JP5070168B2 - Method for producing hydrocarbon oil - Google Patents

Description

  The present invention relates to a method for producing a hydrocarbon oil.

  Attention has been focused on the effective use of biomass energy as a measure to prevent global warming. Among biomass energy, biomass energy derived from plants can effectively use hydrocarbons converted from carbon dioxide by photosynthesis in the growth process of plants, so it does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of life cycle, so-called, It has the property of being carbon neutral.

  Various uses of such biomass energy have been studied in the field of transportation fuel. For example, if a fuel derived from animal and vegetable oils can be used as a diesel fuel, it is expected to play an effective role in reducing carbon dioxide emissions due to a synergistic effect with the high energy efficiency of a diesel engine. As diesel fuel using animal and vegetable oils, fatty acid methyl ester (Fatty Acid Methyl Ester) is known. Fatty acid methyl ester oil is produced by transesterification with methanol using a basic catalyst or the like for a triglyceride structure, which is a general structure of animal and vegetable oils.

  However, in the process for producing fatty acid methyl ester, as described in Patent Document 1 below, it is necessary to treat glycerin produced as a by-product, and it may be costly and energy-consuming to wash the produced oil. It has been pointed out.

  Moreover, in addition to the above problems, there are the following problems in order to use fat and oil components derived from animal and vegetable oils and fuels produced from these components. That is, since the oil and fat component derived from animal and vegetable oils generally has an oxygen atom in the molecule, there is a concern that the oxygen content may adversely affect the engine material, and that the oxygen content is removed to an extremely low concentration. Is difficult. In addition, when using a mixture of oil and fat components derived from animal and vegetable oils and petroleum hydrocarbon fractions, in the conventional technology, the oxygen content in the oil and fat components and the sulfur content in the petroleum hydrocarbon fractions are used. Both contents cannot be reduced sufficiently.

Therefore, a method for producing fuel oil composed of hydrocarbon oil by deoxygenation (hydrodeoxygenation) by hydrotreating oil and fat components derived from animals and plants has been studied (for example, see Patent Documents 2 and 3 below). ).
JP 2005-154647 A EP1395531A2 publication WO2006 / 100584A2 publication

  By the way, when oxygen and chlorine are contained in the raw material oil, acidic water containing water-soluble chlorine-containing compounds such as chlorine, hydrogen chloride or other chloride ions is by-produced during hydrodeoxygenation. Acidic water containing a water-soluble chlorine-containing compound has extremely strong metal corrosivity and may cause corrosion of the reactor. Therefore, conventionally, from the viewpoint of preventing corrosion of the reactor due to acidic water containing a water-soluble chlorine-containing compound, dilution with water at any location downstream from the reactor outlet in the hydrodeoxygenation step or It was considered preferable to neutralize with a basic agent such as ammonia.

  However, according to the study by the present inventors, in the conventional method described above, the region (piping, valve, etc.) from the outlet of the reactor in the hydrodeoxygenation step to the location where dilution with water or neutralization with a basic chemical is performed. Etc.) cannot prevent corrosion of each device, and each device must use a material having high corrosion resistance to water containing a water-soluble chlorine-containing compound in the region. However, a material having high corrosion resistance to water containing a water-soluble chlorine-containing compound is expensive and causes an increase in construction cost.

  In addition, as a method for removing chlorine from the raw material oil, washing and the like can be considered, but according to the study of the present inventors, some of the fats and oils derived from animals and plants contain chlorine that is difficult to remove by washing or the like. It was found to exist. Therefore, in the conventional method, the bad influence of the chlorine content is regarded as a problem, it is necessary to selectively use fats and oils that do not substantially contain the chlorine content, and there is a degree of freedom in the selection of the raw material oil. It gets smaller.

  The present invention has been made in view of such circumstances, and is included in a raw material oil when a hydrocarbon oil is produced using a raw material oil containing an oxygen-containing organic compound and a water-insoluble chlorine-containing compound. It is an object of the present invention to provide a method capable of suppressing corrosion of a reactor caused by a chlorine-containing compound and reducing oxygen content and chlorine content in the resulting product oil.

  In order to solve the above problems, the present invention is selected from a raw material oil containing an oxygen-containing organic compound and a water-insoluble chlorine-containing compound, a porous inorganic oxide, and Group IA, Group IIA and Group IB A first step of contacting the adsorbent comprising at least one metal and adsorbing a water-insoluble chlorine-containing compound to the adsorbent to obtain dechlorinated oil; In the presence, it comprises dechlorinated oil, a carrier containing a porous inorganic oxide, and at least one metal selected from Groups VIA and VIII of the Periodic Table supported on the carrier. A second step of contacting the hydrogenation catalyst to obtain a reaction product containing hydrocarbon oil and water by hydrodeoxygenation of the oxygen-containing organic compound, and separating water from the reaction product, A third step of obtaining a product oil containing oil; To provide a method for manufacturing a hydrocarbon oil, characterized in that it comprises.

  Here, “hydrodeoxygenation” in the present invention means a treatment of removing oxygen atoms constituting the oxygen-containing organic compound and adding hydrogen to the cleaved portion. For example, fatty acid triglycerides and fatty acids each have an oxygen-containing group such as an ester group and a carboxyl group, but hydrodeoxygenation removes oxygen atoms contained in these oxygen-containing groups, and the oxygen-containing organic compound is Converted to hydrocarbons. There are mainly two reaction pathways for hydrodeoxygenation of oxygen-containing groups of fatty acid triglycerides and the like. The first reaction pathway is a hydrogenation pathway that is reduced via an aldehyde or alcohol while maintaining the number of carbon atoms such as fatty acid triglyceride. In this case, oxygen atoms are converted to water. The second reaction route is a decarboxylation route in which oxygen-containing groups such as fatty acid triglycerides are eliminated as carbon dioxide as they are, and oxygen atoms are removed as carbon dioxide. In the hydrodeoxygenation according to the present invention, these reactions proceed in parallel, and hydrocarbons, water, and carbon dioxide are generated in the hydrotreatment of the oil to be treated (raw oil) containing fats and oils derived from animals and plants.

A reaction scheme of hydrodeoxygenation taking the case of an alkyl ester of stearic acid as an example is shown in the following formulas (1) and (2). The reaction scheme represented by the formula (1) corresponds to the first reaction path, and the reaction scheme represented by the formula (2) corresponds to the second reaction path. In the formulas (1) and (2), R represents an alkyl group.
_{C 17 H 35 COOR + 4H 2} → C 18 H 38 + 2H 2 O + RH (1)
_{C 17 H 35 COOR + H 2} → C 17 H 36 + CO 2 + RH (2)

  In the second step according to the present invention, hydroisomerization may occur in addition to hydrodeoxygenation. “Hydroisomerization” in the present invention means isomerization from a linear hydrocarbon chain skeleton to a branched hydrocarbon chain skeleton by hydrotreatment. That is, “hydroisomerization” in the present invention includes not only isomerization from normal paraffin to isoparaffin, but also branched carbonization from the straight hydrocarbon chain of the oxygen-containing organic compound having a straight hydrocarbon chain. An isomerization reaction to a hydrogen chain is also included. In hydroisomerization, the molecular formula does not change between the original system and the production system, and there is no substantial increase or decrease in constituent elements.

  Moreover, in this invention, content of the oxygen content in raw material oil is 15 mass% or less on the basis of the whole quantity of raw material oil, and content of chlorine content in raw material oil is 0.1-50 mass ppm Is preferred.

  Here, the “oxygen content” in the present invention refers to an oxygen content measured according to the method described in UOP-649. The “chlorine content” as used in the present invention refers to a method described in the method described in IPPROPOSED METODOD AK / 81 “Determining of the technical content of light and distributed dispersive by oxidative microcoulometry”.

  In the present invention, the oxygen-containing organic compound contained in the raw material oil is an animal or plant-derived fat and oil, and the ratio of the fatty acid and / or the compound having an ester structure in the animal or plant-derived fat or oil is 90 mol% or more. preferable.

  Moreover, in this invention, it is preferable that the porous inorganic oxide which comprises an adsorbent is comprised including 1 or more types of elements chosen from aluminum, silicon, magnesium, and zinc.

  Moreover, in the said 1st process concerning this invention, it is preferable to make raw material oil and an adsorbent contact on the conditions of reaction temperature 20-200 degreeC.

  Moreover, in this invention, it is preferable that the porous inorganic oxide which comprises a hydrogenation catalyst is comprised including 2 or more types of elements chosen from aluminum, silicon, zirconium, boron, titanium, and magnesium.

  Moreover, in the said 2nd process concerning this invention, hydrogen pressure 2-10MPa, liquid space velocity 0.1-3.0h-1, hydrogen oil ratio 150-1500NL / L, reaction temperature 150-380 degreeC conditions Under this, it is preferable to contact the feedstock and the hydrogenation catalyst.

  In the present invention, the dechlorinated oil is based on the total amount of the dechlorinated oil, the oxygen content in the dechlorinated oil is 15 mass% or less, and the chlorine content is 5 mass ppm or less. It is preferable.

  In the present invention, based on the total amount of the product oil, the content of oxygen in the product oil is 1% by mass or less, the content of chlorine in the product oil is 0.1 mass ppm or less, It is preferable that the iodine value in oil is 0.1 or less.

  Here, “iodine value” as used in the present invention refers to the method described in JIS K 0070 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. The value measured in compliance.

  As described above, according to the method for producing a hydrocarbon oil of the present invention, a hydrocarbon oil is produced using a raw material oil containing an oxygen-containing organic compound and a water-insoluble chlorine-containing compound. It is possible to suppress the corrosion of the reactor caused by the chlorine-containing compound and reduce the oxygen content and the chlorine content in the resulting product oil.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The first step according to the present invention is a feedstock containing an oxygen-containing organic compound and a water-insoluble chlorine-containing compound, a porous inorganic oxide, and at least selected from Group IA, Group IIA, and Group IB This is a step of contacting the adsorbent comprising one or more metals and adsorbing a water-insoluble chlorine-containing compound to the adsorbent to obtain dechlorinated oil.

  In the present invention, a raw material oil containing an oxygen-containing organic compound and a water-insoluble chlorine-containing compound is used. As the oxygen-containing organic compound, a structure having a carboxylic acid group or an ester group is suitable, and examples thereof include oil and fat components derived from animals and plants. Here, the “fat and fat component derived from animal and vegetable oils” refers to a fat and oil component derived from natural animal and vegetable oils, a fat and oil component obtained by separating and purifying it, or a fat and oil derivative produced and produced by chemical conversion using these as raw materials. Furthermore, the composition of these and the component added in order to maintain and improve these product performance is included.

  Examples of the oil and fat component derived from animals and plants include tallow, rapeseed oil, soybean oil, and palm oil. In the present invention, any oil and fat may be used as the oil and fat component derived from animal and vegetable oils, and waste oil after using these oils and fats may be used. However, plant-derived oil and fat components are preferable from the viewpoint of carbon neutral, and rapeseed oil, soybean oil and palm oil are more preferable from the viewpoint of the number of fatty acid alkyl chain carbons and their reactivity. In addition, said fat and oil component may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The fat and oil component derived from animal and vegetable oils generally has a fatty acid triglyceride structure, but may contain other fatty acids and fat and oil components processed into ester bodies such as fatty acid methyl esters. However, when producing fatty acids and fatty acid esters from plant-derived oil and fat components, energy is consumed, leading to the generation of carbon dioxide, and from the viewpoint of reducing carbon dioxide emissions, it inherently has a triglyceride structure. It is preferable to use vegetable oil containing the compound as a main component.

  In the present invention, the proportion of the oxygen-containing organic compound having a fatty acid and / or ester structure in the oxygen-containing organic compound contained in the raw oil is preferably 90 mol% or more, and 92 mol% or more. Is more preferable, and it is still more preferable that it is 95 mol% or more. Furthermore, among oxygen-containing organic compounds having an ester structure, compounds having a triglyceride structure are preferred from the viewpoint of reducing carbon dioxide emissions.

  The feedstock oil may contain, as an oxygen-containing organic compound, a compound derived from chemicals such as plastics and solvents, in addition to the oil and fat components derived from the above-mentioned animal and vegetable oils, and a synthetic gas composed of carbon monoxide and hydrogen. It may contain a synthetic oil obtained via a Fischer-Tropsch reaction using as a raw material.

  The oxygen content contained in the raw material oil is preferably 15% by mass or less, more preferably 13% by mass or less, based on the total amount of the raw material oil. If the oxygen content exceeds 15% by mass, equipment necessary for the treatment of water produced as a by-product in the second step is required, and the catalytic activity of the hydrogenation catalyst decreases due to the interaction between water and the catalyst carrier. Or the catalyst strength tends to decrease.

  The raw material oil contains a water-insoluble chlorine-containing compound. Although the cause of the fact that raw material oil may contain a water-insoluble chlorine-containing compound is not necessarily clear, there may be chlorine-containing compounds involved in the metabolic system of animals and plants, the photosynthesis system of plants, etc. It is estimated that it may be derived from pesticides used during cultivation.

  The ability to use a feedstock containing a water-insoluble chlorine-containing compound in the present invention is also useful in that the degree of freedom in selecting a feedstock to be subjected to hydrodeoxygenation is increased. The raw material oil used in the present invention may further contain a water-soluble chlorine-containing compound. Judgment of whether a chlorine-containing compound is water-soluble or water-insoluble can be made by, for example, mixing a sample with an equal amount of distilled water at room temperature, shaking for a certain time, and then quantifying the chlorine content on the aqueous phase side. It can be carried out.

  The chlorine content contained in the raw material oil is preferably 0.1 to 50 ppm by mass, and more preferably 0.1 to 20 ppm by mass, based on the total amount of the raw material oil. When the chlorine content in the raw material oil exceeds 50 ppm by mass, the adsorption of chlorine-containing compounds by the adsorbent tends not to proceed sufficiently.

  Moreover, the fats and oils derived from animals and plants may include fats and oils having an olefin structure. For this reason, olefin content may exist in the raw material oil containing the fat and oil component derived from animals and plants, but the presence of the olefin content can be confirmed by iodine value. In the present invention, the iodine value of the feedstock oil is preferably 145 or less. If the iodine value exceeds 145, the reaction efficiency of hydrodeoxygenation of oxygen-containing organic compounds or conversion reaction from water-insoluble chlorine-containing compounds to water-soluble chlorine-containing compounds (dechlorination reaction, etc.) tends to decrease. In addition, there is a tendency that heat generation becomes large due to the hydrogenation reaction of olefins, making it difficult to control the reaction.

  Moreover, raw material oil may be comprised only by the fats and oils component derived from animals and plants, and may mix with another base material. The other base material may be a petroleum-based fraction, a fraction obtained by distilling crude oil, or a fraction obtained by subjecting these fractions to a purification process such as hydrodesulfurization or decomposition. The boiling point of the other base material to be mixed is preferably in the range of 100 to 400 ° C, and more preferably in the range of 160 to 390 ° C. When the oil and fat component derived from animals and plants is subjected to the method for producing hydrocarbon oil of the present invention, a fraction having a boiling point corresponding to light oil is mainly obtained, but when the boiling point of the base material to be mixed is lighter than 100 ° C., the light oil There is a possibility that quality standards such as flash point and kinematic viscosity cannot be satisfied as a base material. Further, when the boiling point of the base material to be mixed is heavier than 400 ° C., the exhaust gas deteriorates, such as a decrease in reactivity in the first step and a tendency to generate particulates when used as fuel oil. Is concerned.

  In the first step according to the present invention, an adsorbent comprising a porous inorganic oxide and at least one metal selected from Group IA, Group IIA, and Group IB is used. The porous inorganic oxide constituting the adsorbent is composed of one or more elements selected from aluminum, silicon, magnesium, and zinc from the point that the amount of adsorption of the water-insoluble chlorine-containing compound can be further improved. Preferably it is.

  Zeolite can also be included as the porous inorganic oxide constituting the adsorbent used in the present invention. In the case of using zeolite, it is preferable to use zeolite having a crystal structure such as FAU, BEA, MOR, MFI, MEL, MWW, TON, AEL, MTT among the structure codes defined by the International Zeolite Society.

  The adsorbent used in the present invention contains at least one metal selected from Group IA, Group IIA, and Group IB of the Periodic Table. Among these metals, it is preferable to carry at least one metal selected from Li, Na, K, Mg, Ca, Cu, and Ag, and at least one selected from Na, Mg, Ca, and Ag. More preferred is the above metal. The adsorbent used in the present invention may be a combination of a plurality of adsorbents having different porous inorganic oxides and / or active metal species.

  In the first step according to the present invention, any generally known reactor such as a batch type, a semi-batch type, a fixed bed, a fluidized bed, and a powder bed can be used. Moreover, the reactor may be individual and may combine several. Also, a plurality of types of adsorbents may be combined, and the type and amount of adsorbents used, reaction conditions, etc. may be set according to the difference in raw material oil or chlorine-containing compound concentration in the raw material oil.

  Moreover, it is preferable that the reaction temperature in a 1st process is the range of 20-200 degreeC, and it is more preferable that it is the range of 30-150 degreeC. When the reaction temperature is less than 20 ° C., the fluidity is remarkably lowered depending on the oil type, and the adsorption of the chlorine-containing compound to the adsorbent tends not to proceed sufficiently. On the other hand, the physical adsorption amount of the chlorine-containing compound with respect to the adsorbent decreases at a high temperature, and when it exceeds 200 ° C., the adsorption of the chlorine-containing compound to the adsorbent tends to hardly proceed.

  The dechlorinated oil obtained in the first step has a sufficiently reduced chlorine content, but the remaining chlorine content is highly corrosive chlorine, hydrogen chloride or other chloride ions after the second step. From the viewpoint of preventing apparatus corrosion in the second step and the latter stage of the second step, the chlorine content in the dechlorinated oil is based on the total amount of the dechlorinated oil. Preferably it is 5 mass ppm or less, More preferably, it is 4 mass ppm or less, More preferably, it is 3 mass ppm or less, More preferably, it is 2 mass ppm or less, Most preferably, it is 1 mass ppm or less.

  Further, the oxygen content contained in the dechlorinated oil is equivalent to the oxygen content contained in the raw material oil, but is preferably 15% by mass or less, more preferably 13% by mass or less, based on the total amount of the dechlorinated oil. is there. If the oxygen content exceeds 15% by mass, equipment necessary for the treatment of water produced as a by-product in the second step is required, and the catalytic activity of the hydrogenation catalyst decreases due to the interaction between water and the catalyst carrier. Or the catalyst strength tends to decrease.

  In the second step according to the present invention, in the presence of hydrogen, a dechlorinated oil containing an oxygen-containing organic compound, a carrier containing a porous inorganic oxide, and a periodic table group VIA supported on the carrier. And a hydrocatalyst comprising at least one metal selected from Group VIII, and a reaction product containing hydrocarbon oil and water by hydrodeoxygenation of the oxygen-containing organic compound It is the process of obtaining.

  The second step according to the present invention comprises a support containing a porous inorganic oxide and at least one metal selected from Groups VIA and VIII of the Periodic Table supported on the support. A hydrogenation catalyst is used. As the carrier of the hydrogenation catalyst, aluminum and silicon can be used since the catalytic activity for the hydrodeoxygenation reaction and the conversion reaction from water-insoluble chlorine-containing compounds to water-soluble chlorine-containing compounds (dechlorination reaction etc.) can be further improved. , Zirconium, boron, titanium, magnesium and zeora, preferably two or more selected from inorganic oxides including aluminum and other elements (including complex oxides of aluminum oxide and other oxides) Is more preferable.

  When the porous inorganic oxide contains aluminum as a constituent element, the aluminum content is preferably 10% by mass or more, more preferably 15% by mass in terms of alumina, based on the total amount of the porous inorganic oxide. As mentioned above, More preferably, it is 20 mass% or more. When the aluminum content is less than 10% by mass in terms of alumina, the catalytic acid properties, the strength and surface area of the catalyst become insufficient, and the activity tends to decrease.

  The method for introducing silicon, zirconium, boron, titanium and magnesium, which are carrier constituent elements other than aluminum, is not particularly limited, and a solution containing these elements may be used as a raw material. For example, for silicon, silicic acid, water glass, silica sol, etc., for boron, boric acid, etc., for phosphorous, phosphoric acid and alkali metal salts of phosphoric acid, for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts For zirconium, zirconium sulfate and various alkoxide salts can be used.

  The porous inorganic oxide is preferably composed of at least two elements selected from aluminum, silicon, zirconium, boron, titanium, and magnesium, and at least two of aluminum, silicon, zirconium, and titanium. It is more preferable that the above element is included.

  The hydrogenation catalyst carrier used in the present invention can also contain zeolite as a porous inorganic oxide. In the case of using zeolite, it is preferable to use zeolite having a crystal structure such as FAU, BEA, MOR, MFI, MEL, MWW, TON, AEL, MTT among the structure codes defined by the International Zeolite Society.

  Two or more kinds of metals selected from elements of Group VIA and Group VIII of the periodic table are supported on the porous inorganic oxide as a support. Among these metals, it is preferable to carry at least one metal selected from Ni, Co, Pt, Pd, Ru, Rh, Ir, Mo, and W. Ni, Pt, Pd, Ru, Mo It is more preferable that it is at least one metal selected from Examples of the metal combination include Ni—Mo, Ni—W, Co—Mo, Co—W, Ni—Co—Mo, Pt—Pd, Pt—Ru, Pt—Rh, Pt—Ir, etc. Ni-Mo, Co-Mo, Pt-Pd, and Pt-Ru are more preferable. The hydrogenation catalyst used in the present invention may be a combination of a plurality of types of catalysts having different porous inorganic oxides and / or active metal species.

  The method for supporting the metal on the support is not particularly limited, and a known method applied when producing a normal hydrogenation catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier. These metals can be used as an impregnation solution by dissolving a metal source in the form of nitrate, sulfate or complex in an aqueous solution or an appropriate organic solvent.

  The second step according to the present invention can be suitably performed using, for example, a fixed bed type reactor. Hydrogen can employ either a countercurrent or a cocurrent flow with respect to the oil to be treated (raw oil). Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be individual and may combine several. Furthermore, you may employ | adopt the structure which divided the inside of one reactor into the some catalyst bed. Further, a plurality of types of hydrogenation catalysts may be combined, and the type, amount of use, reaction conditions, etc. of the hydrogenation catalyst may be set according to functions such as hydrodeoxygenation reaction and hydroisomerization reaction.

  In addition, hydrogen gas introduced into the reactor accompanying the feedstock is introduced from the inlet of the first reactor along with the feedstock before or after passing through a heating furnace for setting a predetermined reaction temperature. In addition to this, in addition to controlling the temperature in the reactor, hydrogen gas is introduced from between the catalyst beds or between the reactors in order to maintain the hydrogen pressure throughout the reactor. May be. Alternatively, any or a plurality of mixed oils such as a product oil, an unreacted oil, a reaction intermediate oil, or the like may be used, and a part may be introduced from the reactor inlet, the catalyst bed, the reactor, or the like. Thereby, the reaction temperature can be controlled, and an excessive decomposition reaction or a runaway reaction due to an increase in the reaction temperature can be avoided.

The reaction conditions in the second step are a hydrogen pressure of 2 to 10 MPa, a liquid hourly space velocity (LHSV) of 0.1 to 3.0 h ⁻¹ , and a hydrogen oil ratio (hydrogen / oil ratio) of 150 to 1500 NL / L. More preferably; hydrogen pressure 2 to 8 MPa, liquid hourly space velocity 0.2 to 2.5 h ⁻¹ , hydrogen oil ratio 200 to 1200 NL / L; hydrogen pressure 3 to 7 MPa, liquid hourly space velocity 0. More preferably, the ratio is 3 to 2.0 h ⁻¹ and the hydrogen oil ratio is 250 to 1000 NL / L. These conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen oil ratio are less than the above lower limit values, the reactivity tends to decrease or the activity rapidly decreases. is there. On the other hand, when the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required. Further, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid hourly space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently.

  The reaction temperature in the second step is preferably in the range of 150 to 380 ° C, more preferably in the range of 180 to 370 ° C, still more preferably in the range of 220 to 360 ° C, 260 A range of ˜350 ° C. is particularly preferable. When the reaction temperature is lower than 150 ° C., hydrodeoxygenation reaction, conversion reaction from water-insoluble chlorine-containing compound to water-soluble chlorine-containing compound (dechlorination reaction, etc.), or further olefin hydrogenation reaction proceeds. It tends to be difficult. On the other hand, when the reaction temperature exceeds 380 ° C., excessive decomposition, polymerization of the raw material oil, and other side reactions may proceed, and a reaction involving the by-production of water during hydrodeoxygenation (first reaction) The ratio of decarboxylation reaction (second reaction path, formula (2)) to the reaction path of formula (1)) is increased, and the amount of water by-product for retaining the water-soluble chlorine-containing compound is insufficient. It tends to be.

  The reaction product obtained in the second step includes a hydrocarbon oil produced by hydrodeoxygenation of the oxygen-containing organic compound and water produced as a by-product. The amount of water can be appropriately adjusted by adjusting the above reaction conditions.

  The third step according to the present invention is a step of separating the water produced as a by-product from the reaction product obtained in the second step to obtain a product oil containing hydrocarbon oil.

  When separating water from the reaction product, a method employed in a general petroleum refining process or the like can be applied. For example, after the component distilled from the reactor is gas-liquid separated in a high-temperature and high-pressure separator (separator), the gas phase side is introduced into the separator as it is or via a cooler, and the condensed aqueous phase is separated and recovered. be able to.

  The water separated in the third step may contain water-soluble chlorine-containing compounds such as highly corrosive chlorine, hydrogen chloride or other chloride ions derived from the chlorine-containing compounds remaining in the first step. . From the viewpoint of preventing corrosion of the second step, the third step, and the subsequent device of the third step, the chlorine content in the water is preferably 50 mass ppm or less, based on the total amount of water. Preferably it is 30 mass ppm or less, More preferably, it is 10 mass ppm or less, More preferably, it is 5 mass ppm or less, Most preferably, it is 1 mass ppm or less.

  According to the present invention, when the hydrocarbon oil is produced by using the raw material oil containing the oxygen-containing organic compound and the water-insoluble chlorine-containing compound through the first to third steps, the raw material oil It is possible to sufficiently suppress the corrosion of the reaction apparatus due to the chlorine-containing compound contained in. For example, after the hydrodechlorination step, the reaction fluid is distilled from the reactor and passes through equipment such as piping, heat exchanger, gas-liquid separation tower, cooler, valve, rectification tower, According to the present invention, corrosion of these devices can be sufficiently suppressed. In addition, from the viewpoint of more reliably suppressing corrosion, a material having high corrosion resistance may be selected and used for the above-described equipment as necessary.

  Further, the reaction product obtained in the second step may contain by-products such as carbon dioxide and LPG in addition to hydrocarbon oil and water. In this step, water may be separated at the time of separation, or a separate separation step from the water separation step may be provided.

  The product oil obtained through the first to third steps is one in which the oxygen content and the chlorine content are sufficiently reduced, but from the viewpoint of oxidation stability, the oxygen content in the product oil is: Based on the total amount of product oil, it is preferably 1% by mass or less, more preferably 0.8% by mass or less, still more preferably 0.6% by mass or less, still more preferably 0.4% by mass or less, particularly preferably. It is 0.2 mass% or less.

  Further, from the viewpoint of reducing adverse effects on engine components and exhaust gas treatment catalysts when the produced oil is used as fuel oil, the chlorine content in the produced oil is preferably 0, based on the total amount of produced oil. .1 mass ppm or less.

  The product oil preferably has an increase in acid value after blowing oxygen gas at 115 ° C. for 16 hours, based on the acid value before blowing oxygen gas, of 0.25 mg-KOH / g or less. More preferably, it is 15 mgKOH / g or less. The acid value is an index representing the amount of acidic components in 1 g of a sample, and when the increase in acid value exceeds 0.25 mgKOH / g, the storage stability of the product oil tends to deteriorate. In addition, the "acid value" as used in the field of this invention means the acid value measured based on the method as described in the acid value test method in JIS K2276 "Petroleum products-Aviation fuel oil test method".

  From the viewpoint of oxidation stability, the iodine value of the produced oil is preferably 0.1 or less. When the iodine value exceeds 0.1, the above-described acid value tends to increase remarkably. The iodine value in the present invention was measured in accordance with the method described in JIS K 0070 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. Value.

  The product oil obtained in the present invention is usually composed mainly of a fraction in the boiling range corresponding to light oil, but may contain gas, naphtha fraction, and kerosene fraction in addition to the fraction. is there. Therefore, if necessary, these fractions can be fractionated by providing a gas-liquid separation step, a rectification step, and the like after the second step.

  When the product oil or a fraction thereof is substantially composed of a hydrocarbon oil, it can be suitably used particularly as a diesel light oil or heavy oil base material. In this case, the product oil or a fraction thereof may be used alone as a diesel light oil or heavy oil base material, but can be used as a diesel light oil or a heavy base material mixed with other base materials. As other base materials, a light oil fraction and / or kerosene fraction obtained in a general petroleum refining process and a residual fraction obtained by the method for producing hydrocarbons of the present invention can be mixed. Furthermore, synthetic light oil or synthetic kerosene obtained through a Fischer-Tropsch reaction or the like using so-called synthesis gas composed of hydrogen and carbon monoxide as a raw material can be mixed. These synthetic light oils and kerosene are characterized by containing almost no aromatic content, having a saturated hydrocarbon as a main component, and a high cetane number. In addition, a well-known method can be used as a manufacturing method of synthesis gas, and it is not specifically limited.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

Example 1
Palm oil as raw material oil (density at 15 ° C .: 0.916 g / ml, oxygen content: 11.4 mass%, chlorine content: 8.2 mass ppm, iodine value: 51.1, triglyceride in oxygen-containing organic compound) 200 g of a compound having a structure: 99.6 mol%) was put in a flask and vacuum-dried at 95 ° C. and 0.1 kPa for 30 minutes.

  To the dried raw material oil, 1.0 g of an adsorbent A composed of sodium oxide, silicon dioxide, and aluminum oxide was added, and the mixture was heated and stirred at 140 ° C. and 0.1 kPa for 60 minutes. The oil was filtered to obtain an oil to be treated (dechlorinated oil). Table 1 shows the chlorine content of the oil to be treated.

  A reaction tube (inner diameter 20 mm) filled with 50 ml of the catalyst having the composition shown in Table 2 was attached to a fixed bed flow type reactor. Next, using straight-run gas oil to which dimethyl disulfide was added (sulfur content: 3% by mass), the catalyst layer average temperature was 300 ° C., the hydrogen partial pressure was 6 MPa, the liquid space velocity was 1 h-1, and the hydrogen / oil ratio was 200 NL / L. The catalyst was presulfided for 4 hours.

The treated oil (dechlorinated oil) obtained above is passed through the reactor and hydrogenated under the conditions of a reaction temperature of 310 ° C., LHSV 1.0 h ⁻¹ , a hydrogen pressure of 5 MPa, and a hydrogen oil ratio of 600 NL / L. Processed.

  Next, water was separated from the reaction product after the hydrodeoxygenation treatment to obtain a product oil mainly composed of hydrocarbon oil. Table 1 shows the chlorine content, oxygen content and iodine value of the product oil, and the chlorine content of the separated water.

(Example 2)
The adsorbent was adsorbent B composed of silver, silicon dioxide, and aluminum oxide, and dechlorination, hydrodeoxygenation, and water separation were performed in the same manner as in Example 1 except that the treatment temperature was 50 ° C. It was. Table 1 shows the chlorine content of the oil to be treated (dechlorinated oil), the chlorine content of the product oil, the oxygen content and iodine value, and the chlorine content of the separated water.

(Example 3)
Raw material oil is soybean oil (density at 15 ° C .: 0.923 g / ml, oxygen content: 11.5 mass%, chlorine content: 1.8 mass ppm, iodine value: 136, triglyceride structure in the oxygen-containing organic compound) Dechlorination, hydrodeoxygenation, and water separation were carried out in the same manner as in Example 1 except that the ratio of the compound having: 99.5 mol%). Table 1 shows the chlorine content of the oil to be treated (dechlorinated oil), the chlorine content of the product oil, the oxygen content and iodine value, and the chlorine content of the separated water.

(Comparative Example 1)
Dechlorination, hydrodeoxygenation, and water separation were performed in the same manner as in Example 1 except that the adsorbent was adsorbent C made of silicon dioxide. Table 1 shows the chlorine content of the oil to be treated, the chlorine content, the oxygen content and iodine value of the product oil, and the chlorine content of the separated water.

(Comparative Example 2)
100 ml of palm oil similar to Example 1 and 100 ml of distilled water were placed in a screw tube and shaken for 10 minutes in a constant temperature water bath kept at 35 ° C. After shaking, the oil was recovered, 100 ml of distilled water was added again, and after shaking, the oil was recovered. Table 1 shows the chlorine content of the recovered oil (oil to be treated).

  Next, the recovered oil was subjected to hydrodeoxygenation and water separation in the same manner as in Example 1. Table 1 shows the chlorine content, oxygen content and iodine value of the product oil, and the chlorine content of the separated water.

Claims (10)

A feed oil containing an oxygen-containing organic compound and a water-insoluble chlorine-containing compound, a porous inorganic oxide, and at least one metal selected from Group IA, Group IIA and Group IB A first step of obtaining a dechlorinated oil by contacting the adsorbent and adsorbing the water-insoluble chlorine-containing compound to the adsorbent;
In the presence of hydrogen, the dechlorinated oil, a carrier containing a porous inorganic oxide, and at least one metal selected from Groups VIA and VIII of the periodic table supported on the carrier. A second step of contacting a configured hydrogenation catalyst to obtain a reaction product containing hydrocarbon oil and water by hydrodeoxygenation of the oxygen-containing organic compound;
A third step of separating the water from the reaction product to obtain a product oil containing the hydrocarbon oil;
A method for producing a hydrocarbon oil, comprising:   Based on the total amount of the raw material oil, the content of oxygen in the raw material oil is 15% by mass or less, and the content of chlorine in the raw material oil is 0.1 to 50 ppm by mass. The manufacturing method of the hydrocarbon oil of Claim 1.   Based on the total amount of the dechlorinated oil, the oxygen content in the dechlorinated oil is 15 mass% or less, and the chlorine content in the dechlorinated oil is 5 mass ppm or less. The manufacturing method of the hydrocarbon oil of Claim 1 or 2.   The content of chlorine in the water separated in the third step is 50 mass ppm or less based on the total amount of the water, according to any one of claims 1 to 3. The manufacturing method of hydrocarbon oil as described.   The oxygen-containing organic compound is an animal or plant-derived oil or fat, and the ratio of the fatty acid and / or the compound having an ester structure in the animal or plant-derived oil or fat is 90 mol% or more. A method for producing the hydrocarbon oil according to claim 1.   The porous inorganic oxide constituting the adsorbent in the first step includes one or more elements selected from aluminum, silicon, magnesium, and zinc. The manufacturing method of the hydrocarbon oil of any one of 1-5.   The hydrocarbon according to any one of claims 1 to 6, wherein in the first step, the raw material oil and the adsorbent are brought into contact under a reaction temperature of 20 to 200 ° C. Oil production method.   The porous inorganic oxide is configured to include two or more elements selected from aluminum, silicon, zirconium, boron, titanium, and magnesium. The manufacturing method of hydrocarbon oil as described in any one of.   In the second step, the dechlorinated oil is obtained under the conditions of a hydrogen pressure of 2 to 10 MPa, a liquid space velocity of 0.1 to 3.0 h-1, a hydrogen oil ratio of 150 to 1500 NL / L, and a reaction temperature of 150 to 380 ° C. The method for producing a hydrocarbon oil according to any one of claims 1 to 8, wherein the hydrogenation catalyst is brought into contact with the hydrocarbon catalyst. Based on the total amount of the product oil, the content of oxygen in the product oil is 1% by mass or less, the content of chlorine in the product oil is 0.1 mass ppm or less, as in the product oil The method for producing a hydrocarbon oil according to any one of claims 1 to 9, wherein the prime value is 0.1 or less.