HYDROGENATION AND REFINING TECHNOLOGY OF MIXED OIL INCLUDING WASTE BIO-OIL

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001]This application claims priority under 35 U.S.C. § 119 to Korean Patent Application No. 10-2024-0096171, filed on Jul. 22, 2024, the disclosure of which is incorporated herein by reference in its entirety.

TECHNICAL FIELD

[0002]Embodiments of the present disclosure generally relate to a hydrogenation treatment method of a mixed oil including a waste bio-oil and a waste plastic pyrolysis oil and a method for producing a refined oil.

BACKGROUND

[0003]Since waste plastics have physical properties which gradually deteriorate compared to the initial properties as they are reused, their recyclability is low, and most waste plastics are discarded as trash. Since the discarded waste plastics have low density and large volume, it is difficult to treat them and it takes a long time to decompose them naturally, and thus, they cause serious soil pollution.

[0004]Waste bio refers generally to agricultural by-products, oily wastes, animal and plant fat components, waste organic matter of biological origin, and the like, and since it is inedible and has low industrial value, most of the waste bio is discarded. When the waste bio is discarded, serious foul odor occurs due to decay, and thus, it is very difficult to designate a disposal site and the treatment is difficult.

[0005]In order to address the issues of waste plastics and waste-bio and the issues such as reduction of carbon dioxide which is a material causing global warming worldwide and rising cost of crude oil, a method for converting the waste plastics and the waste-bio into usable oil as a raw material has been proposed.

[0006]However, since the waste plastic pyrolysis oil and the waste bio-oil have a high content of impurities such as chlorine, nitrogen, and metal as compared with a fraction prepared from crude oil by a common method, they may not be used directly as high value-added fuel such as gasoline and diesel, and thus, a refining process should be performed.

[0007]As such, a refining method for removing impurities such as chlorine, nitrogen, and metal contained in waste plastic pyrolysis oil adsorbs and removes chlorine contained in the waste plastic pyrolysis oil, using a dechlorination/denitrification method by reacting waste plastic pyrolysis oil and hydrogen in the presence of a hydrogenation treatment catalyst, or a chlorine adsorbent.

[0008]However, since the waste bio-oil includes a large amount of oxygen having no energy contribution, it is difficult to perform refinement with the same hydrogenation treatment process as the process for the waste plastic pyrolysis oil described above. Hence, new methods are needed.

SUMMARY

[0009]An embodiment of the present disclosure is directed to providing a hydrogenation treatment method of a mixed oil including a waste bio-oil containing a large amount of oxygen and a waste plastic pyrolysis oil.

[0010]Another embodiment of the present disclosure is directed to providing a hydrogenation treatment method of a mixed oil including a waste bio-oil and a method for producing a refined oil by refining the hydrogenated oil.

[0011]Still another embodiment of the present disclosure is directed to providing a refined oil having impurities reduced to a refined raw material level from a mixed oil including a waste bio-oil.

[0012]According to one embodiment of the present disclosure, a hydrogenation treatment method of a mixed oil includes hydrogenating a mixed oil including a waste plastic pyrolysis oil and a waste bio-oil with a reaction gas including a hydrogen gas in the presence of a plurality of molybdenum-based hydrogenation catalysts, wherein the plurality of molybdenum-based hydrogenation catalysts may be two or more molybdenum-based hydrogenation catalysts including different metal supports from each other.

[0013]According to an embodiment of the present disclosure, the plurality of molybdenum-based hydrogenation catalysts may include a molybdenum-based hydrogenation catalyst including an alumina support and a molybdenum-based hydrogenation catalyst including a zirconia support.

[0014]According to an embodiment of the present disclosure, the hydrogenating of a mixed oil may include hydrogenating the mixed oil with a multi-stage catalyst layer formed of the molybdenum-based hydrogenation catalysts including different metal supports in the catalyst layer of each stage.

[0015]In an embodiment of the present disclosure, the multi-stage catalyst layer may include a catalyst layer formed of a molybdenum-based hydrogenation catalyst including an alumina (Al₂O₃) support and a molybdenum-based hydrogenation catalyst including a zirconia (ZrO₂) support.

[0016]According to an embodiment of the present disclosure, the mixed oil may include 0.01 to 50 wt % of the waste bio-oil with respect to the total mass.

[0017]According to an embodiment of the present disclosure, the waste bio-oil may include 10 wt % or more of oxygen impurities with respect to the total mass.

[0018]According to an embodiment of the present disclosure, the waste bio-oil may have a boiling point of 200° C. or higher.

[0019]According to an embodiment of the present disclosure, a reaction temperature in the hydrogenating of a mixed oil may be 330 to 500° C.

[0020]According to an embodiment of the present disclosure, the hydrogen gas introduced to the hydrogenation treatment method of a mixed oil may be 100 bar or less.

[0021]According to an embodiment of the present disclosure, a volume ratio between the hydrogen gas and the mixed oil introduced to the hydrogenation treatment method of a mixed oil may be 300:1 to 3000:1.

[0022]According to an embodiment of the present disclosure, the hydrogenation treatment method of a mixed oil may have a liquid hourly space velocity (LHSV) of 0.1 to 10 h⁻¹. The liquid hourly space velocity (LHSV) denotes the hourly volumetric flow rate of fluid per bed volume of catalyst and serves as an indicator for specifying reactor size and number.

[0023]In another embodiment, a method for producing a refined oil includes producing a product by the hydrogenation treatment method of a mixed oil described above; and removing hydrogenated impurities included in the product.

[0024]According to an embodiment of the present disclosure, the refined oil may include 5 ppm or less of chlorine, 40 ppm or less of nitrogen, 5 ppm or less of sulfur, 5 wt % or less of olefin, 1 wt % or less of conjugated diolefin, and 5 ppm or less of a metal-based compound with respect to the total mass.

[0025]According to an embodiment of the present disclosure, the refined oil may include less than 5 wt % of oxygen with respect to the total mass.

[0026]According to one embodiment of the present disclosure, a method for producing a refined oil from a mixed oil, the method comprises: subjecting a mixed oil to a multi-stage hydrogenation treatment including a first stage and a second stage, each stage including a molybdenum-based hydrogenation catalyst including a different metal support.

[0027]According to an embodiment of the present disclosure, the different metal supports include an alumina support and a zirconia support.

[0028]According to an embodiment of the present disclosure, the mixed oil includes waste bio-oil in an amount of 0.01 to 90 wt % of the total mass of the mixed oil, wherein the waste bio-oil has a boiling point of 200° C. or higher, and at least 5 wt % oxygen.

[0029]According to an embodiment of the present disclosure, a reaction temperature of the hydrogenating treatment of the mixed oil is 330 to 500° C.

[0030]Other features and aspects of the embodiments of the present disclosure will be apparent from the following detailed description, the drawings, and the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

[0031]FIG. 1 is a simplified schematic diagram showing a hydrogenation treatment method of a mixed oil according to an embodiment of the present disclosure.

[0032]FIG. 2 is a simplified schematic diagram showing a hydrogenation treatment method of a mixed oil in the presence of a multi-stage catalyst layer according to an embodiment of the present disclosure.

[0033]FIG. 3 is a simplified schematic diagram showing a method for producing a refined oil according to an embodiment of the present disclosure.

MAIN ELEMENTS OF THE FIGURES

DETAILED DESCRIPTION

[0045]Technical terms and scientific terms described in the present specification have the general meaning understood by a person skilled in the art unless otherwise defined. Descriptions for known functions and configurations which may obscure the present disclosure will be omitted in the following description.

[0046]In addition, the singular form used in the present disclosure may be intended to also include a plural form, unless otherwise indicated in the context.

[0047]In addition, units used in the present disclosure without particular mention are based on weights, and as an example, a unit of % or ratio refers to a wt % or a weight ratio, and wt % refers to wt % of any one component in a total composition, unless otherwise defined.

[0048]In addition, 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 in a form and span 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 from each other. Unless otherwise defined in this specification, values which may be outside a numerical range due to experimental error or rounding off a value are also included in the defined numerical range.

[0049]The term “comprise” 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.

[0050]According to an embodiment of the present disclosure a hydrogenation treatment method of a mixed oil includes hydrogenating a mixed oil of a waste plastic pyrolysis oil and a waste bio-oil with a reaction gas including a hydrogen gas in the presence of a plurality of molybdenum-based hydrogenation catalysts.

[0051]The waste plastic pyrolysis oil refers to a mixture of hydrocarbon fractions produced by pyrolyzing waste plastics. Herein, the waste plastics may include solid or liquid wastes related to synthetic polymer compounds such as waste synthetic resins, waste synthetic fibers, waste synthetic rubber, and waste vinyl.

[0052]The waste plastic pyrolysis oil may include impurities such as chlorine compounds, nitrogen compounds, and metal compounds in addition to the hydrocarbon fractions, and also, may include impurities in the form in which chlorine, nitrogen, metal, and the like are bonded to a hydrocarbon compound included in the waste plastic pyrolysis oil.

[0053]In addition, the waste bio-oil may be prepared by a process such as ester exchange, pyrolysis, and fermentation of waste cooking oils, sewage sludge, insect wastes, agricultural by-products, oily wastes, animal and plant oil components, waste organic matter of biological origin, and the like.

[0054]The waste bio-oil may include impurities such as chlorine, nitrogen, and sulfur similarly to the waste plastic pyrolysis oil described above, and also, may include impurities in the form in which chlorine, nitrogen, sulfur, and the like are bonded to a hydrocarbon compound. In particular, the waste bio-oil may include a large amount of oxygen impurities as compared with the waste plastic pyrolysis oil described above.

[0055]That is, the waste bio-oil needs removal of a large amount of oxygen impurities by a hydrogenation treatment. In addition, the waste bio-oil may require a technology of removing oxygen impurities and impurities other than oxygen by a hydrogenation treatment, even in a mixed oil with the waste plastic pyrolysis oil having high productivity as compared with the waste bio-oil.

[0056]According to an embodiment of the present disclosure, the hydrogenation treatment method of the mixed oil uses a plurality of molybdenum-based hydrogenation catalysts, and the plurality of molybdenum-based hydrogenation catalysts may be two or more molybdenum-based hydrogenation catalysts including different metal supports from each other.

[0057]The molybdenum-based hydrogenation catalyst may include, as an example, one or two or more metal supports selected from alumina (Al₂O₃), silica (SiO₂), silica-alumina (SiO₂—Al₂O₃), titania (TiO₂), molecular sieves, zirconia (ZrO₂), aluminum phosphate (AlPO₄), carbon, niobia (NbO₂), and the like.

[0058]The hydrogenation treatment method of a mixed oil according to the present disclosure hydrogenates a large amount of oxygen impurities and impurities such as nitrogen, chlorine, sulfur, and metal excellently, using a plurality of molybdenum-based hydrogenation catalysts including different metal supports from each other, and then performs refinement. In addition, the hydrogenation treatment method of a mixed oil may easily remove impurities of a mixed oil without any special process, using a plurality of molybdenum-based hydrogenation catalysts having different metal supports.

[0059]According to an embodiment of the present disclosure, the plurality of molybdenum-based hydrogenation catalysts may include a molybdenum-based hydrogenation catalyst including an alumina support and a molybdenum-based hydrogenation catalyst including a zirconia support.

[0060]In an embodiment, the plurality of molybdenum-based hydrogenation catalysts are different from each other and include an alumina (Al₂O₃) support or a zirconia (ZrO₂) support, and may hydrogenate impurities of a mixed oil including a large amount of oxygen impurities with excellent reactivity, as described above.

[0061]In addition, since the plurality of molybdenum-based hydrogenation catalysts which are different from each other and include the alumina (Al₂O₃) support or the zirconia (ZrO₂) support have excellent resistance to water produced by hydrogenating oxygen impurities, a decreased hydrogenation treatment reaction of the catalysts due to the produced water is prevented to hydrogenate the mixed oil for a long time with excellent hydrogenation reactivity.

[0062]According to an embodiment of the present disclosure, the molybdenum-based hydrogenation catalyst may be a catalyst in which metal including a molybdenum metal and one or two or more selected from nickel, tungsten, cobalt, or the like is supported on the metal support described above.

[0063]In addition, the molybdenum-based hydrogenation catalyst may be a catalyst in which molybdenum and nickel or cobalt are supported on the metal support or preferably a catalyst in which a molybdenum-based metal and nickel are supported, in terms of having excellent hydrogenation reactivity of impurities of the mixed oil including the waste plastic pyrolysis oil and the waste bio-oil, but the plurality of molybdenum-based hydrogenation catalysts are not necessarily limited as long as the metal supports are different from each other and the hydrogenation treatment reaction of a mixed oil is not reduced.

[0064]According to another embodiment of the present disclosure, the molybdenum-based hydrogenation catalyst may be a molybdenum-based sulfide hydrogenation catalyst in which sulfur is bonded to molybdenum supported on the metal support and may be preferably a molybdenum-based sulfide-based hydrogenation catalyst, in terms of refining by hydrogenating sulfur impurities and oxygen impurities in the mixed oil with high reactivity.

[0065]The molybdenum-based hydrogenation catalyst may be, for example, one or two or more selected from NiMo/γ-Al₂O₃ and CoMo/γ-Al₂O₃, NiMo/γ-ZrO₂ and CoMo/γ-ZrO₂, and the like, or the plurality of molybdenum-based hydrogenation catalysts may include NiMo/γ-Al₂O₃ and NiMo/γ-ZrO₂. These molybdenum-based catalysts may have excellent hydrogenation reactivity and high water resistance, and may, therefore, be preferred, however, the embodiments may not be necessarily limited in this way unless the hydrogenation treatment reaction of the mixed oil is reduced.

[0066]The hydrogenation treatment method of a mixed oil according to an embodiment of the present disclosure may include hydrogenating a mixed oil with the mixed oil hydrogenation treatment system 1 as shown in FIG. 1.

[0067]Referring to FIG. 1, the hydrogenation treatment method according to an embodiment of the present disclosure may include injecting a mixed oil into a hydrogenation treatment reactor through a mixed oil supply line 20, and hydrogenating the mixed oil injected into the hydrogenation treatment reactor 10 in a catalyst layer 30 formed by a plurality of molybdenum-based hydrogenation catalyst. Thereafter, the product formed by hydrogenating the mixed oil may be discharged through a product discharge line 40.

[0068]The catalyst layer 30 may include a plurality of molybdenum-based hydrogenation catalysts having different metal supports from each other, as described above, and each of the metal supports of the plurality of molybdenum-based hydrogenation catalysts may be an alumina (Al₂O₃) support or a zirconia (ZrO₂) support, but the embodiments are not necessarily limited thereto.

[0069]According to an embodiment of the present disclosure, the hydrogenating of a mixed oil may be hydrogenating the mixed oil with a multi-stage catalyst layer formed of the molybdenum-based hydrogenation catalysts including different metal supports from each other in the catalyst layer of each stage.

[0070]In the hydrogenation treatment method of a mixed oil, according to the embodiment of FIG. 1 described above, the plurality of molybdenum-based hydrogenation catalysts having different metal supports from each other may be formed into one catalyst layer and the mixed oil may be hydrogenated, but a hydrogenation treatment with a multi-stage catalyst layer in which the catalyst layer of each stage is formed of molybdenum-based hydrogenation catalysts including different metal supports from each other may be preferred.

[0071]Since the multi-stage catalyst layer in which the catalyst layer of each stage is formed of the molybdenum-based hydrogenation catalysts having different metal supports from each other may have excellent hydrogenation reactivity to each impurity included in the mixed oil and high resistance to hydrogenated impurities, excellent hydrogenation reactivity may be maintained for a long time.

[0072]The molybdenum-based hydrogenation catalysts having different metal supports from each other, which form the multi-stage catalyst layer have different metal supports from each other and active metals supported on the metal support may be identical to or different from each other, as described above, but it is preferred that the active metals are identical in terms of having excellent hydrogenation treatment reactivity under the same hydrogenation treatment reaction conditions, but the embodiments are not necessarily limited thereto.

[0073]The multi-stage catalyst layer formed by including different molybdenum-based hydrogenation catalysts from each other may selectively hydrogenate impurities such as chlorine, nitrogen, oxygen, sulfur, and metal included in the mixed oil excellently in the catalyst layer of each stage, in the hydrogenation treatment reaction, and thus, is preferred.

[0074]According to an embodiment of the present disclosure, the hydrogenation treatment method of the mixed oil may include hydrogenating the mixed oil with a mixed oil hydrogenation treatment system 1 according to the embodiment illustrated in FIG. 2.

[0075]Referring now to FIG. 2, the hydrogenation treatment method of a mixed oil according to an embodiment of the present disclosure may include injecting a mixed oil into a hydrogenation treatment reactor 10 through a mixed oil supply line 20 and performing a hydrogenation reaction by sequentially bringing the injected mixed oil into contact with an upper catalyst layer 30a and a lower catalyst layer 30b. Thereafter, the product produced by hydrogenating the mixed oil may be discharged to a product discharge line 40.

[0076]According to the embodiment of FIG. 2, it is illustrated that in the mixed oil hydrogenation treatment system 1, the mixed oil is hydrogenated with the upper catalyst layer 30a and the lower catalyst layer 30b, however, the embodiments are not limited to two stage catalyst treatment only and, for example, in a variation of the illustrated embodiment, a multi-stage catalyst layer may form 3 or more catalyst layers (or stages).

[0077]The multi-stage catalyst layer may be formed by the catalyst layer of each stage including molybdenum-based hydrogenation catalysts having different metal supports, as described above.

[0078]The molybdenum-based hydrogenation catalyst included in each stage may be a catalyst in which a molybdenum-based metal and metal including one or two or more selected from nickel, tungsten, cobalt, and the like are supported on a metal support, or a catalyst in which a molybdenum-based metal and nickel or tungsten are supported, or a catalyst in which a molybdenum-based metal and nickel are supported, but the embodiments are not necessarily limited thereto.

[0079]The plurality of molybdenum-based catalysts having different metal supports from each other may have the same metal supported on the metal support, in terms of having excellent hydrogenation reactivity under constant reaction conditions, and as an example, may be preferably a catalyst in which a molybdenum-based metal and nickel are supported, but are not necessarily limited thereto as long as the refined oil including an impurity content targeted in the present disclosure may be produced.

[0080]The two molybdenum-based hydrogenation catalysts including an alumina (Al₂O₃) support or a zirconia (ZrO₂) support may hydrogenate a large amount of oxygen impurities included in the mixed oil with excellent reactivity, as described above. In addition, the multi-stage catalyst layer may be preferred, since each of the molybdenum-based hydrogenation catalyst of the alumina support and the molybdenum-based hydrogenation catalyst of the zirconia support is formed into the catalyst layer of each stage and the catalyst layer of each stage has higher resistance to the hydrogenated impurities.

[0081]According to an embodiment of the present disclosure, the hydrogenation treatment method of a mixed oil may include sequentially bringing the mixed oil into contact with the molybdenum-based hydrogenation catalyst of the alumina metal support and the molybdenum-based hydrogenation catalyst of the zirconia support, in the multi-stage catalyst layer including the molybdenum-based hydrogenation catalyst layer including the alumina metal support and the molybdenum-based hydrogenation catalyst layer including the zirconia support described above.

[0082]In the hydrogenation treatment method of a mixed oil illustrated in FIG. 2 the mixed oil injected into the mixed oil supply line 20 may be hydrogenated by sequentially bringing the mixed oil into contact with the upper catalyst layer 30a and the lower catalyst layer 30b, and the upper catalyst layer 30a may be formed of the molybdenum-based hydrogenation catalyst of the alumina metal support while the lower catalyst layer 30b may be formed of the molybdenum-based hydrogenation catalyst of the zirconia support.

[0083]It has been found that in the hydrogenation treatment method of the mixed oil, when the mixed oil is sequentially brought into contact with the molybdenum-based hydrogenation catalyst of the alumina support and the hydrogenation treatment catalyst of the zirconia support, the oxygen impurities included in the mixed oil may be effectively hydrogenated obtaining excellent hydrogenation of the oxygen impurities, and also the molybdenum-based hydrogenation catalyst layer of the zirconia support show significantly improved or excellent resistance to water, and thus, the mixed oil may have continuous excellent hydrogenation reactivity.

[0084]Therefore, since the hydrogenation treatment method of a mixed oil uses the multi-stage catalyst layer and the molybdenum-based hydrogenation catalysts of different metal supports from each other described above, the mixed oil including waste bio-oil may have excellent hydrogenation reactivity and a refined oil having a very low impurity content may be produced by removing hydrogenated impurities.

[0085]According to an embodiment of the present disclosure, the waste plastic pyrolysis oil may include impurities in the form of a single compound such as nitrogen, chlorine, sulfur, and metal or in the form of being bonded to a hydrocarbon compound, as described above, and may further include an olefin having 6 or less of carbon atoms or a conjugated diolefin having 6 or less carbon atoms.

[0086]The waste plastic pyrolysis oil may contain 300 ppm or more of nitrogen (N), 30 ppm or more of chlorine, and 100 ppm or less of sulfur, and under the conditions of 1 atm and 25° C., contain 20% by mass or more of the olefin and 1% by mass or more of the conjugated diolefin, with respect to the total mass, but since it varies depending on the waste plastics which is the raw material of the waste plastic pyrolysis oil, the embodiment is not necessarily limited thereto.

[0087]The waste plastic pyrolysis oil may have a hydrocarbon fraction content of 10 or more carbon atoms of 30 wt % or more, 40 wt % or more, 50 wt % or more and 95 wt % or less or 90 wt % or less. For example, the content may be 30 to 95 wt %, 40 to 95 wt %, or 50 to 95 wt %.

[0088]The waste plastic pyrolysis oil including the hydrocarbon fraction content having 10 or more carbon atoms in the above range may be preferred since the refined oil produced by performing the hydrogenation treatment and the process of removing hydrogenated impurities may be commercially excellent, but the embodiment is not necessarily limited thereto.

[0089]According to an embodiment of the present disclosure, the waste bio-oil may be produced from waste bio such as waste cooking oil, sewage sludge, insect wastes, agricultural by-products, oily wastes, animal and plant oil components, and waste organic matter of biological origin, as described above.

[0090]The waste bio-oil may be different depending on the waste bio used in the waste bio-oil production but may include 100 ppm or more of nitrogen (N), 10 ppm or more of chlorine (Cl), and 10 ppm or less of sulfur(S) with respect to the total mass.

[0091]According to an embodiment of the present disclosure, the waste bio-oil may include 5 wt % or more, 10 wt % or more, 15 wt % or more, 20 wt % or more and 45 wt % or less, 40 wt % or less, 35 wt % or less, or 30 wt % or less of the oxygen impurities with respect to the total mass. For example, the content may be 10 to 50 wt %, 15 to 50 wt %, or 20 to 50 wt %.

[0092]The waste bio-oil may include a large amount of oxygen impurities in the above content range as well as the impurities such as nitrogen, chlorine, and sulfur. The hydrogenation treatment method of a mixed oil may hydrogenate the mixed oil with excellent reactivity even when the waste bio-oil containing a large amount of oxygen impurities is included within the range described above, and may produce a refined oil having a significantly decreased content of oxygen impurities.

[0093]According to an embodiment of the present disclosure, e the waste bio-oil may have a boiling point of 200° C. or higher, 205° C. or higher, 210° C. or higher, 215° C. or higher, or 220° C. or higher, and though the upper limit is not limited, may have a boiling point of 250° C. or lower or 240° C. or lower.

[0094]Since the waste bio-oil contains a large amount of a hydrocarbon fraction having 14 or more carbon atoms, it may have a high boiling point within the range described above. Since the hydrogenation treatment method of a mixed oil may hydrogenate the mixed oil with excellent reactivity even when the mixed oil to be hydrogenated includes the waste bio-oil having a high boiling point, it may be preferred.

[0095]According to an embodiment of the present disclosure, the mixed oil may include 0.01 wt % or more, 0.1 wt % or more, 0.5 wt % or more, 1 wt % or more, 5 wt % or more, 10 wt % or more, or 20 wt % or more and 50 wt % or less, 80 wt % or less, 90 wt % or less, or 100 wt % or less of the waste bio-oil with respect to the total mass. For example, the waste bio-oil may be included at 0.01 to 90 wt %, 0.1 to 50 wt %, 0.5 to 50 wt %, 1 to 50 wt %, 5 to 50 wt %, 10 to 50 wt %, or 20 to 50 wt %.

[0096]That is, even when the mixed oil includes up to 50 wt % of the waste bio-oil including a large amount of oxygen impurities, the hydrogenation treatment method hydrogenates impurities such as nitrogen, chlorine, sulfur, metal, and, in particular, oxygen included in the mixed oil excellently with an excellent hydrogenation reaction, may later easily remove hydrogenated impurities, and thus, may be preferred, but the embodiment is not necessarily limited as long as the refined oil having decreased impurities targeted in the present disclosure may be produced.

[0097]Therefore, the hydrogenation treatment method of a mixed oil may provide a method for producing a refined oil having a high purity by hydrogenating and refining impurities such as oxygen, nitrogen, chlorine, sulfur, metal, olefin-based compounds, and conjugated diolefin included in the mixed oil including a large amount of oxygen impurities.

[0098]According to an embodiment of the present disclosure, the hydrogenation treatment method of a mixed oil may hydrogenate the mixed oil described above with a reaction gas including a hydrogen gas in the presence of a plurality of molybdenum-based hydrogenation catalysts.

[0099]According to an embodiment of the present disclosure, the hydrogenation treatment method of a mixed oil may be performed under the introduced hydrogen gas of 100 bar or less, 90 bar or less, 80 bar or less, 70 bar or less and 20 bar or more, 30 bar or more, 40 bar or more, or 50 bar or more. For example, the hydrogen gas may be 20 to 100 bar, 20 to 90 bar, 20 to 80 bar, 20 to 70 bar, 30 to 70 bar, 40 to 70 bar, or 50 to 70 bar.

[0100]The pressure of hydrogen gas introduced to the hydrogenation treatment method of a mixed oil may be measured at a temperature of 25° C. in a hydrogenation treatment reactor having a volume of 50 cm³, but the volume of the reactor is an example, and the pressure of the hydrogen gas is not particularly limited as long as it is recognized by a person skilled in the art.

[0101]The hydrogenation treatment method may hydrogenate the included impurities with excellent hydrogenation reactivity of the mixed oil, by introducing the hydrogen gas in the pressure range described above. Since the hydrogenation treatment method operated in the hydrogen pressure range above may secure worker stability and suppress production of NH₄Cl impurities to suppress a differential pressure increase rate in the reactor, it may be preferred, but is not necessarily limited as long as the impurity reduction targeted in the present disclosure is satisfied.

[0102]According to an embodiment of the present disclosure, the hydrogenation treatment method of a mixed oil may have a liquid hourly space velocity (LHSV) of 0.1 h⁻¹ or more, 0.3 h⁻¹ or more, 0.5 h⁻¹ or more, 1.0 h⁻¹ or more, 2.0 h⁻¹ or more and 10.0 h⁻¹ or less, 8.0 h⁻¹ or less, or 5.0 h⁻¹ or less. For example, it may have a liquid hourly space velocity (LHSV) of 0.1 to 10 h^{−1, 0.3} to 8 h⁻¹, or 0.5 to 5 h⁻¹.

[0103]In the process of a hydrogenation treatment at a liquid hourly space velocity in the above range, the mixed oil may be stably hydrogenated and hydrogenated impurities included in the product from hydrogenation of the mixed oil described later may be easily removed to obtain a refined oil having a high purity, and thus, the process may be preferred, but it is only an example, and the embodiments are not necessarily limited thereto.

[0104]According to an embodiment of the present disclosure, the hydrogenation treatment method of a mixed oil may have a volume ratio between the hydrogen gas and the mixed oil introduced (gas oil ratio, GOR) of 300:1 to 3000:1, and in another embodiment, a mass ratio may be 500:1 to 2500:1 or 800:1 to 1500:1.

[0105]The hydrogenation treatment method of a mixed oil satisfying GOR in the above range may have excellent hydrogenation treatment efficiency of the mixed oil, and also may have reaction stability, and thus, may be preferred.

[0106]According to an embodiment of the present disclosure, the hydrogenation treatment method of a mixed oil may have a reaction temperature of 330° C. or higher, 340° C. or higher, 350° C. or higher, 360° C. or higher, 370° C. or higher, 380° C. or higher, 390° C. or higher and 500° C. or lower, 490° C. or lower, 480° C. or lower, 470° C. or lower, 460° C. or lower, 450° C. or lower, 430° C. or lower, or 400° C. or lower. For example, the reaction temperature may be 330 to 500° C., 330 to 450° C., or 350 to 450° C.

[0107]Since the hydrogenation treatment method of a mixed oil satisfying the reaction temperature in the above range has improved hydrogenation treatment efficiency of the mixed oil, it may significantly decrease the impurity content of the refined oil produced by hydrogenating the mixed oil, and thus, may be preferred.

[0108]In addition, since the hydrogenation treatment method satisfying the reaction temperature in the above range has no deterioration of a hydrocarbon fraction having 10 or more carbon atoms included in the mixed oil, it may hydrogenate impurities without further increasing the content of impurities such as olefin and conjugated diolefin, and thus, may be preferred, but the embodiment is not necessarily limited thereto as long as the mixed oil may be hydrogenated.

[0109]Therefore, the hydrogenation treatment method of a mixed oil allows refinement of included impurities by hydrogenating the mixed oil including the waste bio-oil including a large amount of oxygen impurities and the waste plastic pyrolysis oil in the presence of the molybdenum-based hydrogenation catalysts described above and the multi-stage catalyst layer under the hydrogenation treatment reaction conditions.

[0110]An embodiment of the present disclosure may provide a method for producing a refined oil including producing a product by the hydrogenation treatment method of a mixed oil described above; and removing hydrogenated impurities from the product.

[0111]The hydrogenated impurities included in the product may include hydrogenated impurities such as hydrogen sulfide gas (H₂S), hydrogen chloride (HCl), ammonia (NH₃), water vapor (H₂O), and trace amounts of methane (CH₄) and ethane (C₂H₆), which are hydrogenated impurities of nitrogen, chlorine, sulfur, oxygen, and the like included in the mixed oil.

[0112]The hydrogenated impurities may be discharged through a gas and water discharge port of the reactor in the process of removing impurities, thereby finally obtaining the refined oil.

[0113]According to an embodiment of the present disclosure, in the method for producing a refined oil, the refined oil may be produced from the product described above, with the mixed oil hydrogenation treatment system 1 and the impurity removal system 2 according to the embodiment of FIG. 3.

[0114]Referring to FIG. 3, the mixed oil is hydrogenated with the mixed oil hydrogenation treatment system 1, the product produced by the hydrogenation reaction of the mixed oil is injected into a refinement reactor 50 through a product supply line 60, and the hydrogenated impurities included in the injected product are removed through a hydrogenated impurity discharge line 70, thereby obtaining a refined oil from which impurities have been removed.

[0115]In the embodiment of FIG. 3, the product supply line 60 may be connected to a product discharge line 40 of the process of FIG. 2, and since the processes of producing a product by the hydrogenation treatment method of a mixed oil and of removing hydrogenated impurities included in the product of the method for producing a refined oil may be performed by a continuous process, the method may have excellent processability.

[0116]According to an embodiment of the present disclosure, the refined oil may include 5 ppm or less of chlorine, 40 ppm or less of nitrogen, 5 ppm of sulfur, 5 wt % or less of olefin, 1 wt % or less of conjugated diolefin, and 5 ppm or less of a metal-based compound with respect to the total mass.

[0117]The impurity content of the refined oil may be obtained by analyzing the components of the hydrogenated impurities discharged through the hydrogenated impurity discharge line 70 in the embodiment of FIG. 3 by 2D gas chromatography (2D-GC) and calculating the hydrogenated impurity components analyzed by 2D-GC based on boiling points.

[0118]Since the impurities may be hydrogenated by the hydrogenation treatment method described above having excellent processability without adding a particular process, the refined oil from which impurities have been removed to the content in the above range may preferred.

[0119]As another embodiment of the present disclosure, the refined oil may include 5.0 ppm or less, 4.9 ppm or less, 4.5 ppm or less, 4.0 ppm or less, 3.0 ppm or less, 2.5 ppm or less, 2 ppm or less, 1.5 ppm or less, 1.3 ppm or less, 1.0 ppm or less, or 0.8 ppm or less of chlorine with respect to the total mass, and though the lower limit is not limited, may include no chlorine or 0.001 ppm or more, 0.005 ppm or more, or 0.01 ppm or more of chlorine.

[0120]In another embodiment of the present disclosure, the refined oil may include 40.0 ppm or less, 35.0 ppm or less, 34.3 ppm or less, 30.0 ppm or less, 35.0 ppm or less, 30.0 ppm or less, 20.0 ppm or less, 19.2 ppm or less, 19.0 ppm or less, 15.0 ppm or less, 10.0 ppm or less, 7.0 ppm or less, 6.5 ppm or less, 6.4 ppm or less, 6.0 ppm or less, 5.8 ppm or less, 5.6 ppm or less, 5.3 ppm or less, 5.0 ppm or less, 4.5 ppm or less, 4.3 ppm or less, 4.0 ppm or less, 3.5 ppm or less, 3.0 ppm or less, 2.5 ppm or less, 2.0 ppm or less, 1.5 ppm or less, or 1.0 ppm or less of nitrogen with respect to the total mass, and though the lower limit is not limited, may include no nitrogen or 0.001 ppm or more, 0.005 ppm or more, or 0.01 ppm or more of nitrogen.

[0121]In another embodiment of the present disclosure, the refined oil may include 5.0 ppm or less, 4.0 ppm or less, 3.0 ppm or less, 2.8 ppm or less, 2.5 ppm or less, 2.0 ppm or less, 1.6 ppm or less, 1.4 ppm or less, 1.1 ppm or less, 1.0 ppm or less, or less than 1.0 ppm of sulfur with respect to the total mass, and though the lower limit is not limited, may include no sulfur or 0.001 ppm or more, 0.005 ppm or more, or 0.01 ppm or more of sulfur.

[0122]In another embodiment of the present disclosure, the refined oil may include 5.0 ppm or less, 4.8 ppm or less, 4.5 ppm or less, 4.4 ppm or less, 4.0 ppm or less, 3.5 ppm or less, 3.2 ppm or less, 3.1 ppm or less, 3.0 ppm or less, 2.5 ppm or less, 2.0 ppm or less, 1.6 ppm or less, 1.5 ppm or less, 1.0 ppm or less, or less than 1.0 ppm of the metal-based compound, and though the lower limit is not limited, may include no metal-based compound or 0.001 ppm or more, 0.005 ppm or more, or 0.01 ppm or more of the metal-based compound.

[0123]In another embodiment of the present disclosure, the refined oil may include 5.0 wt % or less, 4.0 wt % or less, 3.0 wt % or less, 2.5 wt % or less, 2.2 wt % or less, 2.0 wt % or less, 1.8 wt % or less, 1.5 wt % or less, 1.4 wt % or less, 1.1 wt % or less, 1.0 wt % or less, 0.9 wt % or less, 0.8 wt % or less, 0.6 wt % or less, 0.5 wt % or less, 0.1 wt % or less, or less than 0.1 wt % of olefin with respect to the total mass, and though the lower limit is not limited, may include no olefin or 0.001 ppm or more, 0.005 ppm or more, or 0.01 ppm or more of the olefin.

[0124]According to an embodiment of the present disclosure, the refined oil may include 1.0 wt % or less, 0.8 wt % or less, 0.5 wt % or less, 0.2 wt % or less, 0.1 wt % or less, or less than 0.1 wt % or less of a conjugated diolefin with respect to the total mass, and though the lower limit is not limited, may include no conjugated diolefin or 0.001 ppm or more, 0.005 ppm or more, or 0.01 ppm or more of the conjugated diolefin.

[0125]The refined oil including impurities of chlorine, nitrogen, sulfur, metal, olefin, and conjugated diolefin may be produced with excellent processability without an additional process from the mixed oil including the waste plastic pyrolysis oil and the waste bio-oil.

[0126]The method for producing a refined oil may have an excellent refining rate of impurities such as chlorine, nitrogen, sulfur, metal, olefin, and conjugated diolefin included in the mixed oil including the waste plastic pyrolysis oil and the waste bio-oil, and, in particular, may have an excellent refining rate of chlorine and nitrogen, and thus, is preferred.

[0127]That is, since the refined oil including the impurities of chlorine, nitrogen, sulfur, metal, olefin, and conjugated diolefin in the above range may have impurities removed preferably to the level of refinery raw materials and be used as a raw material for replacing crude oil, it does not cause an environmental pollution problem due to fossil fuels and does not reduce productivity due to crude oil price instability, and thus, may be preferred.

[0128]According to an embodiment of the present disclosure, the refined oil may include less than 5 wt %, less than 4.0 wt %, less than 3.5 wt %, less than 3.0 wt %, less than 2.0 wt %, less than 1.5 wt %, less than 1.2 wt %, less than 1.0 wt %, less than 0.5 wt %, less than 0.4 wt %, 0.3 wt % or less, 0.2 wt % or less, 0.1 wt % or less, or less than 0.1 wt % of oxygen with respect to the total mass, and though the lower limit is not limited, may include no oxygen or 0.001 ppm or more, 0.005 ppm or more, or 0.01 ppm or more of oxygen.

[0129]The oxygen impurities may be removed from the mixed oil so that the refined oil includes oxygen within the range described above, even when the refined oil is produced by hydrogenating the mixed oil including the waste bio-oil including a large amount of oxygen.

[0130]Therefore, even when the waste bio-oil including a large amount of oxygen impurities is mixed with the waste plastic pyrolysis oil, the method for producing a refined oil may produce the refined oil having a high purity, and thus, it may provide diversity of introduced materials so that not only the waste plastic pyrolysis oil is introduced, but the waste bio-oil containing a large amount of oxygen is introduced simultaneously, in the hydrogenation treatment method.

[0131]Hereinafter, the hydrogenation treatment method of a mixed oil according to the present disclosure and the method for producing a refined oil including the same will be described in more detail, through the following examples. However, the examples are provided only as a reference for describing 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 in the present disclosure are only for effectively describing specific examples and are not intended to limit the embodiments of the present disclosure.

Measurement Method

Measurement of Impurities

[0132]Nitrogen, sulfur, chlorine, metal components, olefin, conjugated diolefin and oxygen included in the waste plastic pyrolysis oil, waste bio-oil, and refined oil were measured using a total nitrogen sulfur (TNS) analyzer (NSX-2100V, TS-100V, TS-100), an ion chromatography (Compact IC Pro/AQF-2100H) ICP (Inductively Coupled Plasma) meter (NexIOn 350S), energy dispersive X-ray fluorescence (ED-XRF), and elemental analyzer (EA 2000 Series), and the contents were calculated.

Nitrogent/Surfur Determination Method

[0133]The sample was combusted using a TS-100 instrument (Mitsubishi Chemical Co.), and the resulting NO₂ was quantified by chemiluminescence detection, while SO₂ was quantified by fluorescence detection. The quantification of nitrogen and sulfur (N/S) was performed in accordance with ASTM D4629, D5453, and D5762.

Chloride (Cl) Determination Method

[0134]The sample was completely combusted at high temperature using an 881 Compact IC Pro/AQF-2100H instrument (Metrohm, Thermo Scientific/Nittoseiko Co.). The resulting combustion gases were absorbed into an absorption solution. The chloride ions (Cl⁻) were then separated based on affinity differences using ion exchange principles via ion chromatography (IC), in accordance with ASTM D4327.

Metal Determination Method

[0135]The sample in aerosol form was introduced into an argon plasma generated by a PerkinElmer, Agilent 720 instrument. The inorganic elements in the sample absorbed energy and, upon returning to their ground state, emitted element-specific radiation. This emission was detected to perform qualitative and quantitative analysis of the metal elements, in accordance with ASTM D5185.

Olefin Content Analysis Method

[0136]The analysis of olefins in pyrolysis oil was conducted using two-dimensional gas chromatography (2D-GC; 7890/M3030V, Agilent/ZOEX Co.) and nuclear magnetic resonance (NMR; Agilent/Bruker Co.). The carbon number distribution and the presence of double bonds were identified and analyzed.

Conjugated Diene Content Analysis Method

[0137]The analysis of conjugated diolefins was performed using either the previously described olefin content analysis method or the conjugated diene quantification method specified in UOP Method 326-82. In this method, the conjugated diene functional groups in the sample react with maleic anhydride. The unreacted maleic anhydride is then hydrolyzed to maleic acid, and its quantity is determined by titration. The amount of conjugated dienes is calculated by difference, based on the amount of maleic anhydride that reacted.

Oxygen Content Analysis Method

[0138]The oxygen content in the sample was determined using an elemental analyzer (EA-O) such as the FlashSmart or EA 2000 Series (Thermo Scientific Co.). The sample was combusted at high temperature, and the resulting combustion gases were analyzed to quantify the oxygen content. The analysis was performed in accordance with ASTM D5622 and ASTM D5373.

Example 1

[0139]50 wt % of waste plastic pyrolysis oil and 50 wt % of waste bio-oil were mixed to produce a mixed oil.

[0140]The waste plastic pyrolysis oil was confirmed to include impurities of 1,100 ppm of nitrogen, 80 ppm of sulfur, and 250 ppm of chlorine by the above measurement method. In addition, the waste bio-oil was confirmed to include impurities of 60 ppm of nitrogen, 10 ppm of sulfur, and 10 ppm of chlorine, by measurement with the measurement method.

[0141]An upper catalyst layer formed of a NiMo/γ-Al₂O₃ catalyst and a lower catalyst layer formed of a NiMo/γ-ZrO₂ catalyst were sequentially disposed in a hydrogenation treatment reactor, in the order of the upper catalyst layer and the lower catalyst layer in the feed direction of the introduced mixed oil, as a molybdenum sulfide hydrogenation catalyst.

[0142]Thereafter, the hydrogenation treatment reactor was set at a liquid hourly space velocity of 2.5 h⁻¹, a reaction temperature of 350° C., a hydrogen gas input pressure of 60 bar, and a hydrogen gas mixed oil ratio (GOR) of 1,000 to hydrogenate the mixed oil.

[0143]In the hydrogenation treatment reactor, the produced hydrogenated mixed oil was injected into a separation device. The separation device was operated at 25° C. to remove ammonia, hydrogen sulfide, water, and hydrogen chloride included in the hydrogenated mixed oil and obtain the refined oil to the lower portion of the separation device.

[0144]Thereafter, the impurities in the produced refined oil were measured by the method described above, and the resulting values are shown in the following Table 2.

Example 2

[0145]A refined oil was produced in the same manner as in Example 1, except that the multi-stage catalyst layer was not formed in the hydrogenation treatment reactor and a single catalyst layer was formed by mixing a NiMo/γ-Al₂O₃ catalyst and a NiMo/γ-ZrO₂ catalyst.

[0146]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Example 3

[0147]A refined oil was produced in the same manner as in Example 1, except that the hydrogenation treatment reactor was operated at a reaction temperature of 330° C.

[0148]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Example 4

[0149]A refined oil was produced in the same manner as in Example 1, except that the hydrogenation treatment reactor was operated at a reaction temperature of 450° C.

[0150]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Example 5

[0151]A refined oil was produced in the same manner as in Example 1, except that the hydrogenation treatment reactor was operated at a hydrogen pressure of 150 bar.

[0152]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Example 6

[0153]A refined oil was produced in the same manner as in Example 1, except that the hydrogenation treatment reactor was operated at a reaction temperature of 390° C. and the liquid hourly space velocity (LHSV) of 10 h⁻¹.

[0154]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Example 7

[0155]A refined oil was produced in the same manner as in Example 1, except that the hydrogenation treatment reactor was operated at a GOR of 4000.

[0156]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Example 8

[0157]A refined oil was produced in the same manner as in Example 1, except that the mixed oil included 60 wt % of the waste bio-oil with respect to the total mass.

[0158]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Comparative Example 1

[0159]A refined oil was produced in the same manner as in Example 1, except that the catalyst layer was formed only with a NiMo/γ-Al₂O₃ catalyst in the hydrogenation treatment reactor.

[0160]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

Comparative Example 2

[0161]A refined oil was produced in the same manner as in Example 1, except that a NiMo/γ-Al₂O₃ catalyst was used in the upper catalyst layer and a CoMo/γ-Al₂O₃ catalyst was used in the lower catalyst layer.

[0162]Thereafter, the impurities in the refined oil were measured by the described measurement method, and the resulting values are shown in the following Table 2.

[0163]It was confirmed in Table 2 that the refined oils produced by the methods of Examples 1 to 8 satisfied 40 ppm or less of nitrogen, 5 ppm or less of chlorine, 5 ppm or less of sulfur, 5 ppm or less of metal-based compounds, 5 ppm or less of olefin, and 1 wt % or less of conjugated diolefin, and, in particular, the impurities in the mixed oil were significantly decreased with the oxygen content of 0.3 wt % or less, and preferably, were removed to a level at which the refined oil may be introduced to a crude oil refining process.

[0164]However, it was confirmed in Table 2 that the refined oils produced by the methods of Comparative Examples 1 and 2 had a high impurity content, as compared with the refined oils produced by the methods of Examples 1 to 8.

[0165]Therefore, the hydrogenation treatment method of a mixed oil according to an embodiment and the method for producing a refined oil including the same may allow a hydrogenation treatment with excellent reactivity, even when waste bio-oil containing a large amount of oxygen impurities is included, and the method for producing a refined oil may produce a refined oil having a very low impurity content, and, in particular, having even decreased oxygen impurities.

[0166]The hydrogenation treatment method of a mixed oil according to the present disclosure may continuously hydrogenate a mixed oil including a waste plastic pyrolysis oil and a waste bio-oil for a long time.

[0167]The hydrogenation treatment method of a mixed oil according to the present disclosure may provide a refined oil having a significantly low content of oxygen which is included in a large amount in the mixed oil.

[0168]The method for producing a refined oil according to the present disclosure may provide a refined oil having a significantly low impurity content by refining impurities such as chlorine, nitrogen, sulfur, and metal included in the mixed oil.

[0169]Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the embodiments but may be made in various forms which are different from each other, and those skilled in the art will understand that the present invention may be implemented in other specific forms without departing from the scope or essential features of the present disclosure. Therefore, the embodiments described above are not restrictive, but rather illustrative in all aspects. Furthermore, the embodiments may be combined to form additional embodiments.