturing a blended hydrocarbon composition may further include before operation S1), adding waste plastics to a pyrolysis reactor to manufacture pyrolysis gas; and adding the pyrolysis gas to a hot filter to manufacture waste plastic pyrolysis oil.

[0138] Thus, the method for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure may manufacture high value-added waste plastic pyrolysis oil having a high light hydrocarbon ratio from waste plastics having a large amount of impurities, and a blended hydrocarbon composition having a high light hydrocarbon ratio may be obtained therefrom. In addition, the yield of the obtained waste plastic pyrolysis oil may be significantly improved.

[0139] In addition, the method for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure may manufacture high value-added waste plastic pyrolysis oil from waste plastics including a large amount of impurities, and a blended hydrocarbon composition having decreased impurities may be obtained therefrom.

[0140] The method for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure may improve cracking of medium hydrocarbons among pyrolysis oils, by reintroducing the liquid condensed in the hot filter 15 to the pyrolysis reactor 14. Therefore, waste plastic pyrolysis oil having a high light hydrocarbon ratio may be manufactured, and a blended hydrocarbon composition having a high light hydrocarbon ratio may be obtained therefrom.

[0141] According to an embodiment of the present disclosure, the hot filter may be filled with at least one selected from beads and neutralizers.

[0142] According to another embodiment of the present disclosure, the hot filter may be filled with beads. When the hot filter is filled with beads, the inert effect and the heat transfer effect in the hot filter may be maximized to manufacture pyrolysis oil having a high light hydrocarbon ratio. In addition, the yield of pyrolysis oil may be improved.

[0143] According to an embodiment of the present disclosure, the hot filter may be filled with 50 vol % or more, 60 vol % or more, 70 vol % or more, 80 vol % or more, 85 vol % or more, 90 vol % or more and 95 vol % or less, 93 vol % or less, 91 vol % or less, 90 vol % or less, 89 vol % or less, 87 vol % or less, 85 vol % or less, or 80 vol % or less of the beads, or the beads at a value between the numerical values by the internal volume of the hot filter. Specifically, the hot filter may be filled with beads occupying 70-95 vol %, 80-90 vol %, or 85-90 vol % of its internal volume. However, these ranges are illustrative and not limiting.

[0144] In an embodiment according to the present disclosure, the beads may include at least one selected from the group consisting of silica sand (SiO.sub.2) and aluminum oxide (Al.sub.2O.sub.3). Specifically, when the beads include silica sand (SiO.sub.2), the inert effect and heat transfer effect in the hot filter are maximized, and a stable process operation may be performed without wear even during long-term high-temperature operation.

[0145] According to an embodiment of the present disclosure, the beads may be glass beads, but are not limited thereto.

[0146] According to an embodiment of the present disclosure, the diameter of the beads may be 0.1 mm or more, 1 mm or more, 1.5 mm or more, 2 mm or more, 2.5 mm or more, 3 mm or more and 10 mm or less, 8 mm or less, 6 mm or less, 4 mm or less, 3.5 mm or less, 3 mm or less, 2.5 mm or less, 2 mm or less, or a value between the numerical values, and specifically, may be 1 mm to 5 mm, 2 mm to 4 mm, or 2.5 mm to 3.5 mm, but is not limited thereto. In the operation of manufacturing waste plastic pyrolysis oil of the present disclosure by filling the hot filter with the beads having the particle size, the residence time of pyrolysis gas (gas hourly space velocity, GHSV) may be adjusted to achieve lightening of an oil fraction, and also differential pressure occurrence of the hot filter may be suppressed to improve process operation efficiency.

[0147] According to an embodiment of the present disclosure, in the operation of manufacturing waste plastic pyrolysis oil, the pyrolysis gas may be added to the hot filter filled with the neutralizer to manufacture pyrolysis oil.

[0148] According to an embodiment of the present disclosure, a temperature gradient may be formed in the hot filter. When the temperature gradient is formed in the hot filter, pyrolysis gas moving to the upper stage in the hot filter and a liquid condensed to the lower stage may be efficiently circulated to manufacture pyrolysis oil having a high light hydrocarbon ratio. In addition, the blended hydrocarbon composition having a high light hydrocarbon ratio may be manufactured therefrom. Also, the yield of the pyrolysis oil may be improved.

[0149] According to an embodiment of the present disclosure, the temperature gradient may refer to the temperature in the lower stage of the hot filter being higher than the temperature in the upper stage of the hot filter. According to an embodiment of the present disclosure, the temperature gradient may refer to the temperature in the lower stage of the hot filter being higher than the temperature in the middle stage of the hot filter and the temperature of the middle stage of the hot filter being higher than the temperature of the upper stage of the hot filter. Thus, circulation efficiency and heat transfer efficiency in the hot filter may be improved.

[0150] Referring to FIG. 3, according to an embodiment of the present disclosure, the temperature gradient may be formed by providing at least 2 heaters 17 outside the hot filter 15. According to another embodiment of the present disclosure, the temperature gradient may be formed by providing at least 3 heaters outside the hot filter. When at least 2 heaters are provided outside the hot filter, temperature gradient formation in the hot filter is more easily obtained, and the temperatures in the upper stage, middle stage, and lower stage may be flexibly adjusted depending on the operation situation of the hot filter, and thus, flexible process operation is allowed. For example, the temperature gradient of the hot filter may be formed by independently adjusting the temperatures in the upper stage, middle stage, and lower stage provided with the heaters in each of the upper stage, middle stage, and lower stage of the hot filter.

[0151] According to an embodiment of the present disclosure, the temperature in the lower stage of the hot filter may be 400 C. or higher, 420 C. or higher, 440 C. or higher, 460 C. or higher, 480 C. or higher, 500 C. or higher, 550 C. or higher, 600 C. or higher and 700 C. or lower, 600 C. or lower, 550 C. or lower, 530 C. or lower, 510 C. or lower, or a value between the numerical values.

[0152] According to an embodiment of the present disclosure, the temperature in the upper stage of the hot filter may be 400 C. or higher, 420 C. or higher, 440 C. or higher, 460 C. or higher, 480 C. or higher, 500 C. or higher and 600 C. or lower, 550 C. or lower, 500 C. or lower, 480 C. or lower, 460 C. or lower, 440 C. or lower, 420 C. or lower, or 400 C. or lower.

[0153] According to an embodiment of the present disclosure, the temperature in the middle stage of the hot filter may be 300 C. or higher and 600 C. or lower, 400 C. or higher and 600 C. or lower, 400 C. or higher and 500 C. or lower, 420 C. or higher and 480 C. or lower, or 440 C. or higher and 460 C. or lower.

[0154] In an embodiment of the present disclosure, the method for manufacturing a blended hydrocarbon composition may further include a pretreatment operation (also referred to as a pretreatment operation) of pretreating waste plastics before the pyrolysis operation.

[0155] According to an embodiment of the present disclosure, the pretreatment operation may include, a) reacting waste plastics and a neutralizer; and b) reacting the product of operation a) and a copper compound The pretreatment operation may reduce a Cl content to a level at which the waste plastic raw material may be introduced to an oil refining process by the treatment.

[0156] According to an embodiment of the present disclosure, in operation b), a metal oxide other than the copper compound and an additive or neutralizer such as zeolite may be used.

[0157] The metal oxide may be in the form of a divalent metal oxide, but is not limited thereto.

[0158] The waste plastic may include at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polyvinyl chloride (PVC), and polystyrene (PS). The waste plastic may include organic chlorine (Cl), inorganic Cl, and aromatic Cl, and the chlorine content of the waste plastic may be 10 ppm or more, 50 ppm or more, 100 ppm or more, or 100 to 1,000 ppm, but the embodiments of present disclosure are not limited thereto. In the pyrolysis oil produced by a cracking or pyrolysis reaction of waste plastics such as waste plastic pyrolysis oil, a large amount of impurities resulting from waste plastics are included. In particular, a chlorine component such as organic/inorganic chlorine needs to be removed by pretreatment of the pyrolysis oil. The waste plastics may be divided into domestic waste plastics and industrial waste plastics. The domestic waste plastics are plastics in which PVC, PS, PET, PBT, and the like in addition to PE and PP are mixed, and in the present disclosure, may refer to mixed waste plastics including 3 wt % or more of PVC with PE and PP. Since chlorine derived from PVC has high ratios of organic Cl and inorganic Cl, Cl in the domestic waste plastics may be removed with high efficiency with an inexpensive neutralizer (Ca-based, Zn-based, or Al-based neutralizer). Though most of the industrial waste plastics are occupied by PE/PP, an organic Cl content resulting from an adhesive or dye component is high, and in particular, since a ratio of Cl contained in an aromatic ring (aromatic chlorine) is high, it is difficult to remove the industrial waste plastics with a common inexpensive neutralizer mentioned above.

[0159] The embodiments of the present disclosure are characterized by removing 95 wt % or more, 97 wt % or more, 98 wt % or more, or 99 wt % or more of chlorine, with respect to the total weight of chlorine included in the waste plastics derived from the waste plastics. To this end, it is preferred to remove chlorine contained in the aromatic ring.

[0160] Operation a) includes an operation reacting the waste plastic and the neutralizer, and a large amount of hydrogen chloride produced in the process of melting and pyrolysis of PVC and the like may be removed in the form of a neutralized form.

[0161] The neutralizer may include oxides, hydroxide, carbonates of metal, or a combination thereof, and the metal may be calcium, aluminum, magnesium, zinc, copper, iron, or a combination thereof. Specifically, the neutralizer may be a copper oxide, an aluminum oxide, a calcium oxide, magnesium oxide, a zinc oxide, or an iron oxide. The neutralizer may include a zeolite component. Specifically, the neutralizer may include a waste FCC catalyst (E-cat) including a zeolite component and may further include the waste FCC catalyst in the metal oxide. The neutralizer may be, specifically, a calcium oxide, a waste FCC catalyst, a copper metal, or a copper oxide, or may be a calcium oxide.

[0162] In an embodiment according to the present disclosure, the neutralizer may be added in the pyrolysis operation.

[0163] The neutralizer may be blended at 0.5 to 20 wt %, 1 to 10 wt %, or 1 to 5 wt %, with respect to the total weight of the waste plastic. In addition, the neutralizer may be blended at a mole ratio of a metal element (M) of the neutralizer to a total chlorine element (Cl) in the waste plastic of 1 to 25, specifically 0.7 to 15, and more specifically 0.5 to 5.

[0164] The moles of the total chlorine element (Cl) in the waste plastic may refer to the total moles of the chlorine element of the waste plastic solid raw material before the pretreatment and the pyrolysis.

[0165] In the chlorine removal operation a), a ratio (C.sub.1/C) of a chlorine weight of the product of operation a) (C.sub.1) to 100 wt % of chlorine content (C) of the waste plastic may be 50% or less, 40% or less, or 20 to 30%. Chlorine remaining in the waste plastic after operation a) may be effectively removed in operation b).

[0166] Step b) is an operation reacting the product of operation a) and a copper compound, and a small amount of organic chlorine and aromatic chlorine which have not been removed in operation a) may be removed by the copper compound (catalyst agent). When the copper compound is used with the neutralizer of operation a) or used instead of the neutralizer, the copper compound first reacts with chlorine positioned at the end of a hydrocarbon chain of the organic chlorine and inorganic chlorine (hydrogen chloride), so that it may be difficult to come into contact with aromatic chlorine and the like which are difficult to be removed with a neutralizer. In addition, since the initial pyrolysis point when the inside of the reactor is heated for pretreatment or pyrolysis is a relatively low temperature (250-300 C.), and hydrogen chloride starts to occur at this time, it is preferred to first remove chlorine with a neutralizer. Thereafter, when a real pyrolysis operation proceeds, the temperature is relatively high, and a removal reaction of aromatic chlorine is activated. Thus, it is effective to first remove organic Cl, inorganic Cl, and the like with hydrogen chloride using the neutralizer, and then remove aromatic chlorine and the like with the copper compound.

[0167] The copper compound may include at least one selected from the group consisting of copper metal (Cu), copper oxide (CuO), copper hydroxide (Cu(OH).sub.2), and copper carbonate (CuCO.sub.3), and specifically, may include copper metal (Cu) and/or copper oxide (CuO).

[0168] The copper compound may be blended at 0.1 to 20 wt %, 0.5 to 10 wt %, or 1 to 5 wt %, with respect to the total weight of the product of operation a). In addition, the copper compound may be blended at a mole ratio (N.sub.Cu/N.sub.Cl) of the copper compound to the total chlorine element (Cl) in the waste plastic of 1 to 10, specifically 0.7 to 5, and more specifically 0.5 to 3.

[0169] The moles of the total chlorine element (Cl) in the waste plastic may refer to the total moles of the chlorine element of the waste plastic solid raw material before the pretreatment and the pyrolysis.

[0170] In the chlorine removal operation b), a ratio (C.sub.2/C) of chlorine content of the product of operation b) (C.sub.2) to 100 wt % of chlorine content (C) of the waste plastic may be 10% or less, 5% or less, or 0.5 to 3%.

[0171] According to an embodiment of the present disclosure, operation a) may proceed at a temperature of 200 to 320 C., and operation b) may proceed at a temperature of 400 to 550 C. When operations a) and b) proceed in each of the temperature range, chlorine in the waste plastic may be effectively removed.

[0172] According to an embodiment of the present disclosure, in the pyrolysis operation, a) reacting the waste plastic and the neutralizer; and b) reacting the product of operation a) and the copper compound may proceed.

[0173] In the present disclosure, the pretreatment operation may further include a crushing operation of adding waste plastics to a screw reactor to perform crushing. A crushing process known in the art may be applied to the crushing of the waste plastics, and for example, waste plastics may be added to a pretreatment reactor and heated to about 300 C. to manufacture a hydrocarbon flow precursor in a pellet form, but the embodiment is not limited thereto.

[0174] According to an embodiment of the present disclosure, the crushing operation may be performed at room temperature.

[0175] As an example, the crushing operation may be blending the waste plastic and the neutralizer and adding the blend to the pretreatment reactor. When the waste plastics, calcium oxide as the neutralizing agent, and the like are mixed and pulverized at room temperature, mechanochemical reaction may occur to produce hydrocarbon and CaOHCl, which has an effect of stably fixing chlorine in the waste plastic raw material to CaOHCl.

[0176] Subsequently, in the pretreatment operation, the crushed waste plastic may be added to the pretreatment reactor and heated, and the solid waste plastic raw material may be physiochemically treated to remove chlorine and manufacture a hydrocarbon flow precursor (pyrolysis raw material). The hydrocarbon flow precursor may refer to a waste plastic melt, and the waste plastic melt may refer to all or a part of crushed or finely crushed solid waste plastics being converted into liquid waste plastics.

[0177] As an example, the pretreatment operation may be adding each of the crushed or not-crushed waste plastics and the neutralizer to the pretreatment reactor and heating them. In addition, the pretreatment operation may be adding the crushed or not-crushed waste plastics and the neutralizer to a pretreatment reactor to perform a first pretreatment (heating) and then adding a copper compound to the pretreatment reactor to perform a second pretreatment (heating).

[0178] The heating may be performed at a temperature of 200 to 320 C. under normal pressure. Specifically, the heating may be performed at a temperature of 250 to 320 C. or 280 to 300 C. In general, the pretreatment temperature of waste plastics is at least 250 C., but in the hydrocarbon after the dechlorination, the pretreatment may be easily performed even at a lower temperature of 200 C. to generate hydrogen or methane gas.

[0179] The pretreatment reactor may be an extruder, an autoclave reactor, a batch reactor, or the like, and as an example, may be an auger reactor, but the embodiments of the present disclosure are not limited thereto.

[0180] The pyrolysis operation may be adding a pyrolysis raw material which is classified into a gas phase, a liquid phase (oil+wax+water), and a solid phase material to a pyrolysis reactor, and specifically, may include an operation adding the unpretreated or pretreated waste plastics to the pyrolysis reactor and heating them.

[0181] As an example, the pyrolysis operation may include blending the pretreated waste plastic and a divalent metal compound, specifically a copper compound, adding the blend to the pyrolysis reactor, and heating it. In addition, the pyrolysis operation may include performing first pyrolysis of pyrolyzing the waste plastic blended with the neutralizer, adding the blend to the pyrolysis reactor, and heating it, and then performing second pyrolysis of adding the divalent metal compound, specifically the copper compound to the pyrolysis reactor and heating them, and may be continuously or discontinuously performing pyrolysis at least twice.

[0182] The heating may be performed at a temperature of 320 to 900 C., specifically 350 to 700 C., and more specifically 400 to 550 C. under a non-oxidizing atmosphere. In addition, the heating may be performed under normal pressure. The non-oxidizing atmosphere is an atmosphere in which waste plastics are not oxidized (not burn), and for example, maybe an atmosphere having an oxygen concentration adjusted to 1 vol % or less or an inert gas atmosphere such as nitrogen, vapor, carbon dioxide, and argon.

[0183] When the heating temperature is 400 C. or higher, fusion of chlorine-containing plastic may be prevented, and on the contrary, when the heating temperature is 550 C. or lower, chlorine in the waste plastic may remain in pyrolysis residues (char) in the form of XCl.sub.2 wherein X is a divalent metal cation, specifically, CaCl.sub.2, CuCl.sub.2, or the like.

[0184] The pyrolysis reactor may be an autoclave reactor, a batch stirred reactor, a fluidized-bed reactor, a packed-bed reactor, and the like, and specifically, may include all reactors capable of stirring and heating control. According to an embodiment the pyrolysis reactor may be a batch reactor.

[0185] According to an embodiment, the pyrolysis reactor may include at least two batch reactors.

[0186] According to an embodiment, the pyrolysis may include performing a switch operation of at least two batch reactors. Thus, the pyrolysis operation may secure process continuity even at a high temperature.

[0187] In the method for manufacturing a blended hydrocarbon composition according to an embodiment of the present disclosure, the pyrolysis operation or the operation of manufacturing waste plastic pyrolysis oil may further include at least an operation selected form the group consisting of a pyrolysis gas recovery operation of recovering a pyrolysis gas phase and a pyrolysis liquid phase as gas and a separation operation of separating a pyrolysis solid phase (solid content) into fine particles and coarse particles.

[0188] In the gas recovery operation, pyrolysis gas including low-boiling point hydrocarbon compounds such as methane, ethane, and propane from gas phases produced in the pyrolysis operation or the operation of manufacturing waste plastic pyrolysis oil may be recovered. Generally, the pyrolysis gas may include combustible materials such as hydrogen, carbon monoxide, and low-molecular weight hydrocarbon compounds. An example of the hydrocarbon compound may include methane, ethane, ethylene, propane, propene, butane, butene, and the like. Since the pyrolysis gas includes the combustible materials, it may be used as a fuel.

[0189] In the separation operation, a solid content of the solid phase produced in the pyrolysis operation or in the operation of manufacturing the waste plastic pyrolysis oil, for example, a carbide and the neutralizer and/or a copper compound may be separated into fine particles and coarse particles. Specifically, sorting may be performed using a sieve which is larger than an average particle diameter of a chlorine-containing plastic and also is smaller than an average particle diameter of the neutralizer and the copper compound, thereby separating the solid content produced by a pyrolysis reaction into fine particles and coarse particles.

[0190] In the separation operation, it is preferred that the solid content is separated into fine particles which include more chlorine-containing neutralizer and copper compound, and coarse particles which include more carbide. The fine particles and the coarse particles may be retreated, if necessary, and may be reused in the pyrolysis operation, used as a fuel, or discarded, and the embodiments of the present disclosure are not limited thereto.

[0191] The operation of manufacturing waste plastic pyrolysis oil may be performed at a temperature of 400 to 550 C. under normal to 0.5 bar, and the oxygen-free atmosphere may be an inert gas atmosphere of an oxygen-free closed system atmosphere. In the temperature range in the operation of manufacturing waste plastic pyrolysis oil, lightening of pyrolysis gas may proceed well to improve blockage and differential pressure occurrence caused by wax may be improved.

[0192] The operation of manufacturing waste plastic pyrolysis oil may have gas volumetric flow rate (GHSV) of 0.3 to 1.2/hr or 0.5 to 0.8/hr. Thus, the waste plastic pyrolysis product may be lightened or impurities (such as Cl) therein may be reduced without performing a separate post-treatment process, and the residence time of the pyrolysis gas (GHSV) may be adjusted to manufacture the pyrolysis gas having a high ratio of light hydrocarbons and the blended hydrocarbon composition having a high ratio of light hydrocarbons, which are intended advantages in the present disclosure.

[0193] The neutralizer which fills the hot filter may have a particle size of 400 to 900 m or a particle size of 500 to 800 m. In the operation conditions of the operation of manufacturing waste plastic pyrolysis oil of the present disclosure, by filling the hot filter with the neutralizer having the above particle size, the residence time of pyrolysis gas (GHSV) may be adjusted to achieve lightening of an oil fraction, and also differential pressure occurrence of the hot filter may be suppressed to improve process operation efficiency.

[0194] The particle size may refer to D50, and D50 refers to a diameter of a particle with a cumulative volume of 50% when cumulated from the smallest particle in measurement of a particle size distribution by a laser scattering method. Herein, D50 may be obtained by collecting a sample for the prepared carbonaceous material according to the standard of KS A ISO 13320-1 and measuring a particle size distribution, using Mastersizer 3000 from Malvern Panalytical Ltd. Specifically, a volume density may be measured after dispersion is performed using ethanol as a solvent, and, if necessary, using an ultrasonic disperser.

[0195] According to another embodiment of the present disclosure, the hot filter may be filled with the beads and the neutralizer.

[0196] In the relevant technical field, it is common that the hot filter serves to separate gas and residues (char) from the product of the pyrolysis operation, but in the present disclosure, a hot filter filled with at least one selected from the group consisting of beads and a neutralizer in order to remove impurities such as chlorine simultaneously with lightening is applied, and thus, as described above, operation conditions such as the temperature of the hot filter and the particle size of the neutralizer are adjusted to specific ranges.

[0197] The operation of manufacturing waste plastic pyrolysis oil may satisfy the following Relation 1 and Relation 2:

[00001]$\begin{array}{cc}50<\left(A_2-A_1\right)/A_1\left(\%\right)<100& \mathrm{Relation}1\end{array}$$\begin{array}{cc}-80<\left(B_2-B_1/B_1\right)\left(\%\right)<-50& \mathrm{Relation}2\end{array}$

wherein A.sub.1 is a total amount (wt %) of naphtha (boiling point: 150 C.) and kerosene (boiling point: 150-265 C.) of the pyrolysis gas, A.sub.2 is a total amount (wt %) of naphtha (boiling point: 150 C.) and kerosene (boiling point: 150-265 C.) of the pyrolysis oil, B.sub.1 is a content (ppm) of chlorine in the pyrolysis gas, and B.sub.2 is a content (ppm) of chlorine in the pyrolysis oil.

[0198] In Relations 1 and 2, specifically, 60<(A.sub.2A.sub.1)/A.sub.1 (%) <90, 65<(A.sub.2A.sub.1)/A.sub.1 (%)<85, or 70<(A.sub.2A.sub.1)/A.sub.1 (%)<80 may be satisfied, and 75<(B.sub.2B.sub.1/B.sub.1) (%)<55, 70<(B.sub.2B.sub.1/B.sub.1) (%)<55, or 65<(B.sub.2B.sub.1/B.sub.1) (%)<55 may be satisfied.

[0199] Relations 1 and 2 represent lightening and weighing degrees of the waste plastic pyrolysis product caused by the use of the hot filter filled with at least one selected from the group consisting of the beads and the neutralizer of the present disclosure, as numerical values. The embodiments of the present disclosure have an advantageous technical characteristic of manufacturing pyrolysis oil having a high ratio of light hydrocarbons, by adjusting the oil fraction composition and the chlorine content of the pyrolysis gas added to the hot filter and the organic/inorganic material including chlorine.

[0200] The pyrolysis oil manufactured in the operation of manufacturing waste plastic pyrolysis oil may include 30 to 50 wt % of naphtha (bp150 C.), 30 to 50 wt % of kerosene (bp 150-265 C.), 10 to 30 wt % of light gas oil (LGO) (bp 265-380 C.), and 0 to 10 wt % of UCO-2/AR (bp 380 C.), specifically, 35 to 50 wt % of naphtha (bp150 C.), 35 to 50 wt % of kerosene (bp 150-265 C.), 10 to 30 wt % of light gas oil (LGO) (bp 265-380 C.), and 0 to 8 wt % of UCO-2/AR (bp 380 C.), or 35 to 45 wt % of naphtha (bp150 C.), 35 to 45 wt % of kerosene (bp 150-265 C.), 10 to 20 wt % of light gas oil (LGO) (bp 265-380 C.), and 0 to 6 wt % of UCO-2/AR (bp 380 C.). In addition, the pyrolysis gas may have a weight ratio of the light oil fraction (sum of naphtha and kerosene) to a heavy oil fraction (sum of LGO and UCO-2/AR) of 2.5 to 5, 2.5 to 4, or 3 to 3.8.

[0201] The waste plastic pyrolysis oil manufactured in the operation of manufacturing waste plastic pyrolysis oil may include less than 100 ppm, 80 ppm or less, 60 ppm or less, 5 to 50 ppm, or 10 to 50 ppm of total chlorine, and less than 90 ppm, 70 ppm or less, 50 ppm or less, 5 to 50 ppm, or 5 to 40 ppm of organic chlorine, with respect to the total weight.

[0202] According to an embodiment of the present disclosure, the pyrolysis operation and the operation of manufacturing waste plastic pyrolysis oil may satisfy the following Relation 3:

[00002]$\begin{array}{cc}0.7<T_2/T_1<1.3& \mathrm{Relation}3\end{array}$

wherein T.sub.1 and T.sub.2 are temperatures where the pyrolysis operation and the operation of manufacturing waste plastic pyrolysis oil proceed, respectively.

[0203] When the pyrolysis operation and the operation of manufacturing waste plastic pyrolysis oil proceed so that the T.sub.2/T.sub.1 value satisfies 0.7 or less, the temperature of the pyrolysis operation may be relatively high, or the temperature of the operation of manufacturing waste plastic pyrolysis oil may be low. In this case, the ratio of being condensed in the hot filter and circulated to the pyrolysis reactor is increased, and the final boiling point of the pyrolysis oil may be excessively low. However, when the operation proceeds so that the T.sub.2/T.sub.1 value satisfies 1.3 or more, a loss ratio in a gas phase is excessively increased to lower the yield of pyrolysis oil.

[0204] Specifically, the T.sub.2/T.sub.1 may be 0.7 to 1.2, 0.8 to 1.2, 0.8 to 1.1, 0.9 to 1.1, or as an example, 1. Thus, the effects described above may be further improved.

[0205] In an embodiment according to the present disclosure, the method for manufacturing a blended hydrocarbon composition may further include before operation S3), a distillation operation of distilling the refined pyrolysis oil to produce a refined hydrocarbon derived from the refined pyrolysis oil.

[0206] The refined hydrocarbon derived from the refined pyrolysis oil may be included in at least one boiling point range selected from the group consisting of gasoline, kerosene, aviation fuel, diesel, lube base oil, marine fuel oil, asphalt, and wax.

[0207] Among the refined hydrocarbons derived from the refined pyrolysis oil, gasoline may be a material having a boiling point in a range of 36 to 180 C., obtained by distilling the refined pyrolysis oil.

[0208] Among the refined hydrocarbons derived from the refined pyrolysis oil, kerosene may be a material having a boiling point in a range of 150 to 265 C., obtained by distilling the refined pyrolysis oil.

[0209] Among the refined hydrocarbons derived from the refined pyrolysis oil, aviation fuel may be a material having a boiling point in a range of 150 to 260 C., obtained by distilling the refined pyrolysis oil.

[0210] Among the refined hydrocarbons derived from the refined pyrolysis oil, diesel may be a material having a boiling point in a range of 220 to 380 C., obtained by distilling the refined pyrolysis oil.

[0211] Among the refined hydrocarbons derived from the refined pyrolysis oil, lube base oil may be a material having a boiling point in a range of 380 to 450 C., obtained by distilling the refined pyrolysis oil.

[0212] Among the refined hydrocarbons derived from the refined pyrolysis oil, marine fuel oil may be a material having a boiling point in a range of 380 C. or higher, obtained by distilling the refined pyrolysis oil.

[0213] Among the refined hydrocarbons derived from the refined pyrolysis oil, asphalt may be a material having a boiling point in a range of 540 C. or higher, obtained by distilling the refined pyrolysis oil.

[0214] Among the refined hydrocarbons derived from the refined pyrolysis oil, wax may be a material having a boiling point in a range of 380 C. or higher, obtained by distilling the refined pyrolysis oil.

[0215] In addition, in an embodiment according to the present disclosure, the method for manufacturing a blended hydrocarbon composition may be blending the refined hydrocarbon with the petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition in operation S3).

[0216] The description of the method for manufacturing a blended hydrocarbon composition may be identically applied to the description of the manufacturing system of a blended hydrocarbon composition within the overlapping range.

[0217] An embodiment of the present disclosure provides a manufacturing system of a blended hydrocarbon composition including a dehydrator which applies voltage to a first blended solution in which waste plastic pyrolysis oil is blended with washing water and a demulsifier to dehydrate the first blended solution; a hydrotreating device which hydrotreats a second blended solution in which the dehydrated first blended solution and a sulfur source are blended to manufacture refined pyrolysis oil from which impurities have been removed; and a blending device which blends the refined pyrolysis oil with a petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition.

[0218] The dehydrator according to an embodiment of the present disclosure may be provided with a vertical electrode. The number of the vertical electrodes provided in the dehydrator according to an embodiment of the present disclosure may be at least 2, specifically 4 or more, more specifically 6 or more, and as the upper limit, 20 or less, but is not necessarily limited thereto.

[0219] The dehydrator according to an embodiment of the present disclosure may include a coalescer inside. The coalescer is a device which collects fine droplets to form large droplets, may be a commonly used device in the industry, and the embodiment is not particularly limited thereto.

[0220] A first blended solution dehydrated in the dehydrator is introduced to the coalescer according to an embodiment of the present disclosure to produce a further dehydrated first blended solution. When the dehydrator including the coalescer is used, the further dehydrated first blended solution is introduced to the hydrogenation treatment reactor with hydrogen gas, of course.

[0221] The manufacturing system of the blended hydrocarbon composition according to an embodiment of the present disclosure may further include a separator which performs gas-liquid separation of the refined pyrolysis oil from which impurities produced from the hydrotreating device have been removed.

[0222] The number of the separators according to an embodiment of the present disclosure may be 2 to 4, specifically 3 or 4, and more specifically 4. When the range is satisfied, since the refined pyrolysis oil contains a trace amount of NH.sub.3 and HCl, production of the ammonium salt may be minimized even in low temperature conditions for oil-water separation. In addition, a blending process using refined pyrolysis oil as a raw material may be stably performed without adding a separate salt remover to the refined pyrolysis oil later.

[0223] The manufacturing system of a blended hydrocarbon composition according to an embodiment of the present disclosure may further include a recycle gas compressor which recovers unreacted hydrogen gas from the gas stream separated from the separator and adds the hydrogen gas to the hydrotreating device.

[0224] In an embodiment according to the present disclosure, the manufacturing system of a blended hydrocarbon composition may further include a pyrolysis reactor which manufactures pyrolysis gas by adding waste plastics; and a hot filter which manufactures waste plastic pyrolysis oil by adding the pyrolysis gas.

[0225] The manufacturing system of the present disclosure may produce high value-added waste plastic pyrolysis oil having a high light hydrocarbon ratio from waste plastics having a large amount of impurities, and a blended hydrocarbon composition having a high light hydrocarbon ratio may be manufactured therefrom. In addition, the manufacturing system of the present disclosure may improve the yield of pyrolysis oil obtained from the waste plastics.

[0226] In addition, in an embodiment of the present disclosure, the manufacturing system of a blended hydrocarbon composition may further include a connection pipe which connects the hot filter and the pyrolysis reactor so that a liquid condensed in the hot filter may be reintroduced to the pyrolysis reactor.

[0227] In another embodiment of the present disclosure, the manufacturing system of a blended hydrocarbon composition may further include a pretreatment reactor.

[0228] Referring to FIG. 2, a supply raw material 11 is injected into a supply raw material injector 12, and screw blending may be performed. Crushed waste plastics and an additive are added to a pretreatment reactor 13, and then pretreatment may be performed. The pretreated waste plastics may be added to the pyrolysis reactor 14, and pyrolysis may be performed to produce pyrolysis gas. The produced pyrolysis gas (see VAPOR stream in FIG. 2) may be added to a hot filter 15 and then be lightened. Thereafter, the lightened pyrolysis gas (see GAS in FIG. 2) may be introduced to a condenser 16 to obtain waste plastic pyrolysis oil in the pyrolysis oil recovery part 18. The liquid condensed (Condensing liquid) in the hot filter 15 may be reintroduced to the pyrolysis reactor 14 through a connection pipe 19.

[0229] Referring to FIG. 4, the obtained waste plastic pyrolysis oil from a feed tank 21 may be added to a dehydrator 22 and stirred to prepare a first blended solution. The first blended solution may be separated into oil and water by applying alternating current voltage through a vertical electrode. Thereafter, the separated water layer may be removed to perform dehydration. The first blended solution dehydrated in the dehydrator 22 and dimethyl sulfide are blended to prepare a second blended solution, and then the second blended solution may be hydrated in the dehydrator 23. Thereafter, hydrotreated pyrolysis oil may be introduced to a first separator 24-1 to separate the hydrotreated pyrolysis oil into liquid and gas. The liquid separated in the first separator 24-1 may be introduced to a third separator 24-3 and then introduced to a blending device 25. The gas separated in the first separator 24-1 may be introduced to the second separator 24-2. Impurities including NH.sub.3 and HCl contained in gas separated in the first separator 24-1 may be removed with water in the second separator 24-2. Additional separation is performed in a fourth separator 24-4, and then oil fraction recovered from gas may be introduced to the blending device 25 to manufacture a blended hydrocarbon composition.

[0230] Referring to FIG. 5, the refined pyrolysis oil recovered in the first separator to the fourth separator 24-1 to 24-4 may be added to a distillation device 26, before being added to the blending device 25. The distillation device 26 may produce refined hydrocarbon derived from the refined pyrolysis oil by distilling the refined pyrolysis oil. The blending device 25 may blend the refined hydrocarbon with the petroleum-based hydrocarbon to produce a blended hydrocarbon composition.

[0231] According to an embodiment of the present disclosure, the hot filter may be filled with beads. When the hot filter is filled with beads, the inert effect and the heat transfer effect in the hot filter may be maximized to manufacture pyrolysis oil having a high light hydrocarbon ratio. In addition, the yield of pyrolysis oil may be improved.

[0232] According to an embodiment of the present disclosure, the beads may include at least one selected from the group consisting of silica sand (SiO.sub.2) and aluminum oxide (Al.sub.2O.sub.3).

[0233] According to an embodiment of the present disclosure, the manufacturing system may be provided with at least two heaters outside the hot filter. In addition, the manufacturing system may be provided with at least three heaters outside the hot filter. When at least 2 heaters are provided outside the hot filter, temperature gradient formation in the hot filter is easily performed, and the temperatures in the upper stage, middle stage, and lower stage may be flexibly adjusted depending on the operation situation of the hot filter, and thus, flexible process operation is allowed.

[0234] According to an embodiment of the present disclosure, the manufacturing system of a blended hydrocarbon composition may further include a distillation device which distills the refined pyrolysis oil to produce a refined hydrocarbon derived from the refined pyrolysis oil.

[0235] In addition, according to an embodiment of the present disclosure, the blending device may blend the refined hydrocarbon with the petroleum-based hydrocarbon to manufacture a blended hydrocarbon composition.

[0236] Hereinafter, the manufacturing method and the manufacturing system of the blended hydrocarbon composition according to the present disclosure will be described in more detail through the following examples. However, the following examples are only a reference for illustrating the embodiments of the present disclosure in detail, and the embodiments are not limited thereto and may be implemented in various forms. In addition, unless otherwise defined, all technical terms and scientific terms have the same meanings as those commonly understood by a person skilled in the art to which the present disclosure pertains. In addition, the terms used herein are only for effectively describing certain embodiments and are not intended to limit the embodiments of the present disclosure.

Example 1

[0237] Domestic waste plastics used as a feed included 73.4 wt % of PE, 10.4 wt % of PP, 9.8 wt % of PVC, 2.3 wt % of PET, 2.1 wt % of nylon, and 2.0 wt % of PU.

[0238] 600 g of the domestic waste plastic feed was added to a batch pyrolysis reactor, and was pyrolyzed at 500 C. The produced pyrolysis gas was added to a 1.3 L hot filter at 500 C., which was filled with 20 g of Cao having a particle size (D50) of 400-900 m, collected in a condenser, and recovered in a recovery part as waste plastic pyrolysis oil.

[0239] The yield of the pyrolysis oil is shown in Table 2, and the results of performing GC-Simdis analysis (HT 750) for confirming the molecular weight distribution of the pyrolysis oil are shown in Table 3.

[0240] The waste plastic pyrolysis oil, washing water, and polyethylene glycol having a weight average molecular weight of 500 were added to a dehydrator at a volume ratio of 1:0.25:0.0001 under the conditions of 150 C. and 10 bar, and stirring was performed to prepare a first blended solution. An alternating current voltage of 15 kV was applied to the first blended solution to perform oil-water separation, and a water layer was removed to perform dehydration.

[0241] At this time, the waste plastic pyrolysis oil had a moisture content of about 5,000 ppm or more and a high concentration of impurities of 500 ppm or more of nitrogen (N), 200 ppm of chlorine (Cl), and 20 vol % or more of olefins.

[0242] 0.04 parts by weight of dimethyl disulfide was blended with respect to 100 parts by weight of the first blended solution dehydrated in the dehydrator to prepare a second blended solution, which was hydrotreated under the conditions of 300 C. and 70 bar to produce refined pyrolysis oil from which the impurities had been removed. The results of measuring impurity contents in the refined pyrolysis oil are shown in Table 1-1.

[0243] Gasoline (boiling point: 36 to 180 C.) in the refined pyrolysis oil from which the impurities had been removed was separated by distillation and blended with petroleum-based gasoline at a weight ratio of 0.01:1 to obtain a blended hydrocarbon composition.

Examples 2 and 3

[0244] Blended hydrocarbon compositions were obtained in the same manner as in Example 1, except that waste plastic pyrolysis oil, washing water, and polyethylene glycol were added to the dehydrator at volume ratios described in Table 1-1.

Example 4

[0245] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that direct current voltage was applied through a horizontal electrode.

Example 5

[0246] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that the dehydration of the first blended solution was performed under the temperature condition of 120 C.

Example 6

[0247] A blended hydrocarbon composition was obtained in the same manner as in Example 5, except that the waste plastic pyrolysis oil was added at a volume ratio of 1:0.00001 and hydrotreatment was performed under the condition of a pressure of 180 bar.

Example 7

[0248] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that the first blended solution was dehydrated and then further dehydrated through a coalescer.

Example 8

[0249] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that the liquid condensed in the hot filter was reintroduced to the pyrolysis reactor.

Example 9

[0250] The process was performed in the same manner as in Example 1, except that a 1.3 L hot filter was filled with glass beads having a diameter of 3 mm instead of Cao at 88 vol % of the internal volume of the hot filter, the upper stage temperature, the middle stage temperature, and the lower stage temperature of the hot filter were maintained at 430 C., and the liquid condensed in the hot filter was reintroduced to the pyrolysis reactor.

Example 10

[0251] The process was performed in the same manner as in Example 1, except that a 1.3 L hot filter was filled with glass beads having a diameter of 3 mm instead of CaO at 88 vol % of the internal volume of the hot filter, the upper stage temperature of the hot filter was maintained at 430 C., the middle stage temperature and the lower stage temperature of the hot filter were maintained at 500 C., and the liquid condensed in the hot filter was reintroduced to the pyrolysis reactor.

Example 11

[0252] The process was performed in the same manner as in Example 1, except that a 1.3 L hot filter was filled with glass beads having a diameter of 3 mm instead of CaO at 88 vol % of the internal volume of the hot filter, the upper stage temperature of the hot filter was maintained at 430 C., the middle stage temperature of the hot filter was maintained at 450 C., and the lower stage temperature of the hot filter was maintained at 500 C., and the liquid condensed in the hot filter was reintroduced to the pyrolysis reactor.

Example 12

[0253] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that kerosene (boiling point: 150 to 265 C.) in the refined pyrolysis oil from which impurities had been removed was separated by distillation and blended with petroleum-based kerosene at a weight ratio of 0.1:1.

Example 13

[0254] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that an aviation fuel (boiling point: 150 to 260 C.) in the refined pyrolysis oil from which impurities had been removed was separated by distillation and blended with a petroleum-based aviation fuel at a weight ratio of 0.0001:1.

Example 14

[0255] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that diesel (boiling point: 220 to 380 C.) in the refined pyrolysis oil from which impurities had been removed was separated by distillation and blended with petroleum-based diesel at a weight ratio of 0.1:1.

Example 15

[0256] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that lube base oil (boiling point: 380 to 450 C.) in the refined pyrolysis oil from which impurities had been removed was separated by distillation and blended with a petroleum-based lube base oil at a weight ratio of 0.5:1.

Example 16

[0257] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that marine fuel oil (boiling point: 380 C. or higher) in the refined pyrolysis oil from which impurities had been removed was separated by distillation and blended with a petroleum-based marine fuel oil at a weight ratio of 0.0001:1.

Example 17

[0258] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that asphalt (boiling point: 540 C. or higher) in the refined pyrolysis oil from which impurities of the same have been removed, was separated by distillation and blended with petroleum-based asphalt at a weight ratio of 0.00001:1.

Example 18

[0259] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that wax (boiling point: 380 C. or higher) in the refined pyrolysis oil from which impurities Wax been removed, was separated by distillation and blended with petroleum-based wax at a weight ratio of 0.01:1.

Comparative Example 1

[0260] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that washing water was not added.

Comparative Example 2

[0261] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that polyethylene glycol was not added.

Comparative Example 3

[0262] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that voltage was not applied.

Comparative Example 4

[0263] A blended hydrocarbon composition was obtained in the same manner as in Example 1, except that dimethyl sulfide was not blended with the dehydrated first blended solution.

Evaluation Example

Measurement Method

[0264] The composition of the waste plastic feed was analyzed using a Flake analyzer available from RTT, Germany, among the NIR analyzers.

[0265] To confirm the composition of the pyrolyzed product related to measurement of the waste plastic pyrolysis oil yield, GC-Simdis analysis (HT 750) was performed.

[0266] After completing the dehydration process, for analysis of the contents of moisture and impurities of Cl, S, N, and O in the obtained blended solution and the contents of impurities of Cl, S, N, and O in the finally obtained refined pyrolysis oil, ICP, TNS, EA-O, and XRF analyses were performed. A total Cl content was measured in accordance with ASTM D5808, a N content was measured in accordance with ASTM D4629, and a S content was measured in accordance with ASTM D5453.

[0267] A catalytic activity maintenance time was shown by performing total nitrogen % sulfur (TNS element) analysis on the refined pyrolysis oil and performing measurement in hours based on the time when a nitrogen content in the refined pyrolysis oil exceeded 10 ppm.

[0268] In addition, the processes of the examples and the comparative examples were operated for 3 months, and a particle fixation rate was measured according to the following Equation 1:

[00003]$\begin{array}{cc}\mathrm{Particle}\mathrm{fixation}\mathrm{rate}\left(\%\right)=\left(\mathrm{amount}\mathrm{of}\mathrm{impurity}\mathrm{particles}\mathrm{fixed}\mathrm{to}\mathrm{electrode}/\mathrm{amount}\mathrm{of}\mathrm{impurity}\mathrm{particles}\mathrm{in}\mathrm{pyrolysis}\mathrm{oil}\right)*100& \mathrm{Equation}1\end{array}$

[0269] The measurement results are shown in the following Table 1-1 and 1-2.

TABLE-US-00001 TABLE 1-1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Dehydration Washing water 0.25 0.50 0.25 0.25 0.25 0.25 0.25 (volume ratio) Demulsifier 0.0001 0.0001 0.00001 0.0001 0.0001 0.00001 0.0001 (volume ratio) Temperature 150 150 150 150 120 120 150 ( C.) Pressure 10 10 10 10 10 10 10 (bar) Voltage Type Alternating Alternating Alternating Direct Alternating Alternating Alternating current current current current current current current Electrode Vertical Vertical Vertical Horizontal Vertical Vertical Vertical Presence of x x x x x x coalescer Hydrotreatment Sulfur source blending Temperature 300 300 300 300 300 300 300 ( C.) Pressure 70 70 70 70 70 180 70 (bar) Moisture content 556 743 618 559 678 850 474 (ppm) after dehydration Cl content (ppm) 528 522 570 529 605 703 442 after dehydration Catalytic activity >720 >720 >720 >720 >720 >720 >720 maintenance time (hr) Cl content (ppm) in <1 <1 <1 <1 <1 <1 <1 refined pyrolysis oil Particle attachment 0.20 0.20 0.19 3.3 0.20 0.19 0.18 rate (%)

TABLE-US-00002 TABLE 1-2 Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Dehydration Washing water 0.25 0.25 0.25 (volume ratio) Demulsifier 0.0001 0.0001 0.0001 (volume ratio) Temperature 150 150 150 150 ( C.) Pressure 10 10 10 10 (bar) Voltage Type Alternating Alternating Alternating current current current Electrode Vertical Vertical Vertical Presence of x x x x coalescer Hydrotreatment Sulfur source x blending Temperature 300 300 300 300 ( C.) Pressure 70 70 70 70 (bar) Moisture content 2283 4011 3570 578 (ppm) after dehydration Cl content (ppm) 920 1008 1030 532 after dehydration Catalytic activity <576 <576 <576 <336 maintenance time (hr) Cl content (ppm) in 12.7 16.4 15.5 11.1 refined pyrolysis oil Particle attachment 0.24 0.23 0.20 rate (%)

[0270] As seen from Table 1-1 and 1-2, Comparative Examples 1 to 3 had differences, an addition of the washing water, addition of the demulsifier, and application of voltage, respectively, and as a result, showed poor moisture and Cl removal results. Since the waste plastic pyrolysis oil including a large amount of impurities were hydrotreated, the Cl content in the refined pyrolysis oil was high, and the hydrotreating catalyst was relatively rapidly deactivated. Though in Comparative Example 4, the moisture and some impurities in the waste plastic pyrolysis oil were sufficiently removed in the dehydration operation, when the hydrogenation catalyst was deactivated within a short time due to an insufficient sulfur content to maintain the purification process for a long time, the Cl content in the refined pyrolysis oil was shown to be high, like other comparative examples. In addition, since Cl included in a large amount in the refined pyrolysis oil may cause corrosion of a distillation tower, the content of the refined pyrolysis oil in the blended oil added to the distillation tower is expected to be limited.

[0271] However, in Examples 1 to 7 according to the method for manufacturing a blended hydrocarbon composition from the waste plastic of the present disclosure, a significant amount of moisture contained in the waste plastic pyrolysis oil was removed by the dehydration operation, a sulfur source was added, and thus, the activity of the hydrotreating catalyst lasted for a significantly long time. In addition, since some water-soluble impurities are preemptively removed in the dehydration operation, and the excellent activity of the catalyst used in the hydrotreatment lasted for a long time, a high-quality blended hydrocarbon composition having a very low impurity content was able to be obtained.

[0272] Moreover, when an alternating current voltage was applied using a vertical electrode, even when the process proceeded for 3 months or more, the char-derived impurity particle fixation rate in the pyrolysis oil on the surface of the electrode was confirmed to be very low. Thus, it was found that when alternating current voltage was applied, or a vertical electrode was used, process shutdown for washing the inside of the reactor was not required, and better process efficiency was able to be shown. That is, the use of AC voltage and/or vertical electrodes significantly reduces maintenance requirements and improves long-term operational stability.

[0273] In addition, Example 6 had poor dehydration results as compared with other examples, but since it proceeded under the high hydrotreating pressure conditions, the impurity Cl content in the refined pyrolysis oil was very low. However, since ammonia and hydrogen chloride were produced in excessive amounts due to high pressure, it was confirmed that the ammonium salt was produced in a relatively large amount even at a temperature at which the hydrotreatment was performed.

[0274] Since additional dehydration was performed using a coalescer in Example 7, moisture and the chlorine content after dehydration was shown to be low as compared with other examples, and thus, it was expected that the activation time of the catalyst, process stability, and refined pyrolysis oil quality were better than those of other examples.

TABLE-US-00003 TABLE 2 Exam- Exam- Exam- Exam- Exam- ple 1 ple 8 ple 9 ple 10 ple 11 Yield of 51.9 55.0 57.2 60.5 62.0 pyrolysis oil (wt %)

TABLE-US-00004 TABLE 3 Composition ratio of refined pyrolysis oil (wt %) Example 1 Example 8 Example 9 Example 10 Example 11 Naphtha (boiling 26.8 32.6 37.3 40.3 40.4 point of 150 C. or lower) Kerosene (boiling 32.3 35.5 33.8 39.3 42.1 point of 150 to 265 C.) LGO (boiling point 21.1 17.9 13.1 7.8 8.0 of 265 to 340 C.) VGO (boiling point 19.7 14.2 112.8 7.3 4.5 of 340 C. or higher) Sum of naphtha and 59.1 681.1 71.1 79.6 82.5 kerosene

[0275] Referring to Tables 2 and 3, it was confirmed that Example 1 in which the hot filter was not filled with beads and the liquid condensed in the hot filter was not reintroduced to the pyrolysis reactor had the lowest waste plastic pyrolysis oil yield and the lowest ratio of a light oil fraction including naphtha and kerosene.

[0276] It was also confirmed that Example 8 in which the liquid condensed in the hot filter was reintroduced to the pyrolysis reactor was able to achieve a better waste plastic pyrolysis oil yield and a better ratio of light hydrocarbons including naphtha and kerosene than those of Example 1.

[0277] It was further confirmed that Example 9, in which the liquid condensed in the hot filter was reintroduced to the pyrolysis reactor and the hot filter was filled with beads, showed a better waste plastic pyrolysis oil yield and a ratio of light hydrocarbons including naphtha and kerosene than those of Example 8.

[0278] Examples 10 and 11 in which the liquid condensed in the hot filter was reintroduced to the pyrolysis reactor, the hot filter was filled with beads, and a temperature gradient that was formed in the hot filter showed a better waste plastic pyrolysis oil yield and a better ratio of light hydrocarbons including naphtha and kerosene than those of Examples 8 and 9.

[0279] In particular, it was confirmed that Example 11 in which the upper stage of the hot filter was maintained at 430 C., the middle stage temperature of the hot filter was maintained at 450 C., and the lower stage temperature of the hot filter was maintained at 500 C. showed the best waste plastic pyrolysis oil yield and the best ratio of the light hydrocarbons including naphtha and kerosene. The manufacturing method and the manufacturing system of a blended hydrocarbon composition according to the present disclosure may minimize production of an ammonium salt (NH.sub.4Cl) in the process of refining waste plastic pyrolysis oil containing impurities including chlorine, nitrogen, and the like.

[0280] Since the deactivation of the catalyst used in the process is prevented, the manufacturing method and the manufacturing system of a blended hydrocarbon composition according to the present disclosure have excellent refining efficiency and allows long-term operation of the process.

[0281] Since the manufacturing method and the manufacturing system of a blended hydrocarbon composition according to the present disclosure have very low contents of impurities, such as chlorine, nitrogen, oxygen, and metal, and olefins from waste plastic pyrolysis oil, they may provide a blended hydrocarbon composition having excellent quality.

[0282] According to an embodiment of the present disclosure, high value-added waste plastic pyrolysis oil having a high light hydrocarbon ratio may be manufactured from waste plastics having a large amount of impurities, and a blended hydrocarbon composition having a high light hydrocarbon ratio may be obtained therefrom.

[0283] According to another embodiment of the present disclosure, since a blended hydrocarbon composition having a high light hydrocarbon ratio may be obtained from waste plastics, the economic feasibility of the process may be improved.

[0284] According to an embodiment of the present disclosure, a waste plastic pyrolysis oil yield obtained from waste plastics may be improved.

[0285] The manufacturing method and the manufacturing system of a blended hydrocarbon composition according to the present disclosure may be used in eco-friendly oil refining and production of petrochemical products using waste plastics as a raw material.

[0286] Hereinabove, the embodiments of the present disclosure have been described, but the embodiments of the present disclosure are not limited thereto, and those with ordinary skill in the art will understand that various changes and modification are possible within the range which is not out of the concept and the scope of the present disclosure. Furthermore, the embodiments may be combined to form additional embodiments.