Fouling reduction agent for heat exchanger in co-processing

Abstract

To provide a fouling reduction agent for a heat exchanger in co-processing which refines oil from a combination of biomass-derived oil and crude oil-derived oil.SOLUTION: A fouling reduction agent for a heat exchanger in co-processing, which refines oil from a combination of biomass-derived oil and crude oil-derived oil, contains a fatty acid ester inclusion.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an agent for reducing the fouling of heat exchangers in co-processing and a method for reducing the fouling of heat exchangers in co-processing. [Background technology]

[0002] The trend toward decarbonization is accelerating worldwide. In order to achieve low-carbon products at oil refineries, the introduction of co-processing technology, which co-processes low-carbon base materials such as biomass-derived oil, recycled waste plastic oil, and synthetic fuels with crude oil, is expected to expand in the future.

[0003] In the co-processing technology, for example, crude oil-derived oil obtained by high-temperature refining treatment of crude oil or the like as a feedstock in a vacuum distillation unit or the like and a low-carbon base material such as biomass-derived oil are mixed and processed in a secondary unit such as a fluid catalytic cracking unit (FCC) to obtain refined oils such as gasoline, kerosene, and diesel, and petrochemical feedstocks such as naphtha. In addition, before being fed into the FCC, the mixture of the crude oil-derived oil and the low-carbon base material is preheated to around 350°C in a heat exchanger (or in some cases, a heat exchanger and a heating furnace).

[0004] Here, FCC is used as a device in the normal oil refining process, where feedstock heavy oil is brought into contact with a fluid catalytic cracking catalyst at a high temperature of 430°C or higher, and the heavy oil is cracked and converted (produced) into low-boiling point hydrocarbons such as gasoline. In co-processing technology, the feedstock oil to be processed by the FCC mentioned above is low-carbon base materials such as vacuum gas oil (VGO) after desulfurization, biomass-derived oil, recycled waste plastic oil, and synthetic fuel, which are preheated to around 350°C in a heat exchanger (or in some cases, a heat exchanger and a heating furnace) before being fed into the FCC.

[0005] Here, in the petroleum refining process, crude oil, etc. is generally used as a feedstock oil in various refining apparatuses such as atmospheric distillation apparatuses and vacuum distillation apparatuses, and refining treatment is performed at high temperatures using crude oil, etc. as a feedstock oil. In order to improve the treatment efficiency in each apparatus, the feedstock oil to be treated is preheated in a heat exchanger beforehand and then sent to each apparatus. However, since the feedstock oil, such as crude oil, contains very heavy components, it is known that when it is preheated using a heat exchanger, deposits (also called dirt, fouling, or fouling) adhere to the heat exchange parts, and the heat exchange efficiency is likely to decrease. If the heat exchange efficiency decreases, the crude oil, etc., fed into various refining apparatuses is not sufficiently heated, and more energy is required for treatment in the refining apparatus. This leads to an increase in production costs and a decrease in productivity, as it is necessary to heat the crude oil, etc., separately in a heating furnace in advance, or to reduce the treatment amount of the refining apparatus if there is no heating furnace. Therefore, a fouling inhibitor for the heat exchanger for preheating the feedstock oil in the petroleum refining process, which can sufficiently suppress the adhesion of dirt to the preheating heat exchanger, is being developed. For example, it is known that fouling can be reduced by adding an antifouling agent such as a terpene compound having a boiling point of 200° C. or higher to the feedstock oil (Patent Document 1).

[0006] However, because the properties of the low-carbon base material used in coprocessing technology are different from those of crude oil, it is possible that corrosion, sludge, coke, etc. will be generated, which may lead to fouling. Furthermore, as mentioned above, fouling in heat exchangers is an obstacle to energy conservation in refineries, and suppressing fouling is important for achieving decarbonization, but there is little knowledge about fouling behavior during coprocessing.

[0007] Under these technical circumstances, there is a demand for technology that can reduce the adhesion of fouling to preheating system heat exchangers in co-processing technology, which refines oil from a combination of biomass-derived oil and crude oil-derived oil. [Prior art documents] [Non-patent literature]

[0008] [Patent Document 1] JP 2022-067630 A Summary of the Invention [Problem to be solved by the invention]

[0009] SUMMARY OF THE PRESENT EMBODIMENTS Accordingly, the present invention aims to provide a fouling reducing agent and method for heat exchanger fouling reduction used in co-processing to refine oil from a combination of biomass-derived oil and crude-derived oil. [Means for solving the problem]

[0010] As a result of intensive research into the above-mentioned problems, the present inventors have found that fouling of a heat exchanger in co-processing can be reduced by adding a fatty acid ester-containing substance to the feed oil. The present invention is based on this finding.

[0011] The present invention includes the following inventions. [1] A fouling reducing agent for a heat exchanger in co-processing of refined oil from a combination with biomass-derived oil, the fouling reducing agent comprising a fatty acid ester-containing material. [2] The stain-reducing agent according to [1], wherein the concentration of fatty acid ester-containing matter in the raw oil used in the coprocessing is 10 volume % or more. [3] The stain-reducing agent described in [2], wherein the raw oil is a combination of biomass-derived oil and crude oil-derived oil. [4] The stain-reducing agent according to any one of [1] to [3], wherein the fatty acid ester-containing material comprises at least one selected from the group consisting of fatty acid methyl esters (also known as FAMEs), fatty acid ethyl esters, and glycerides. [5] The stain-reducing agent according to any one of [1] to [4], wherein the fatty acid ester-containing material is at least one selected from the group consisting of biofuel, waste cooking oil, and vegetable oil. [6] A method for reducing fouling of a heat exchanger in co-processing of a combination of biomass-derived oil and crude-derived oil, comprising: providing a feedstock having added thereto an effective amount of a fatty acid ester content that reduces heat exchanger fouling; Supplying the feedstock to a heat exchanger. The method comprising: [7] The method for reducing fouling of a heat exchanger described in [6], wherein the concentration of fatty acid ester-containing substances in the raw oil is 10 volume % or more. [8] A method for producing refined oil and / or petrochemical feedstock by co-processing a combination of biomass-derived oil and crude oil, comprising: providing a feedstock having added thereto an effective amount of a fatty acid ester content that reduces heat exchanger fouling; feeding the feedstock to a heat exchanger; and Supplying the heated feedstock to a refinery. The method comprising: [9] A method for producing refined oil and / or petrochemical raw materials according to [8], wherein the concentration of fatty acid ester-containing matter in the raw oil is 10 volume % or more. Effect of the Invention

[0012] According to the present invention, it is possible to provide an agent for reducing fouling of a heat exchanger in coprocessing for refining oil from a combination of a biomass-derived oil and an oil derived from a crude oil. In addition, according to the present invention, it is possible to provide a method for reducing fouling of a heat exchanger in the above-mentioned coprocessing. In addition, according to the present invention, it is possible to provide a method for producing refined oil and / or petrochemical raw materials by the above-mentioned coprocessing. [Brief description of the drawings]

[0013] [Figure 1] The figure shows the Hot Liquid Process Simulator (HLPS) testing equipment used for the fouling evaluation. [Diagram 2]1 is a graph showing the results of fouling evaluation (change in Ud / Uc) of biodiesel fuel (BDF) containing fatty acid methyl ester (FAME) and vacuum gas oil after desulfurization treatment (hereinafter also referred to as desulfurized vacuum gas oil) obtained in Test Example 1. [Diagram 3] 1 is a graph showing the results of the fouling evaluation of Test Example 1 (changes in Ud / Uc) together with the mixture of desulfurized vacuum gas oil and BDF obtained in Test Example 2. [Figure 4] 1 is a graph showing the results of fouling evaluation (changes in Ud / Uc) of mixtures of desulfurized vacuum gas oil and BDF (80:20, 90:10) and desulfurized vacuum gas oil obtained in Test Example 3. [Diagram 5] 1 is a graph showing the results of fouling evaluation (changes in Ud / Uc) of waste edible oil and desulfurized vacuum gas oil obtained in Test Example 4. Description of the Invention

[0014] One of the features of the fouling reducing agent for a heat exchanger in coprocessing of the present invention is that it contains a fatty acid ester-containing substance.

[0015] Co-processing According to one embodiment of the present invention, the reduction of heat exchanger fouling of the present invention is the reduction of heat exchanger fouling in co-processing.

[0016] As a technology for decarbonizing refineries, CO2-based fuels such as biomass-derived oil, recycled waste plastic oil, and synthetic fuels are being developed in addition to crude oil. 2 There is a co-processing technology that mixes and co-processes low-emission base materials (low-carbon base materials).

[0017] In the co-processing technology, for example, in a vacuum distillation unit or the like, crude oil-derived oil obtained by high-temperature refining treatment using crude oil as a feedstock oil and at least one low-carbon base material selected from the group consisting of biomass-derived oil, waste plastic recycled oil, and synthetic fuel can be mixed and treated in the refining unit to obtain refined oils such as naphtha, gasoline, kerosene, and diesel, and / or petrochemical raw materials. The crude oil-derived oil is preferably atmospheric residual oil obtained in an atmospheric distillation unit, diesel (vacuum gas oil; VGO) obtained in a vacuum distillation unit, desulfurized vacuum gas oil, and residual oil obtained in a vacuum distillation unit. In addition, the refining unit is preferably a secondary unit such as a fluid catalytic cracking (FCC) unit. Here, FCC is a unit that brings a feedstock oil into contact with a fluid catalytic cracking catalyst at a high temperature of, for example, 430°C or higher, cracks the feedstock oil, and converts (produces) it into low-boiling point hydrocarbons such as gasoline.

[0018] According to one embodiment of the present invention, in the co-processing technology, the feedstock oil to be treated by the FCC includes a combination of biomass-derived oil and crude oil-derived oil. The combination of the low-carbon substrate and crude oil-derived oil is preheated to about 350°C in a heat exchanger (or in some cases, a heat exchanger and a heating furnace) and then fed into the FCC.

[0019] Oil derived from crude oil According to one embodiment of the present invention, the oil derived from the crude oil of the present invention includes oil obtained by refining crude oil as a feedstock oil at high temperatures using various refining apparatuses such as atmospheric distillation units, vacuum distillation units, fluid catalytic cracking units (FCC), hydrocracking units (HDC), and thermal cracking units (Coker) or combinations thereof in a conventional petroleum refining process. Examples of such crude oil-derived oil include LPG, naphtha, gasoline, kerosene, light diesel oil, heavy diesel oil, A-class fuel oil, atmospheric residual oil (residual oil obtained by atmospheric distillation of crude oil) (preferably atmospheric residual oil (DSAR) after desulfurization), vacuum gas oil (gas oil obtained by further vacuum distillation of atmospheric residual oil; VGO) (preferably vacuum gas oil after desulfurization), vacuum residual oil, hydrotreated oils thereof, and thermal cracking oils, as well as mixtures thereof, preferably VGO and DSAR.

[0020] Low Carbon Substrate According to one embodiment of the present invention, the low carbon substrate of the present invention is 2 There are no particular limitations on the base material as long as it is one that produces a small amount of emissions, and it is preferably a biomass-derived oil.

[0021] The biomass-derived oil is not particularly limited, and examples thereof include oils derived from plants or animals, which may be subjected to pyrolysis or methyl esterification. Examples of the plant-derived oil include palm oil, rapeseed oil, soybean oil, tall oil, algae oil, corn oil, grapeseed oil, rubber seed oil, wood pyrolysis oil, and other vegetable oils and their waste edible oils. Examples of the animal-derived oil include animal oils such as lard and tallow. In addition, the biomass-derived oil may be FAME obtained by methyl esterification of waste edible oil, palm oil, rapeseed oil, soybean oil, or other such oils, or biofuels containing FAME. The biomass-derived oil is preferably FAME, biofuel, vegetable oil, and its waste edible oil.

[0022] Feedstocks used in coprocessing According to one embodiment of the present invention, the feedstock oil used in the coprocessing of the present invention is not particularly limited, and is preferably a combination of a biomass-derived oil and a crude oil-derived oil. More preferably, the feedstock oil is a combination of at least one biomass-derived oil selected from FAME-containing biofuel, waste edible oil, and vegetable oil, and at least one crude oil-derived oil selected from vacuum gas oil, atmospheric residual oil, and desulfurized atmospheric residual oil. The combination of the biomass-derived oil and the crude oil-derived oil may be configured as a mixture or may be configured as separate entities. Specifically, the biomass-derived oil and the crude oil-derived oil may be supplied separately to the heat exchanger, or may be supplied as a mixture of the biomass-derived oil and the crude oil-derived oil, preferably as a mixture.

[0023] According to another embodiment of the present invention, the concentration of biomass-derived oil in the feedstock oil used in the coprocessing of the present invention is, for example, 10% by volume or more, 20% by volume or more, 20 to 90% by volume, 30 to 80% by volume, or 40 to 70% by volume.

[0024] Refined oils and / or petrochemical feedstocks obtained through co-processing According to one embodiment of the present invention, refined oil and / or petrochemical feedstock is obtained by the coprocessing of the present invention. The refined oil obtained by the coprocessing of the present invention is preferably gasoline, kerosene, diesel, etc. The petrochemical feedstock obtained by the coprocessing of the present invention is preferably naphtha, etc. In this specification, "refined oil and / or petrochemical feedstock" refers to refined oil, petrochemical feedstock, or a combination of refined oil and petrochemical feedstock.

[0025] heat exchanger Examples of heat exchangers in coprocessing to which the fouling reducing agent of the present invention is applicable (preferably, a heat exchanger for preheating feedstock oil) include, for example, a heat exchanger for an atmospheric distillation unit (preferably, a heat exchanger for preheating feedstock oil for an atmospheric distillation unit), a heat exchanger for a vacuum distillation unit (preferably, a heat exchanger for preheating feedstock oil for a vacuum distillation unit), a heat exchanger for a fluid catalytic cracking unit (FCC) (preferably, a heat exchanger for preheating feedstock oil for an FCC), a heat exchanger for a direct desulfurization unit (preferably, a heat exchanger for preheating feedstock oil for a direct desulfurization unit), or a heat exchanger for an indirect desulfurization unit (preferably, a heat exchanger for preheating feedstock oil for an indirect desulfurization unit), a heat exchanger for a hydrocracker (HDC), a heat exchanger for a thermal cracker (Coker), and the like. Preferably, it is an FCC heat exchanger or an HDC heat exchanger.

[0026] Purification equipment According to one embodiment of the present invention, the feedstock oil heated in the heat exchanger is supplied to a refinery to produce refined oil and / or petrochemical feedstock. The refinery is preferably a secondary unit used in coprocessing, such as an atmospheric distillation unit, a vacuum distillation unit, a fluid catalytic cracking unit (FCC), a hydrocracking unit (HDC), etc., and is preferably an FCC or HDC. Here, the vacuum distillation unit, etc., includes a heating furnace in its configuration.

[0027] Fatty acid ester content The fouling reducing agent for the heat exchanger in the co-processing of the present invention contains a fatty acid ester. According to a preferred embodiment of the present invention, the fouling reducing agent of the present invention can reduce the adhesion of fouling substances to the heat exchanger. That is, the fouling reducing agent of the present invention can reduce fouling (fouling in the heat exchanger).

[0028] The fatty acid ester in the fatty acid ester-containing material is not particularly limited, but may be, for example, an ester of a monohydric to trihydric alcohol and a fatty acid. Specific examples of such fatty acid esters include esters of methanol and a fatty acid (fatty acid methyl esters), esters of ethanol and a fatty acid (fatty acid ethyl esters), and esters of glycerin and a fatty acid (glycerin fatty acid esters, also called glycerides), and are preferably fatty acid methyl esters, fatty acid ethyl esters, and glycerides. The glycerides may be monoglycerides, diglycerides, or triglycerides, or may be mixtures thereof.

[0029] The number of carbon atoms of the fatty acid constituting the fatty acid methyl ester includes, for example, 14 to 25 carbon atoms, preferably 14 to 20 carbon atoms, and more preferably 16 to 18 carbon atoms. Examples of the fatty acid methyl ester composed of the above fatty acids include fatty acid methyl esters derived from waste cooking oil, rapeseed oil, soybean oil, palm oil, tall oil, etc., and preferably fatty acid methyl esters derived from waste cooking oil. The above fatty acid methyl esters can be obtained by methyl esterification of vegetable oils such as waste cooking oil and rapeseed oil.

[0030] According to one embodiment of the present invention, the ratio of the fatty acid ester having a fatty acid with 14 carbon atoms is not particularly limited, but may be, for example, 2.5% by mass or less, 0 to 1% by mass, based on the total amount of fatty acid esters. The ratio of the fatty acid ester having a fatty acid with 16 carbon atoms is not particularly limited, but may be, for example, 30% by mass or less, 5 to 15% by mass, based on the total amount of fatty acid esters. The ratio of the fatty acid ester having a fatty acid with 18 carbon atoms is not particularly limited, but may be, for example, 70% by mass or more, 80 to 95% by mass, based on the total amount of fatty acid esters. The ratio of the fatty acid ester having a fatty acid with 20 carbon atoms is not particularly limited, but may be, for example, 3% by mass or less, 0 to 2% by mass, based on the total amount of fatty acid esters. The ratio of the fatty acid ester having a fatty acid with 22 carbon atoms is not particularly limited, but may be, for example, 3% by mass or less, 0 to 2% by mass, based on the total amount of fatty acid esters. The ratio of the fatty acid ester having a fatty acid with 25 carbon atoms is not particularly limited, but may be, for example, 3% by mass or less, 0 to 2% by mass, based on the total amount of fatty acid esters.

[0031] In the present invention, the content of fatty acid esters having fatty acids with specific carbon numbers can be measured by comprehensive two-dimensional gas chromatography (GCxGC). Examples of conditions for comprehensive two-dimensional gas chromatography are shown below. <Condition> Equipment:GC:Agilent6890N MS: JEOL AccuTOF GC GCxGC:ZOEX KT2004 Autosampler: GERSTEL MPS2 Column: Primary column: DBWAXETR (30m x 0.25mm x 0.2μm) Secondary column: DB-1 (1m x 0.1mm x 0.1μm) Modulation period: 12 seconds Detector: Flame ionization detector Temperature: Oven: 35℃ (4 min) → 3℃ / min, 240℃ (48 min) Inlet: 280℃ Detector: 320℃ Carrier gas: He (constant flow mode)

[0032] According to one embodiment of the present invention, the fatty acid ester-containing material of the present invention may contain other components such as fatty acids (e.g., free fatty acids) and water together with fatty acid esters. Such fatty acid ester-containing materials are not particularly limited as long as they contain fatty acid esters, and examples thereof include waste edible oil, biofuels (e.g., biodiesel fuels), and vegetable oils, and preferably biodiesel fuels and waste edible oils. Here, it is known that the main component of vegetable oils and waste edible oils is glyceride, and the content of glyceride in waste edible oils is 70% by mass or more, preferably 80% by mass or more, and more preferably 85% by mass or more. The glyceride in waste edible oils may include triglyceride.

[0033] According to one embodiment of the present invention, the content of the fatty acid ester in the fatty acid ester-containing material of the present invention is not particularly limited, but is, for example, 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass, based on the total fatty acid ester-containing material. The upper limit of the content of the fatty acid ester in the fatty acid ester-containing material is not particularly limited, but can be, for example, 100% by mass.

[0034] According to a preferred embodiment of the present invention, the fatty acid ester-containing material of the present invention may be, for example, biofuel, waste cooking oil, vegetable oil, or a combination thereof, and is preferably biofuel, waste cooking oil, or vegetable oil.

[0035] According to one embodiment of the present invention, the fatty acid ester-containing product of the present invention and the biomass-derived oil may be the same.

[0036] According to one embodiment of the present invention, the "stain-reducing agent" of the present invention may be a "stain-reducing composition" when it is a mixture of multiple components.

[0037] According to one embodiment of the present invention, the content of the unsaturated fatty acid ester in the fatty acid ester is not particularly limited, but is, for example, 60 to 99% by mass, preferably 75 to 95% by mass, and more preferably 80 to 90% by mass, based on the total amount of the fatty acid ester. According to another embodiment of the present invention, when the fatty acid ester-containing material contains a fatty acid together with the fatty acid ester, the content of the unsaturated fatty acid and the unsaturated fatty acid ester is, for example, not particularly limited, but is, for example, 60 to 99% by mass, preferably 75 to 95% by mass, and more preferably 80 to 90% by mass, based on the total amount of the fatty acid and the fatty acid ester. The concentrations of the saturated fatty acid, the saturated fatty acid ester, the unsaturated fatty acid, and the unsaturated fatty acid ester can be measured by a method known in the art, for example, a gas chromatographic method. In this case, for more accurate concentration measurement, it is desirable to use a calibration curve created based on the measured values ​​of several control samples having known concentrations.

[0038] According to one embodiment of the present invention, the content of the monounsaturated fatty acid ester in the fatty acid ester of the present invention is not particularly limited, but is, for example, 40 to 70 mass%, preferably 45 to 65 mass%, more preferably 50 to 60 mass%, based on the total amount of the fatty acid ester. According to another embodiment of the present invention, when the fatty acid ester-containing material contains fatty acid together with the fatty acid ester, the content of the monounsaturated fatty acid and the monounsaturated fatty acid ester is, for example, 40 to 70 mass%, preferably 45 to 65 mass%, more preferably 50 to 60 mass%, based on the total amount of the fatty acid and the fatty acid ester, but is not particularly limited.

[0039] According to one embodiment of the present invention, the content of the polyunsaturated fatty acid ester in the fatty acid ester of the present invention is not particularly limited, but is, for example, 15 to 55 mass%, preferably 20 to 45 mass%, more preferably 25 to 40 mass%, based on the total amount of the fatty acid ester. According to another embodiment of the present invention, when the fatty acid ester-containing material contains fatty acid together with the fatty acid ester, the content of the polyunsaturated fatty acid and the polyunsaturated fatty acid ester is, for example, not particularly limited, but is, for example, 15 to 55 mass%, preferably 20 to 45 mass%, more preferably 25 to 40 mass%, based on the total amount of the fatty acid and the fatty acid ester.

[0040] According to one embodiment of the present invention, the content of the saturated fatty acid ester in the fatty acid ester of the present invention is not particularly limited, but is, for example, 3 to 25 mass%, preferably 5 to 20 mass%, more preferably 10 to 15 mass%, based on the total amount of all fatty acid esters. According to another embodiment of the present invention, when the fatty acid ester-containing material contains fatty acids together with fatty acid esters, the content of the saturated fatty acid and the saturated fatty acid ester is not particularly limited, but is, for example, 3 to 25 mass%, preferably 5 to 20 mass%, more preferably 10 to 15 mass%, based on the total amount of fatty acid and fatty acid ester.

[0041] According to one embodiment of the present invention, the initial boiling point of the distillation property of the fatty acid ester-containing material of the present invention is not particularly limited, but may be, for example, 270 to 380° C., and preferably 290 to 360° C. When the fatty acid ester-containing material is a biodiesel fuel, the initial boiling point may be, for example, 270 to 380° C., and preferably 290 to 330° C. When the fatty acid ester-containing material is a waste edible oil, the initial boiling point may be, for example, 340 to 380° C., and preferably 300 to 360° C. The initial boiling point can be measured by a method known in the art, for example, based on the provisions of JIS K2254:1998.

[0042] According to one embodiment of the present invention, the end point of the distillation property of the fatty acid ester-containing material of the present invention is not particularly limited, but may be, for example, 530 to 700° C., and preferably 560 to 670° C. When the fatty acid ester-containing material is a biodiesel fuel, the end point may be, for example, 530 to 700° C., and preferably 560 to 600° C. When the fatty acid ester-containing material is waste edible oil, the end point may be, for example, 530 to 700° C., and preferably 610 to 670° C. The end point can be measured by a method known in the art, for example, based on the provisions of JIS K2254:1998.

[0043] According to one embodiment of the present invention, the density (15°C) of the fatty acid ester-containing material of the present invention is not particularly limited, but is, for example, 0.830 to 0.980 g / cm 3 and preferably 0.860 to 0.950 g / cm 3 When the fatty acid ester-containing material is a biodiesel fuel, its density (15°C) is, for example, 0.830 to 0.980 g / cm 3 and preferably 0.860 to 0.900 g / cm 3 When the fatty acid ester-containing material is waste edible oil, its density (15°C) is, for example, 0.830 to 0.980 g / cm 3 and preferably 0.910 to 0.950 g / cm 3 The density (15°C) can be measured by a method known in the art, for example, based on the provisions of JIS K 2249-1:2011.

[0044] According to one embodiment of the present invention, the water content in the fatty acid ester-containing material of the present invention is not particularly limited, but may be, for example, 50 to 2000 ppm by mass, preferably 100 to 1800 ppm by mass. When the fatty acid ester-containing material is a biodiesel fuel, the water content may be, for example, 50 to 500 ppm by mass, preferably 100 to 300 ppm by mass. When the fatty acid ester-containing material is a waste edible oil, the water content may be, for example, 1200 to 2000 ppm by mass, preferably 1500 to 1800 ppm by mass. The water content can be measured by a method known in the art, for example, based on the provisions of JIS K 2275-3:2015.

[0045] According to one embodiment of the present invention, the total chlorine content in the fatty acid ester-containing material of the present invention is not particularly limited, but for example, 200 mass ppm or less, preferably 100 mass ppm or less. When the fatty acid ester-containing material is a biodiesel fuel, the total chlorine content is, for example, 200 mass ppm or less, preferably 100 mass ppm or less. When the fatty acid ester-containing material is waste edible oil, the total chlorine content is, for example, 200 mass ppm or less, preferably 100 mass ppm or less. The lower limit of the total chlorine content is not particularly limited, but can be, for example, 0 mass ppm. The total chlorine content can be measured by a method known in the art, for example, ion chromatography.

[0046] According to one embodiment of the present invention, the inorganic chlorine content in the fatty acid ester-containing material of the present invention is not particularly limited, but for example, 10 mass ppm or less, preferably 5 mass ppm or less. When the fatty acid ester-containing material is a biodiesel fuel, the inorganic chlorine content is, for example, 10 mass ppm or less, preferably 5 mass ppm or less. When the fatty acid ester-containing material is waste edible oil, the inorganic chlorine content is, for example, 10 mass ppm or less, preferably 5 mass ppm or less. The lower limit of the inorganic chlorine content is not particularly limited, but can be, for example, 0 mass ppm. The total inorganic chlorine content can be measured by a method known in the art, for example, ion chromatography after extraction with water.

[0047] According to one embodiment of the present invention, the sulfur content in the fatty acid ester-containing material of the present invention is not particularly limited, but may be, for example, 200 ppm by mass or less, preferably 100 ppm by mass or less. When the fatty acid ester-containing material is a biodiesel fuel, the sulfur content may be, for example, 50 ppm by mass or less, preferably 10 ppm by mass or less. When the fatty acid ester-containing material is waste edible oil, the sulfur content may be, for example, 200 ppm by mass or less, preferably 100 ppm by mass or less. The lower limit of the sulfur content is not particularly limited, but may be, for example, 0 ppm by mass. The sulfur content can be measured based on a method known in the art, for example, "Crude oil and petroleum products-Sulfur content test method-Part 6: Ultraviolet fluorescence method" as specified in JIS K 2541-6:2003.

[0048] According to one embodiment of the present invention, the C (carbon) content (residual carbon content) in the fatty acid ester-containing material of the present invention is not particularly limited, but may be, for example, 25 to 200 mass ppm, preferably 50 to 100 mass%. When the fatty acid ester-containing material is a biodiesel fuel, the C (carbon) content may be, for example, 25 to 200 mass ppm, preferably 50 to 100 mass%. When the fatty acid ester-containing material is a waste edible oil, the C (carbon) content may be, for example, 25 to 200 mass ppm, preferably 50 to 100 mass%. The C (carbon) content (residual carbon content) can be measured by a method known in the art, for example, based on the provisions of JIS M 8819:1997.

[0049] According to one embodiment of the present invention, the H (hydrogen) content in the fatty acid ester-containing material of the present invention is not particularly limited, but may be, for example, 5 to 25 mass ppm, and preferably 10 to 20 mass%. When the fatty acid ester-containing material is a biodiesel fuel, the H (hydrogen) content may be, for example, 5 to 25 mass ppm, and preferably 10 to 20 mass%. When the fatty acid ester-containing material is waste edible oil, the H (hydrogen) content may be, for example, 5 to 25 mass ppm, and preferably 10 to 20 mass%. The H (hydrogen) content can be measured by a method known in the art, for example, based on the provisions of JIS M 8819:1997.

[0050] According to one embodiment of the present invention, the O (oxygen) content in the fatty acid ester-containing material of the present invention is not particularly limited, but may be, for example, 5 to 25 ppm by mass, and preferably 10 to 20% by mass. When the fatty acid ester-containing material is a biodiesel fuel, the O (oxygen) content may be, for example, 5 to 25 ppm by mass, and preferably 10 to 20% by mass. When the fatty acid ester-containing material is a waste edible oil, the O (oxygen) content may be, for example, 5 to 25 ppm by mass, and preferably 10 to 20% by mass. The O (oxygen) content can be measured by a method known in the art, for example, based on the provisions of JIS M 8819:1997.

[0051] According to one embodiment of the present invention, the nitrogen content (trace nitrogen) in the fatty acid ester-containing material of the present invention is not particularly limited, but is, for example, 5 to 100 ppm by mass, preferably 10 to 50 ppm by mass. When the fatty acid ester-containing material is a biodiesel fuel, the nitrogen content is, for example, 5 to 50 ppm by mass, preferably 10 to 20% by mass. When the fatty acid ester-containing material is waste edible oil, the nitrogen content is, for example, 10 to 100 ppm by mass, preferably 20 to 50% by mass. The nitrogen content can be measured according to a method known in the art, for example, the "Crude oil and petroleum products - Nitrogen analysis test method" (chemiluminescence method) specified in JIS K 2609 (1998).

[0052] According to one embodiment of the present invention, a use mode can be mentioned in which raw oil containing the fouling reducing agent according to the present invention is supplied to and circulated in a heat exchanger to which it is applied, and such an embodiment can reduce (or suppress) adhesion of fouling substances to the inner wall surface of the heat exchanger. According to the above embodiment of the fouling reducing agent according to the present invention, the fouling reducing effect (preferably the fouling prevention effect) of the heat exchanger can be exhibited while the heat exchanger is continuously operated, so that the fouling reducing agent according to the present invention is preferably supplied to and circulated in a state in which it is blended with raw oil in a heat exchanger to which it is applied.

[0053] Thus, the fouling reducing agent according to the present invention is preferably used for the purpose of reducing (preferably preventing) adhesion of fouling substances to the inner wall surface of a heat exchanger in coprocessing. The reduction in fouling by the fouling reducing agent of the present invention can be evaluated, for example, in an HLPS test apparatus described below. The ratio (Ud / Uc) of the overall heat transfer coefficient (Ud) after 5 hours to the initial value (Uc) in the HLPS test apparatus is preferably 0.95 to 1.00.

[0054] When the raw oil containing the fouling reducing agent according to the present invention is supplied to a heat exchanger to which it is applied, the concentration of the fatty acid ester-containing material as the fouling reducing agent according to the present invention in the raw oil can be, for example, 10% by volume or more, 20% by volume or more, 20 to 90% by volume, 30 to 80% by volume, or 40 to 70% by volume. By having the concentration of the fouling reducing agent in the raw oil within the above range, the adhesion of fouling substances to the inner wall surface of the heat exchanger by the raw oil can be further reduced.

[0055] According to another embodiment of the present invention, when the raw oil containing the fouling reducing agent according to the present invention is supplied to the heat exchanger to which it is applied, the concentration of the fatty acid ester in the fouling reducing agent according to the present invention in the raw oil is, for example, 9% by volume or more, 10% by volume or more, 20% by volume or more, 20 to 90% by volume, 30 to 80% by volume, or 40 to 70% by volume. By having the concentration of the fouling reducing agent in the raw oil within the above range, the adhesion of fouling substances to the inner wall surface of the heat exchanger by the raw oil can be further reduced.

[0056] Methods for reducing heat exchanger fouling in co-processing. According to another aspect of the present invention, there is provided a method for reducing fouling of a heat exchanger in co-processing a combination of biomass-derived oil and crude-derived oil, the method preferably comprising the steps of providing a feedstock having added thereto an effective amount of fatty acid ester content to reduce fouling of the heat exchanger, and feeding the feedstock to a heat exchanger.

[0057] In the method for reducing fouling of heat exchangers in coprocessing, the effective amount of fatty acid ester-containing material for reducing fouling of heat exchangers is similar to the concentration of fatty acid ester-containing material in the feedstock blended with the fouling-reducing agent described above.

[0058] Method for producing refined oils and / or petrochemical feedstocks while reducing heat exchanger fouling in co-processing - Patent Application 20070233633 According to another aspect of the present invention, there is provided a method for producing refined oil and / or petrochemical feedstock by co-processing a combination of biomass-derived oil and crude oil-derived oil. The method for producing refined oil and / or petrochemical feedstock preferably includes the steps of preparing a feedstock oil to which an effective amount of fatty acid ester content for reducing fouling of a heat exchanger has been added, feeding the feedstock oil to a heat exchanger, and feeding the heated feedstock oil to a refinery.

[0059] In the method for producing refined oil and / or petrochemical feedstock by the above-mentioned coprocessing, the effective amount of fatty acid ester-containing material for reducing fouling of a heat exchanger is similar to the concentration of fatty acid ester-containing material in the feedstock oil blended with the above-mentioned fouling reducing agent. EXAMPLES

[0060] The present invention will be described in more detail below with reference to examples and test examples, but the present invention is not limited to these test examples. The measurement methods and units of the present invention are in accordance with the provisions of the Japanese Industrial Standards (JIS) unless otherwise specified.

[0061] In the following test examples, fouling evaluation was carried out using a Hot Liquid Process Simulator (HLPS) test device, which is shown in Figure 1. The test oil in the test oil tank 1 (500 mL) is pumped by a constant flow pump 2 into a test tube with a heater rod 3 installed in the center. Thermometers 5-7 are installed at the inlet and outlet of the test tube 4 and inside the heater rod. When fouling substances in the test oil adhere to and accumulate on the heater, the heat transfer efficiency from the heater deteriorates and the outlet temperature drops. From this, the overall heat transfer coefficient (Ud), which is an index of heat transfer efficiency, was calculated from the temperature, flow rate, and physical properties of the test oil, and the change from the initial value (Uc) was obtained. Specifically, the fouling behavior of each feedstock oil was evaluated by comparing the time-dependent change in the ratio (Ud / Uc) of the overall heat transfer coefficient (Ud) to the initial value (Uc). Regarding the test temperature, the temperature of the heater thermometer 7 was set to 465°C, and the temperature of the outlet thermometer 6 of the HLPS test equipment was set to 340-350°C, referring to the operating temperature of the secondary equipment where coprocessing is expected to be performed. The test flow rate was set to 1 mL / min, and the run time was set to 5 hours.

[0062] In the following test examples, the test oils used were biodiesel fuel (hereinafter also referred to as Bio Diesel Fuel, BDF), diesel oil obtained by further vacuum distillation and desulfurization of atmospheric residual oil obtained by distilling crude oil (hereinafter also referred to as desulfurized vacuum diesel oil), and waste cooking oil. BDF was obtained by methyl esterifying waste cooking oil with methanol to generate fatty acid methyl ester (FAME), and separating and removing methanol and glycerin. Desulfurized vacuum diesel was obtained by distilling atmospheric residual oil obtained as residual oil when crude oil is treated in an atmospheric distillation unit, using it as a raw material, distilling it in a vacuum distillation unit, and desulfurizing it.

[0063] The general properties of BDF, waste edible oil, and desulfurized vacuum diesel are shown in Table 1. The physical properties shown in Table 1 were measured by the methods described below.

[0064] (Distillation properties: initial boiling point, end point) Measurements were performed based on the standards of JIS K 2254:1998.

[0065] (Density at 15℃) Measurements were performed based on the provisions of JIS K 2249-1:2011.

[0066] (moisture) Measurements were performed based on the provisions of JIS K 2275-3:2015.

[0067] (Total Chlorine) The measurement was carried out using ion chromatography.

[0068] (Inorganic Chlorine) After extraction with water, the content was measured using ion chromatography.

[0069] (Sulfur (sulfur content)) Measurements were performed based on "Crude petroleum and petroleum products - Sulfur content test method - Part 6: Ultraviolet fluorescence method" specified in JIS K 2541-6:2003.

[0070] (C(carbon)(residual carbon)) Measurements were performed based on JIS M 8819:1997.

[0071] (H(hydrogen)) Measurements were performed based on JIS M 8819:1997.

[0072] (O(oxygen)) Measurements were performed based on JIS M 8819:1997.

[0073] (Trace nitrogen (nitrogen content)) "Crude oil and petroleum products - Nitrogen analysis test method" specified in JIS K 2609 (1998) (chemiluminescence method) was used for the measurement.

[0074] [Table 1]

[0075] The proportions of fatty acid esters in BDF and fatty acids and fatty acid esters in waste cooking oil are shown in Table 2. The molecular structures of the fatty acids and fatty acid esters shown in Table 2 were determined by gas chromatography. First, the fatty acids and fatty acid esters in the sample (waste cooking oil) were saponified with a 0.5 mol / L solution of sodium hydroxide in methanol, methyl esterified with a solution of boron trifluoride methanol complex in methanol, and then extracted with hexane to obtain a sample for gas chromatography. The sample (BDF) was extracted with hexane to obtain a sample for gas chromatography. Gas chromatography (detection: hydrogen flame ionization detector) was then performed. The analysis was entrusted to the Japan Food Analysis Center, a general incorporated association.

[0076] [Table 2] The FAME content in BDF is 91% by mass.

[0077] The carbon number distribution of the fatty acids constituting the FAME in BDF is shown in Table 3. The carbon number distribution of the fatty acids constituting the fatty acid esters shown in Table 3 was measured and calculated under the following conditions using comprehensive two-dimensional gas chromatography (GCxGC).

[0078] <Condition> Equipment:GC:Agilent6890N MS: JEOL AccuTOF GC GCxGC:ZOEX KT2004 Autosampler: GERSTEL MPS2 Columns: 1st column: DBWAXETR (30m x 0.25mm x 0.2μm) Second column: DB-1 (1m x 0.1mm x 0.1μm) Modulation period: 12 seconds Detector: Flame ionization detector Temperature: Oven: 35℃ (4 min) → 3℃ / min, 240℃ (48 min) Inlet: 280℃ Detector: 320℃ Carrier gas: He (constant flow mode) [Table 3]

[0079] Test example 1: Fouling evaluation of a single substrate (change in overall heat transfer coefficient) Fouling evaluation was carried out using an HLPS test device. The test oils used were BDF and, as a comparative example, desulfurized vacuum gas oil. The results of the fouling evaluation are shown in Figure 2. As a result, the rate of decrease in Ud / Uc increased in the desulfurized vacuum gas oil.

[0080] Test example 2: Fouling evaluation under co-processing conditions (change in overall heat transfer coefficient) Fouling evaluation was carried out using an HLPS test device. The test oil used was a mixture of desulfurized vacuum gas oil and BDF (desulfurized vacuum gas oil:BDF (volume ratio) = 60:40). The results of the fouling evaluation are shown in Figure 3. As a result, it was found that when BDF is co-processed together with desulfurized vacuum gas oil, the progression of fouling of the desulfurized vacuum gas oil during coprocessing can be greatly suppressed, in other words, fouling can be reduced.

[0081] Test Example 3: Fouling evaluation under co-processing conditions (change in overall heat transfer coefficient) (examination of the ratio of desulfurized vacuum gas oil to BDF) Fouling evaluation was carried out using an HLPS test device. The test oil used was a mixture of desulfurized vacuum gas oil and BDF (desulfurized vacuum gas oil:BDF (volume ratio) = 90:10, 80:20). The results of the fouling evaluation are shown in Figure 4. As a result, it was found that even when BDF was set to 10 vol%, the progression of fouling of desulfurized vacuum gas oil during coprocessing could be greatly suppressed, that is, fouling could be reduced.

[0082] Test Example 4: Fouling evaluation under co-processing conditions (change in overall heat transfer coefficient) (examination of waste cooking oil) Fouling evaluation was carried out using an HLPS test device. The test oils used were a mixture of desulfurized vacuum gas oil and waste cooking oil (desulfurized vacuum gas oil: waste cooking oil (volume ratio) = 60:40), and desulfurized vacuum gas oil. The results of the fouling evaluation are shown in Figure 5. As a result, it was found that even when 40 volume% waste cooking oil was used, the progression of fouling of desulfurized vacuum gas oil during coprocessing could be greatly suppressed, that is, dirt could be reduced. [Explanation of symbols]

[0083] 1 Test oil tank 2 Constant flow pump 3 Heater Rod 4. Test Tube 5 Inlet thermometer 6 outlet thermometer 7 Heater Thermometer 8. Flow

Claims

1. A fouling reducing agent for a heat exchanger in co-processing of oil refined from a combination of biomass-derived oil and crude-derived oil, the fouling reducing agent comprising a fatty acid ester content.

2. The stain reducing agent according to claim 1 , wherein the concentration of fatty acid ester-containing substances in the feedstock oil used in the coprocessing is 10% by volume or more.

3. 3. The stain reducing agent of claim 2, wherein the feedstock is a combination of biomass-derived oil and crude-derived oil.

4. 3. The stain-reducing agent according to claim 1, wherein the fatty acid ester-containing substance comprises at least one selected from the group consisting of fatty acid methyl esters, fatty acid ethyl esters, and glycerides.

5. The stain-reducing agent according to claim 4, wherein the fatty acid ester-containing material is at least one selected from the group consisting of biofuel, waste cooking oil, and vegetable oil.

6. 1. A method for reducing fouling of a heat exchanger in co-processing a combination of biomass-derived oil and crude-derived oil to produce oil, comprising: providing a feedstock having added thereto an effective amount of a fatty acid ester content that reduces heat exchanger fouling; Supplying the feedstock to a heat exchanger. The method comprising:

7. 7. The method for reducing fouling of a heat exchanger according to claim 6, wherein the concentration of fatty acid ester-containing substances in the feed oil is 10% by volume or more.

8. 1. A method for producing refined oil and / or petrochemical feedstock by co-processing a combination of biomass-derived oil and crude-derived oil, comprising: providing a feedstock having added thereto an effective amount of a fatty acid ester content that reduces heat exchanger fouling; feeding the feedstock to a heat exchanger; and Supplying the heated feedstock to a refinery. The method comprising:

9. 9. The method for producing refined oil and / or petrochemical raw material according to claim 8, wherein the concentration of fatty acid ester-containing matter in the raw oil is 10% by volume or more.

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