KR101362950B1 - Hydrorefining process - Google Patents

Abstract

The hydrogenation purification method of the present invention is a porous inorganic oxide composed of an oil to be treated containing an oxygen-containing hydrocarbon compound in the presence of hydrogen, and two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium. And a catalyst containing a carrier containing at least one metal selected from elements of Groups 6A and 8 of the periodic table supported on the carrier, hydrogen pressure 2 to 13 MPa, liquid space velocity 0.1 to 3.0 h ⁻¹ , hydrogen The refined oil is characterized in that a refined oil is obtained through a hydrogenation purification step of contacting under a ratio of 150 to 1500 NL / L and a reaction temperature of 150 to 380 ° C.

Hydrogenation Purification Method, Porous Inorganic Oxide, Carrier, Crystalline Molecular.

Description

Hydrogenation Purification Process

The present invention relates to a hydrogenation purification method.

As a measure to prevent global warming, attention is focused on effective utilization of biomass energy. Among the biomass energy, the biomass energy derived from plants can be effectively utilized for the hydrocarbons converted from carbon dioxide by photosynthesis in the growing process of the plant. Therefore, from the viewpoint of the life cycle, the so-called biomass energy, which does not lead to increase in the atmospheric carbon dioxide It has a property called carbon neutral.

The use of such biomass energy has been examined variously in the field of fuel for transportation. For example, if a fuel derived from animal or vegetable oil can be used as diesel fuel, it is expected to play an effective role in reduction of carbon dioxide emissions by a synergy effect with a high energy efficiency of a diesel engine. Fatty acid methyl ester oil is known as a diesel fuel using animal and vegetable oils. Fatty acid methyl ester oil is produced by transesterification with methanol by alkali etc. with respect to the triglyceride structure which is a general structure of animal and vegetable oil. However, in the process for producing a fatty acid methyl ester oil, as described in Patent Document 1 below, it has been pointed out that treatment of glycerin as a by-product is required, and cost and energy are required for cleaning the produced oil.

Patent Document 1: JP-A-2005-154647

Problems to be solved by the invention

In addition to the above-mentioned problems, there are the following problems in using a fuel oil derived from animal and vegetable oil or a fuel produced from the fuel oil. In other words, the holding component derived from animal and plant oil generally has an oxygen atom in the molecule, so that there is a concern that the oxygen component adversely affects the constituent members of the engine and that it is difficult to remove the oxygen component to a very low concentration. In the case where a fat or oil component derived from a plant or animal oil and a petroleum hydrocarbon fraction are mixed and used, conventional techniques cannot sufficiently reduce both the oxygen content and the sulfur content in the petroleum hydrocarbon fraction in the fat and oil component.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a hydrogenation purification method capable of obtaining a hydrogenated refined oil in which oxygenates are sufficiently reduced when using a treating oil containing an oxygen-containing hydrocarbon compound.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, this invention is a porous which consists of a to-be-processed oil containing an oxygen containing hydrocarbon compound, and 2 or more types of elements chosen from aluminum, silicon, zirconium, boron, titanium, and magnesium in presence of hydrogen. A catalyst containing an inorganic oxide and a catalyst containing at least one metal selected from elements of Groups 6A and 8 of the Periodic Table supported on the support include hydrogen pressure of 2 to 13 MPa and a liquid space velocity of 0.1 to 3.0 h ^−1. And a hydrogenation purification process, wherein the refined oil is obtained through a hydrogenation purification step of contacting under a hydrogen oil ratio of 150 to 1500 NL / L and a reaction temperature of 150 to 380 ° C.

According to the hydrogenation and purification method of the present invention, by contacting the oil to be treated containing an oxygen-containing hydrocarbon compound with the specific catalyst, hydrogenated refined oil having sufficiently reduced oxygen content can be economically obtained very effectively.

In addition, the carrier preferably contains a crystalline molecular sieve (molecular sieve). As a result, the oxygen content is sufficiently reduced, and hydrogenated refined oil having sufficiently low temperature performance, which is sufficiently practical, can be economically obtained very effectively. In addition, in the case of the conventional hydrogenation purification method which does not have this constitution, the paraffin component obtained has a low temperature performance such as a cloud point or the like There is a concern that this cannot be said to be practical enough.

Further, in the hydrogenation purification method of the present invention, it is preferable that the oxygen content is 0.1 to 15% by mass based on the whole amount of the oil to be treated. It is preferable that the content of the subject oil is sufficiently low even if sulfur is not contained or contained, and it is preferable that the sulfur content is 50 mass ppm or less based on the total amount of the oil to be treated. If the amounts of the oxygenates and the sulfur substances to be treated are within the above ranges, the stable deoxygenation activity can be maintained over a long period of time.

Further, in the hydrogenation purification method of the present invention, from the viewpoint of effective utilization of biomass energy, it is preferable that the oxygen-containing hydrocarbon compound is a sustaining component derived from animal and plant oil.

Further, since the energy required for processing the raw material can be reduced, the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is preferably 90 mol% or more.

Further, in the hydrogenation purification method of the present invention, the ratio of isoparaffin to normal paraffin (the mass of isoparaffin / the normal paraffin of normal paraffin) in the paraffin component contained in the oil fraction at 150 to 350 DEG C of the purified oil obtained from the above- It is preferable to perform the said hydrorefining process so that (the mass of) may be 0.2 or more. Thereby, the improvement of low-temperature performance as a fuel represented by cloud point of refined oil etc. can be fully achieved.

Further, in the hydrogenation purification method of the present invention, the crystalline molecular sieve constituting the catalyst contains a zeolite containing silicon, and the zeolite has a ratio of silicon to constituent elements other than oxygen and silicon Atom number / oxygen and atomic number of elements other than silicon) are preferably 3 or more. Thereby, excessive decomposition reaction can be suppressed and efficient fuel production and improvement of low temperature performance can be achieved more fully.

Moreover, in the hydrogenation purification method of this invention, it is preferable that the said metal which comprises the said catalyst contains 1 or more types of elements chosen from Pd, Pt, Rh, Ir, Au, Ni, and Mo. As a result, the hydrogenation deoxygenation reaction is promoted, and at the same time, the improvement in the low temperature performance such as the hydrogenation isomerization reaction and the paraffin decomposition and elimination reaction can be more sufficiently achieved.

In addition, the metal monoxide adsorption amount per 1 g of the catalyst in the reduced state is preferably in the range of 0.003 to 0.05 mmol. Thereby, sufficient activity can be exhibited stably for a long time.

Further, in the hydrogenation purification method of the present invention, the hydrogenation purification step may include a first hydrogenation step of removing 70 wt% or more of the initial oxygen content contained in the processed oil to obtain a first purified oil, A second hydrogenation step of removing the oxygen content remaining in the first refined oil to obtain a second refined oil so as to remove 95 mass% or more, wherein the second hydrogenation process is performed at 150 to 350 ° C. of the second refined oil. In the paraffin powder contained in the oil fraction of, it is preferable that the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is 0.2 or more. Thereby, the improvement of low-temperature performance as a fuel represented by cloud point of refined oil etc. can be fully achieved.

Effects of the Invention

According to the present invention, there is provided a hydrogenation purification method capable of economically and highly effectively obtaining a hydrogenated refined oil in which oxygenates are sufficiently reduced when a processing oil containing an oxygen-containing hydrocarbon compound is used.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail.

In this invention, the to-be-processed oil containing an oxygen containing hydrocarbon compound is used. As the oxygen-containing hydrocarbon compound, a sustaining component derived from animal or plant oil is suitable. Herein, the fat-retaining component of the present invention includes, but is not limited to, animal and vegetable oils and fats and oils and fats and oils that are produced or produced naturally or artificially, components retained and produced from such fat, And components added for the purpose.

Examples of the fat-and-oil-derived fat-and-oil component include, for example, tallow, vegetable oil, soybean oil and palm oil. In the present invention, any kind of oil may be used as the oil-and-fat-derived oil or oil-derived oil, and waste oil after use of such a oil is preferable. However, from the viewpoint of carbon neutral, vegetable oil is preferable, and from the viewpoint of the number of alkyl chain of fatty acid carbon atoms and the reactivity thereof, more preferred is vegetable oil, soybean oil and palm oil. The above-mentioned fats and oils may be used singly or in a mixture of two or more kinds.

The fat-and-oil-derived fat-and-oil-derived fat-and-fat component generally has a fatty acid triglyceride structure, but may contain a fat or oil-retaining component processed with an ester such as other fatty acids or fatty acid methyl esters. However, since carbon dioxide is generated when producing fatty acids or fatty acid esters from plant fats and oils, it is preferable that a component having a triglyceride structure is the main component of the plant fats and oils from the viewpoint of reducing the carbon dioxide emission. In the present invention, the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound contained in the treated oil is preferably 90 mol% or more, more preferably 92 mol% or more, further preferably 95 mol% or more.

The oil to be treated is an oxygen-containing hydrocarbon compound, which may contain a compound derived from a chemical such as plastic or a solvent, in addition to the above-mentioned oil-and-fat-derived oil-retaining component, and may be a petroleum product containing a synthesis gas composed of carbon monoxide and hydrogen as a raw material And may contain a synthetic oil obtained via a Fischer-Tropsch reaction.

In addition, the to-be-processed oil may contain the petroleum hydrocarbon fraction. As the petroleum hydrocarbon fractions, oil fractions obtained in general petroleum refining processes can be used. For example, it is possible to use a distillation column obtained from an atmospheric distillation apparatus or a distillation apparatus having a predetermined boiling point range obtained from the distillation apparatus or from a hydrodesulfurization apparatus, a hydrocracking apparatus, a residual oil direct desulfurization apparatus, You may use the oil content corresponding to a predetermined boiling range. The oil fractions obtained from the respective devices may be used singly or in a mixture of two or more. The amount of the oil component can be arbitrarily set as long as the oxygen component and the sulfur component contained in the oil to be treated satisfy a predetermined concentration range. In addition, you may mix this fraction with the synthetic oil obtained via the said chemical substance derived from a chemicals, or the Fischer-Tropsch reaction.

The oxygen content contained in the processed oil is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, further preferably 3 to 14% by mass, particularly preferably 0.1 to 15% by mass, Is 5 to 13 mass%. If the oxygen content is less than 0.1% by mass, it tends to be difficult to stably maintain the deoxygenation activity and the desulfurization activity. On the other hand, when the content of the oxygen content exceeds 15% by mass, the equipment required for the treatment of by-product water is required, or the interaction between water and the catalyst carrier is excessive, and the activity is lowered or the catalyst strength is lowered. The content of oxygen content can be measured by a general element analyzer. For example, the sample can be measured using a thermal conductivity detector after converting the sample from platinum carbon to carbon monoxide or converting it to carbon dioxide again.

In addition, the to-be-processed oil may contain the sulfur containing hydrocarbon compound as needed. The sulfur-containing hydrocarbon compound is not particularly limited, and specific examples thereof include sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene and derivatives thereof. The sulfur containing hydrocarbon compound contained in the to-be-processed oil may be a single compound, or a mixture of 2 or more types may be sufficient. Moreover, you may mix petroleum hydrocarbon fraction containing a sulfur content with to-be-processed oil.

The content of sulfur in the processed oil is preferably 50 mass ppm or less, more preferably 20 mass ppm or less, and even more preferably 10 mass ppm or less, based on the total amount of the processed oil. If the content of sulfur is more than 50 mass ppm, it tends to be difficult to stably maintain the deoxygenation activity, and the sulfur content of the hydrogenated refined oil tends to increase. When used as a fuel for a diesel engine or the like There is a fear of adverse effects on the engine exhaust gas purification device. In the present invention, the term "sulfur content" means the content of the sulfur content measured in accordance with the method described in JIS K 2541 "Sulfur Test Method" or ASTM-5453.

In the case of containing a sulfur-containing hydrocarbon compound in the treated oil, the sulfur-containing hydrocarbon compound may be premixed with the feed oil and the mixture may be introduced into the reactor of the hydrogenation purification apparatus, or when introducing the feed oil into the reactor, You may supply in.

The treated oil used in the present invention preferably contains oil having a boiling point of 300 캜 or higher and preferably does not contain a heavy oil fraction having a boiling point exceeding 700 캜. When a processed oil not containing an oil fraction having a boiling point of 300 DEG C or higher is used, it tends to be difficult to obtain a sufficient yield by excessive decomposition. On the other hand, when the oil to be treated contains a heavy oil fraction having a boiling point exceeding 700 캜, precipitation of carbon in the catalyst is promoted by the heavy component, and the activity tends to decrease. The boiling point in the present invention is a value measured in accordance with JIS K 2254 "Distillation Test Method" or ASTM-D86.

In the hydrogenation purification method of the present invention, a carrier containing a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and a carrier containing Group 6A and A catalyst containing at least one metal selected from the group 8 elements is used.

As the carrier of the catalyst used in the present invention, a porous inorganic oxide composed of at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium is used as described above. The porous inorganic oxide is preferably at least two kinds selected from aluminum, silicon, zirconium, boron, titanium and magnesium in view of further improving the deoxidizing activity and the desulfurizing activity, And an inorganic oxide (composite oxide of aluminum oxide and another oxide) is more preferable.

The carrier included in the catalyst used in the present invention preferably contains crystalline molecular sieves. It is preferable that the crystalline molecular sieve contain at least silicon in order to impart sufficient hydrogenation deoxygenation activity and hydrogenation isomerization activity. It is preferable that the crystalline molecular sieve contains at least one of aluminum, zirconium, boron, titanium, gallium, zinc and phosphorus as constituent elements other than silicon and aluminum, zirconium, It is more preferable to contain 1 or more types of phosphorus. Since the crystalline molecular sieve contains these elements, the hydrogenation deoxygenation reaction and the skeleton isomerization reaction of the hydrocarbon can be promoted at the same time, so that the improvement of the low temperature performance of the refined oil can be more sufficiently achieved. As such a crystalline molecular sieve, zeolite is preferable, and zeolite containing silicon and aluminum, that is, aluminosilicate is more preferable.

(The number of atoms of silicon / the number of atoms of elements other than silicon and silicon) relative to constituent elements excluding oxygen and silicon is 3 or more with respect to an element other than oxygen among the elements constituting the crystalline molecular sieve It is preferable, it is more preferable that it is 10 or more, and it is further more preferable that it is 30 or more. When the ratio is less than 3, the decomposition reaction of paraffin is promoted, which may cause a decrease in activity due to caulking.

Moreover, it is preferable that it is 0.8 nm or less, and, as for the pore diameter of a crystalline molecular sieve, it is more preferable that it is 0.65 nm or less. When the pore diameter is larger than 0.8 nm, the decomposition reaction of paraffin may occur. The crystal structure of the crystalline molecular sieve is not particularly limited and FAU, AEL, MFI, MMW, TON, MTW, * BEA, MOR and the like can be mentioned in the structure defined by the International Zeolite Society.

The method for synthesizing the crystalline molecular sieve constituting the catalyst used in the present invention is not particularly limited and a hydrothermal synthesis method using a constituent material and an amine compound as a structure indicating agent can be used have. Examples of the constituent raw materials include sodium silicate, colloidal silica and silicate alkoxide in the case of a silicon-containing compound, and aluminum hydroxide and sodium aluminate in the case of aluminum. Tetrapropylammonium salt etc. are mentioned as a structural indicator.

The crystalline molecular sieve may be subjected to hydrothermal treatment with steam or the like, immersion treatment with an alkaline or acidic aqueous solution, ion exchange, surface treatment with a basic or acidic gas such as chlorine gas or ammonia, Alternatively, the physical properties can be adjusted by combining a plurality of processes.

In the catalyst used in the present invention, examples of the constituent other than the crystalline molecular sieve include inorganic oxides containing an element selected from aluminum, silicon, zirconium, boron, titanium and magnesium. Such an inorganic oxide is used as a bonding agent in molding the crystalline molecular sieve and also has a function as an active component promoting hydrogenation deoxygenation and hydroisomerization, and it is preferable to use aluminum, silicon, zirconium, boron, It is preferable to include two or more elements selected from titanium and magnesium.

The content of the crystalline molecular sieve in the whole catalyst is preferably 2 to 90 mass%, more preferably 5 to 85 mass%, and even more preferably 10 to 80 mass%, based on the whole amount of the catalyst Do. When the content is less than 2 mass%, the hydrodeoxygenation activity and the hydrogenation isomerization activity as a catalyst tend to be lowered. When the content is more than 90 mass%, the catalyst formability is lowered, There is concern.

There is no particular limitation on the method of introducing silicon, zirconium, boron, titanium and magnesium, which are constituent elements other than aluminum, into the carrier with respect to a constituent other than the crystalline molecular sieve in the catalyst used in the present invention. It is good to use the solution containing an element as a raw material. For example, with respect to silicon, silicic acid, water glass, silica sol, etc. for boron, boric acid for boron and the like, alkali metal salts of phosphoric acid and phosphoric acid for phosphorus, titanium, titanium tetrachloride and various alkoxides Zirconium sulfate, various alkoxide salts, etc. can be used about zirconium, such as a salt.

It is preferable to add the raw material of a carrier component other than aluminum oxide in the process before baking of a support | carrier. For example, an aluminum hydroxide gel containing such components may be prepared in advance of adding the raw materials to an aqueous aluminum solution, and the raw materials may be added to the combined aluminum hydroxide gel. Alternatively, in the step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading the mixture, it is preferable to add the raw material, but it is more preferable to coexist in the step of combining the aluminum hydroxide gel . The mechanism of the effect of the carrier component other than aluminum oxide is not necessarily clarified, but it is presumed that it forms a complex oxide state with aluminum, and this causes an increase in the surface area of the carrier or interaction with the active metal, I think it is crazy.

The carrier containing the crystalline molecular sieve contains at least one metal selected from the elements of Groups 6A and 8 of the Periodic Table. Among these metals, at least one metal selected from Pd, Pt, Rh, Ir, Au, Ni and Mo is preferably used, and it is more preferable to use a combination of two or more metals selected therefrom. Suitable combinations include, for example, Pd-Pt, Pd-Ir, Pd-Rh, Pd-Au, Pd-Ni, Pt-Rh, Pt-Ir, Pt-Au, Pt-Ni, Rh-Ir, Rh- Au, Rh-Ni, Ir-Au, Ir-Ni, Au-Ni, Ni-Mo, Pd-Pt-Rh, Pd-Pt-Ir, Pd-Pt-Ni, etc. are mentioned. Among them, a combination of Pd-Pt, Pd-Ni, Pt-Ni, Pd-Ir, Pt-Rh, Pt-Ir, Rh-Ir, Pd-Pt-Rh, Pd-Pt-Ir, Pt-Pd-Ni The combination of Pd-Pt, Pd-Ni, Pt-Ni, Pd-Ir, Pt-Ir, Pd-Pt-Ir and Pt-Pd-Ni is more preferable.

The total content of the active metals based on the catalyst mass is preferably from 0.1 to 2% by mass, more preferably from 0.2 to 1.5% by mass, and still more preferably from 0.5 to 1.3% by mass as a metal. If the total amount of metals supported is less than 0.1% by mass, the active sites tend to be reduced and sufficient activity tends to be not obtained. On the other hand, when it exceeds 2 mass%, the metal does not disperse effectively, and there is a tendency for sufficient activity not to be obtained.

The method of incorporating such an active metal into the catalyst is not particularly limited, and a known method applied when producing a conventional desulfurization catalyst can be used. A method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably adopted. The equilibrium adsorption method, the pore-filling method, the incipient-wetness method and the like are also preferably adopted. For example, the pore-filling method is a method of measuring the pore volume of a carrier in advance and impregnating a metal salt solution having the same volume as this. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method depending on the amount of metal supported or the physical properties of the catalyst carrier.

It is preferable that the said catalyst used by this invention carries out the reduction process of the active metal contained in a catalyst before providing to reaction. The reduction treatment is not particularly limited, but is reduced by treating at a temperature of 200 to 400 ° C. under a hydrogen stream. In addition, it is preferable to perform such a reduction process in the range of 240-380 degreeC. When the reduction temperature is lower than 200 ° C, the reduction of the active metal does not sufficiently proceed, and there is a possibility that the hydrogenation deoxygenation and hydrogenation isomerization activity can not be sufficiently exhibited. On the other hand, when the reduction temperature is higher than 400 ° C, agglomeration of the active metal proceeds and there is a possibility that the same activity can not be sufficiently exhibited.

When the active metal of the catalyst used in the present invention is in a reduced state, the adsorption amount of carbon monoxide per 1 g of the catalyst is preferably 0.003 to 0.05 mmol, more preferably 0.005 to 0.04 mmol, even more preferably 0.009 to 0.03 mmol Do. If the amount of such adsorption is less than 0.003 mmol, metal tends to aggregate and the active point tends to decrease. On the other hand, when adsorption amount exceeds 0.05 mmol, it exists in the tendency for activity fall to accelerate | stimulate with passage of reaction time. The measurement of carbon monoxide adsorption amount can apply the general measuring method used for a catalyst carrying a reducing metal. Concretely, a certain amount of the catalyst can be recovered by a pulsed method or a fixed method after cooling at a temperature of 350 ° C under a hydrogen stream and then cooling to 50 ° C.

In addition, in the present invention, in addition to the above catalyst (hydrogenation purification catalyst), if necessary, a scale component flowing into the processing oil may be trapped, or a guard catalyst may be used for the purpose of supporting the hydrogenation purification catalyst A metal catalyst and an inert filler may be used. These may be used alone or in combination.

Conditions for contacting the oil to be treated with the catalyst in the presence of hydrogen include a hydrogen pressure of 2 to 13 MPa, a liquid space velocity (LHSV) of 0.1 to 3.0 h ⁻¹ , a hydrogen oil ratio (hydrogen / oil ratio) of 150 to 1500 NL / L, preferably hydrogen pressure 2 to 13 MPa, liquid space velocity (LHSV) 0.1 to 3.0 h ⁻¹ , hydrogen oil ratio (hydrogen / oil ratio) 250 to 1500 NL / L, and more preferably, hydrogen pressure 2.5 To 10 MPa, liquid space rate 0.5 to 2.0 h ^-1 , hydrogen flow rate 300 to 1200 NL / L, more preferably, hydrogen pressure 3 to 8 MPa, liquid space speed 0.8 to 1.8 h ^-1 , hydrogen flow rate 350 to 1000 NL / L All of these conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen ratio do not reach the lower limit, the reactivity tends to decrease or the activity rapidly decreases. On the other hand, when the hydrogen pressure and the hydrogen ratio exceed the above upper limits, excessive equipment investment such as a compressor tends to be necessary. In addition, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is lower than the lower limit, a reactor having a very large inner volume is required, and excessive facility investment tends to be required. When exceeding an upper limit, there exists a tendency for reaction not to fully advance.

In addition, the temperature conditions at the time of contacting a to-be-processed oil and a catalyst in presence of hydrogen are 150-380 degreeC. Preferably it is 170-360 degreeC, More preferably, it is 220-350 degreeC. If the temperature is lower than 150 ° C, the deoxidizing activity tends to become insufficient. On the other hand, if the temperature is higher than 380 ° C, the oil to be treated is excessively decomposed to produce oils useful for the production of liquid fuel (for example, The yield of oil in the range of 350 ° C. tends to be lowered.

The reactor may be of a fixed-bed type. That is, hydrogen may employ either a countercurrent or cocurrent type with respect to the oil to be treated. It is also possible to use a plurality of reactors, or a combination of countercurrent and cocurrent. As a general format, it is down flow, and it is possible to employ a gas-liquid double-flow type. The reactors may be used alone or in combination of two or more, and a structure in which the inside of one reactor is divided into a plurality of catalyst phases may be adopted.

The hydrogenated refined oil that has been hydrogenated and refined in the reactor is fractionated into hydrogenated refined oil containing a predetermined oil fraction through a gas-liquid separation process or a rectification process. For example, it is divided into light oil fraction and residue oil fraction. If necessary, the gas, naphtha fraction, and kerosene fraction may be fractionated. Hydrogen can be produced by modifying a part of the generated light hydrocarbon fraction produced in a steam reforming apparatus. Hydrogen produced in this manner has a feature of being a carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and the load on the environment can be reduced. In addition, water, carbon monoxide, carbon dioxide, hydrogen sulfide and the like may be generated depending on the reaction of oxygen or sulfur contained in the oil to be treated. However, in a plurality of reactor or product recovery processes, a gas- It can be installed well. The gaseous powder from which the by-product gas was removed by the by-product gas removal apparatus may be mixed with the to-be-processed oil, and may be recycled and used. It may also be used after increasing the hydrogen purity contained in the gas by a membrane separation device or a pressure swing adsorption device at the front end mixed with the oil to be treated. The concentration of carbon monoxide contained in the gas to be recycled is preferably 0.5% by volume or less, more preferably 0.1% by volume or less, from the viewpoint of maintaining the catalytic activity.

Hydrogen gas is generally introduced from the inlet of the first reactor with the oil to be treated before or after passing through the furnace, but apart from this, the purpose is to control the temperature in the reactor and maintain the hydrogen pressure throughout the reactor. As a result, hydrogen gas may be introduced between the catalyst beds or between the plurality of reactors. The hydrogen thus introduced is generally referred to as quench hydrogen. The ratio of the quench hydrogen to the hydrogen gas introduced along with the treated oil is preferably 10 to 60% by volume, more preferably 15 to 50% by volume. When the ratio of the quench hydrogen is less than 10% by volume, the reaction at the subsequent reaction site tends not to proceed sufficiently. When the ratio of the quench hydrogen exceeds 60% by volume, the reaction near the inlet of the reactor tends not to proceed sufficiently have.

When using the hydrogenated refined oil manufactured by this invention as a diesel oil base material, it contains the oil which has a boiling point of at least 260-300 degreeC, sulfur content is 10 mass ppm or less, and oxygen content is 0.3 mass% or less More preferably 7 mass ppm or less of sulfur content and 0.3 mass% or less of oxygen content, more preferably 3 mass ppm or less of sulfur content and 0.2 mass% or less of oxygen content. When the sulfur content and the oxygen content exceed the above upper limit value, there is a possibility of affecting the filter or catalyst used in the exhaust gas treatment apparatus of the diesel engine, and also the engine and other constituent members.

In addition, when using the hydrogenated refined oil manufactured by this invention as a base oil fraction, the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is 0.2 in the paraffin powder contained in the said fraction. It is preferable that it is the above, It is more preferable that it is 0.5 or more, It is further more preferable that it is 1.0 or more. If the ratio is less than 0.2, the fluidity of the oil can not be maintained in a low-temperature environment, or clogging or the like may occur in the fuel filtering apparatus of the diesel engine due to crystals deposited under a low-temperature environment, which may cause troubles.

The hydrogenated refined oil produced by the present invention can be suitably used particularly as diesel light oil or heavy oil base material. Hydrogenated refined oil may be used singly as diesel light oil or heavy oil base material, but it can be used as diesel light oil or heavy base material in which components such as other base materials are mixed. As another substrate, a light oil fraction and / or a kerosene fraction obtained in a general petroleum refining step and a residue fraction obtained by the hydrogenation purification method of the present invention may be mixed. In addition, a synthetic gas oil or synthetic kerosene, which is composed of hydrogen and carbon monoxide, which is obtained through a Fischer Tropsch reaction or the like, may be mixed with a so-called synthesis gas as a raw material. Such synthetic light oil or synthetic kerosene contains almost no aromatic component, and is characterized by a saturated hydrocarbon as a main component and a high cetane number. As a method for producing the synthesis gas, a known method can be used and is not particularly limited.

In the present invention, the hydrogenation purification process for hydrogenating and purifying the crude oil includes a first hydrogenation process for removing 70 mass% or more of the initial oxygen content contained in the object oil to obtain a first purified oil, % Of the second refined oil by removing oxygen remaining in the first refined oil to obtain a second refined oil, wherein the second refined oil is obtained by heating the second refined oil at a temperature of 150 to 350 DEG C , The ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is preferably 0.2 or more. If the oxygen removal rate in the first hydrogenation process is less than 70 mass%, the hydrogenation deoxygenation and the hydrogenation isomerization in the second hydrogenation process may not proceed sufficiently.

In the hydrogenation and purification method of the present invention, at least one of the first hydrogenation step and the second hydrogenation step is carried out in the presence of hydrogen, the oil to be treated containing the oxygen-containing hydrocarbon compound and crystalline molecular sieve. And a catalyst containing at least one metal selected from the elements of Groups 6A and 8 of the Periodic Table of Elements carried on the carrier. That is, you may perform either process of a 1st hydrogenation process and a 2nd hydrogenation process using catalysts other than the said catalyst.

In the first hydrogenation step, a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and a porous inorganic oxide containing at least one element selected from the group consisting of Group 6A and 8 It is preferable to use a catalyst containing at least one metal (active metal) selected from the group elements. Here, as the active metal, it is more preferable that it is at least one element selected from Pd, Pt, Rh, Ir, Au, Ni, and Mo.

In the second hydrogenation step, the carrier containing the crystalline molecular sieve and the elements selected from the elements of Group 6A and Group 8 (preferably the Group 8 elements) of the periodic table supported on the carrier are selected Preference is given to using catalysts containing at least one metal. A plurality of catalysts may be used in the second hydrogenation step, and a catalyst having a hydrogenating activity may be added to the end of the second hydrogenation step for the purpose of improving the stability of the refined oil.

Example

Hereinafter, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to the following examples.

[Examples 1 and 2 and Comparative Examples 1 to 4]

(Preparation of catalyst)

<Catalyst A-1>

185 g of water glass No. 3 was added to 3000 g of aqueous sodium aluminate solution having a concentration of 5% by mass, and placed in a container kept at 65 ° C. On the other hand, 3000 g of an aqueous aluminum sulfate solution having a concentration of 2.5% by mass was prepared in a separate container kept at 65 캜, and an aqueous solution containing the above-mentioned sodium aluminate was added dropwise thereto. The point of time when the pH of the mixed solution reached 7.0 was regarded as an end point, and the resultant slurry-like product was passed through a filter to obtain a cake-like slurry.

The slurry on the cake was transferred to a vessel equipped with a reflux condenser and 150 ml of distilled water and 10 g of a 27% aqueous ammonia solution were added and the mixture was heated and stirred at 75 占 폚 for 20 hours. The slurry was placed in a kneading apparatus and kneaded while heating at 80 ° C. or higher to remove moisture to obtain a kneaded product in clay form. The obtained kneaded product was extruded in the form of a cylinder having a diameter of 1.5 mm by an extruder, dried at 110 DEG C for 1 hour and then calcined at 550 DEG C to obtain a molded carrier.

50 g of the obtained molding carrier was placed in a branch flask and the metal was impregnated with 35 ml of a mixed aqueous solution of tetraammine platinum (II) chloride and tetraamminepalladium (II) chloride while degassing with a rotary evaporator. The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst A-1. The supported amounts of platinum and palladium in catalyst A-1 were 0.5 mass% and 0.7 mass%, respectively, based on the catalyst mass. Table 1 shows the physical properties of the prepared catalyst A-1.

<Catalyst B-1>

3000 g of a sodium aluminate aqueous solution having a concentration of 5% by mass was placed in a container kept at 65 占 폚. On the other hand, 3000 g of an aqueous aluminum sulfate solution having a concentration of 2.5% by mass was prepared in a separate container kept at 65 캜, and the aqueous sodium aluminate solution was added dropwise thereto. The slurry phase product obtained was passed through a filter to obtain a slurry on the cake, with the starting point at which the pH of the mixed solution reached 7.0.

The cake slurry was transferred to a vessel equipped with a reflux condenser, and 150 ml of distilled water and 10 g of a 27% aqueous ammonia solution were added thereto, followed by heating and stirring at 75 ° C. for 20 hours. The slurry was placed in a kneading apparatus and heated to 80 ° C. or higher to knead while removing moisture to obtain a kneaded product in clay form. The obtained kneaded product was extruded in the form of a cylinder having a diameter of 1.5 mm by an extruder, dried at 110 DEG C for 1 hour and then calcined at 550 DEG C to obtain a molded carrier.

50 g of the obtained shaped support was placed in an eggplant-shaped flask, and metal was impregnated with 35 ml of a mixed aqueous solution of dinitroamine platinum (II) and dinitroamine palladium (II) while being degassed by a rotary evaporator. The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst B-1. The loading amount of platinum and palladium in the catalyst B-1 was 0.5% by mass and 0.7% by mass, respectively, based on the catalyst mass. Table 1 shows the physical properties of the prepared catalyst B-1.

(Example 1)

A first reaction tube (inner diameter of 20 mm) filled with catalyst A-1 (50 ml) and a second reaction tube (inner diameter of 20 mm) filled with catalyst A-1 (50 ml) were mounted in a fixed bed flow reactor in series. It was. Thereafter, the reduction treatment of the catalyst was carried out for 6 hours under conditions of an average catalyst layer temperature (reaction temperature) of 320 DEG C, a hydrogen partial pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min.

After the reduction treatment of the catalyst, hydrogenation purification was performed using palm oil (the ratio of the compound which has the triglyceride structure occupied by an oxygen containing hydrocarbon compound: 98 mol%) as to-be-processed oil. 15 degreeC density of the to-be-processed oil was 0.916g / ml, and content of oxygen content was 11.4 mass%. In addition, the conditions of hydrorefining made the reaction temperature of the 1st and 2nd reaction tube 250 degreeC, the pressure 5.5 MPa, and liquid space velocity 0.8h- ¹ . In addition, the capacity ratio (quench hydrogen ratio) of the hydrogen gas introduced between the first reaction tube and the second reaction tube is 20% by volume of the total introduced hydrogen, and the hydrogen / oil ratio determined by the total introduced hydrogen is 600NL /. L was set. The results obtained are shown in Table 2.

(Example 2)

A mixed oil obtained by mixing 70 volumes of palm oil and 30 volumes of petroleum-based desulfurized diesel oil, which was the same as that used in Example 1, was used as the oil to be treated and the reaction temperature of the first and second reaction tubes was changed to 260 ° C. In the same manner as in 1, hydrogenation purification was performed. The petroleum-derived desulfurized light oil has a density of 0.838 g / ml at 15 ° C, a sulfur content of 15 mass ppm, and the colostral and end points are 211 ° C and 365 ° C, respectively. The density of the to-be-processed oil is 0.893 g / ml, the content of oxygen content is 8.2 mass% and the content of sulfur content is 4.2 mass ppm.

(Comparative Example 1)

Hydrogenation and purification were carried out in the same manner as in Example 1 except that Catalyst B-1 was used instead of Catalyst A-1. The results obtained are shown in Table 2.

(Comparative Example 2)

Hydrogenation purification was carried out in the same manner as in Example 1 except that the reaction temperature of the first and second reaction tubes was changed to 120 캜 at the time of hydrogenation purification. The results obtained are shown in Table 2.

(Comparative Example 3)

Hydrogenation purification was carried out in the same manner as in Example 1 except that the reaction temperature of the first and second reaction tubes was changed to 400 캜 at the time of hydrogenation purification. The results obtained are shown in Table 2.

(Comparative Example 4)

Hydrogenation and purification were carried out in the same manner as in Example 2, except that Catalyst B-1 was used instead of Catalyst A-1. The results obtained are shown in Table 2.

[Examples 3 to 5 and Comparative Example 5]

(Preparation of catalyst)

<Catalyst A-2>

A commercially available boehmite powder (manufactured by Shokubai Chemical Co., Ltd.) and silica alumina powder (manufactured by Shokubai Chemical Industry Co., Ltd.) were added to a polytetrafluoroethylene beaker in such a manner that the ratio of the number of atoms of silicon / The mixture was mixed, distilled water was added, concentrated and kneaded while heating to obtain a clay-like kneaded product. To the kneaded product, protonated ZSM-5 (a ratio of the number of atoms of silicon / aluminum: 40) synthesized as a zeolite was added so as to be 65% by mass of the total catalyst in terms of oxide, and kneaded again. The obtained kneaded product was extruded in the form of a cylinder having a diameter of 1.5 mm by an extruder, dried at 110 DEG C for 1 hour, and then calcined at 500 DEG C to obtain a molded carrier.

10 g of the obtained molded support was placed in an eggplant type flask, and a mixed aqueous solution of tetraammine platinum (II) chloride and tetraammine palladium (II) chloride was injected into the flask while deaeration with a rotary evaporator to impregnate the molded carrier with metal, After drying at, it was calcined at 350 ° C. to obtain catalyst A-2. The supported amount of platinum and palladium in the catalyst A-2 was 0.5% by mass of platinum and 0.7% by mass of palladium based on the whole amount of the catalyst.

<Catalyst B-2>

A commercially available boehmite powder (manufactured by Shokubai Chemical Co., Ltd.) and silica alumina powder (manufactured by Shokubai Chemical Industry Co., Ltd.) were added to a polytetrafluoroethylene beaker in such a manner that the ratio of the number of atoms of silicon / The mixture was mixed, distilled water was added, concentrated and kneaded while heating to obtain a clay-like kneaded product. To the kneaded product, the proton-type ZSM-22 (ratio of the number of atoms of silicon / aluminum: 45) synthesized as zeolite was added so as to be 65% by mass of the entire catalyst in terms of oxide, and then kneaded again. The obtained kneaded product was extruded in the form of a cylinder having a diameter of 1.5 mm by an extruder, dried at 110 DEG C for 1 hour, and then calcined at 500 DEG C to obtain a molded carrier. 10 g of the obtained molding carrier was supported with platinum and palladium in the same manner as in the catalyst A-2 to obtain a catalyst B-2. The supported amount of platinum and palladium in the catalyst B-2 was 0.5% by mass of platinum and 0.7% by mass of palladium based on the whole amount of the catalyst.

<Catalyst C-2>

A mixed solution obtained by adding 18.0 g of water glass No. 3 to 3000 g of a sodium aluminate aqueous solution having a concentration of 5% by mass was added dropwise to an aqueous solution of aluminum sulfate at a concentration of 2.5% by mass kept at 65 캜 until the pH became 7.0. The slurry product obtained was filtered through a filter to obtain a cake slurry.

The slurry on the cake was transferred to a vessel equipped with a reflux condenser and 150 ml of distilled water and 10 g of a 27% aqueous ammonia solution were added and the mixture was heated and stirred at 75 占 폚 for 20 hours. The slurry was placed in a kneading apparatus and heated at 80 DEG C or higher to remove water and kneaded to obtain a kneaded product in the form of a clay. The obtained kneaded product was extruded in the shape of a cylinder having a diameter of 1.5 mm by an extruder, dried at 110 DEG C for 1 hour and then calcined at 550 DEG C to obtain a molded carrier. The aluminum content of the shaped support was 90.1% by mass in terms of aluminum oxide, and the silicon content was 9.9% by mass in terms of silicic acid.

50 g of the obtained molded support was placed in an eggplant type flask, and a mixed aqueous solution of tetraammineplatinum (II) chloride and tetraammine palladium (II) chloride was injected into the flask while being degassed by a rotary evaporator to impregnate the molded support with metal, After drying at, it was calcined at 350 ° C. to obtain a catalyst C-2. The loading amount of platinum and palladium in the catalyst C-2 was 0.5% by mass of platinum and 0.7% by mass of palladium based on the whole amount of the catalyst.

(Example 3)

A second reaction tube (inner diameter 20 mm) filled with the catalyst A-2 (50 ml) and a second reaction tube (inner diameter 20 mm) filled with the same catalyst A-2 (50 ml) It was. Thereafter, the catalyst was subjected to a reduction treatment for 6 hours under the conditions of an average catalyst bed temperature of 320 ° C, a hydrogen partial pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min. Further, the carbon monoxide adsorption amount per 1 g of the catalyst A-2 in the reduced state was 0.037 mmol.

After the catalytic reduction operation, hydrogenation purification was performed using palm oil (the ratio of the compound which has the triglyceride structure occupied by an oxygen containing hydrocarbon compound: 98 mol%) as to-be-processed oil. The 15 degreeC density of the to-be-processed oil was 0.916 g / ml, the oxygen content was 11.4 mass%, and the sulfur content was 0.2 mass ppm or less. Further, the conditions of the hydrogenation purification, and the first and the second reaction tube, a reaction temperature of 310 ℃, 5MPa pressure, liquid space velocity of 0.7h ^-1 to. In addition, the capacity ratio (quench hydrogen ratio) of the hydrogen gas introduced between the first reaction tube and the second reaction tube is 20% by volume of the total introduced hydrogen, and the hydrogen / oil ratio determined by the total introduced hydrogen is 600NL /. L was set. The results obtained are shown in Table 3.

(Example 4)

Hydrogenation and purification were carried out in the same manner as in Example 3 except that Catalyst B-2 was used instead of Catalyst A-2. The results obtained are shown in Table 3. In addition, the carbon monoxide adsorption amount per 1 g of catalyst B-2 in a reduced state was 0.035 mmol.

(Example 5)

The hydrogenation purification was carried out in the same manner as in Example 3, except that the first reaction tube was charged with 50 ml of the catalyst C-2, and the second reaction tube was charged with 50 ml of the catalyst A-2. The results obtained are shown in Table 3. Further, the carbon monoxide adsorption amount per 1 g of the catalyst C-2 in the reduced state was 0.038 mmol.

(Comparative Example 5)

Hydrogenation purification was carried out in the same manner as in Example 3 except that the catalyst C-2 was used instead of the catalyst A-2, the reaction temperature of the first reaction tube was 200 ° C and the reaction temperature of the second reaction tube was 310 ° C . The results obtained are shown in Table 3.

(Evaluation of low temperature performance)

The refined oil obtained by the hydrogenation purification of Examples 3 to 5 and Comparative Example 5 was obtained by removing distillate which is harder than boiling point by distillation at 150 캜 and then filtering the crude oil with JIS K2269 It was measured according to the "pouring point of the product and the petroleum product cloud point test method". Further, regarding the paraffin content in the residue, the mass ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) was measured. The results are shown in Table 3.

Claims (10)

In the presence of hydrogen, To-be-processed oil containing an oxygen-containing hydrocarbon compound, A carrier comprising a porous inorganic oxide comprising at least two elements selected from the group consisting of aluminum, silicon, zirconium, boron, titanium and magnesium, and a carrier selected from elements selected from Groups 6A and 8 of the Periodic Table of Elements Catalyst containing more than one species of metal, Hydrogenation which obtains refined oil through the hydrogenation purification process contacted under the conditions of hydrogen pressure of 2-13 MPa, liquid space velocity 0.1-3.0 h <^-1> , hydrogen oil ratio 150-1500 NL / L, reaction temperature 150-380 degreeC Purification method, Wherein the hydrogen contains hydrogen gas introduced along with the treated oil and hydrogen gas introduced as quench hydrogen and the ratio of the quench hydrogen to the hydrogen gas introduced along with the treated oil is 10 To 60% by volume of the hydrogenation purification method. The process according to claim 1, characterized in that the carrier contains a crystalline molecular sieve. The hydrogenation purification method according to claim 1 or 2, wherein the content of oxygen content is 0.1 to 15 mass% and the content of sulfur content is 50 mass ppm or less based on the total amount of the oil to be treated. The hydrogenation purification method according to claim 1 or 2, wherein the oxygen-containing hydrocarbon compound is a fat or oil component derived from animal and vegetable oils. The hydrogenation purification method according to claim 1 or 2, wherein the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is 90 mol% or more. The method according to claim 1 or 2, wherein the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) in paraffins contained in the oil at 150 to 350 DEG C of the purified oil is 0.2 or more A hydrogenation purification method, characterized in that to carry out the hydrogenation purification step. The method according to claim 2, wherein the crystalline molecular sieve contains zeolite containing silicon and the zeolite has a ratio of silicon to constituent elements other than oxygen and silicon (number of silicon atoms / oxygen and elements other than silicon Number of atoms of is 3 or more, hydrogenation purification method. The hydrogenation purification method according to claim 1 or 2, wherein the metal comprises at least one element selected from Pd, Pt, Rh, Ir, Au, Ni and Mo. The hydrogenation purification method according to claim 1 or 2, wherein the amount of carbon monoxide adsorbed per 1 g of the catalyst in which the metal is in a reduced state is in the range of 0.003 to 0.05 mmol. The process according to claim 1 or 2, wherein the hydrogenation purification step comprises a first hydrogenation step of removing at least 70 mass% of the initial oxygen content contained in the processed oil to obtain a first refined oil, and And a second hydrogenation step of removing oxygen remaining in the first purified oil so that 95 mass% or more of the initial oxygen content is removed, thereby obtaining a second refined oil, Wherein the second hydrogenation step is carried out such that the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) in the paraffin component contained in the oil of the second refined oil at 150 to 350 占 폚 is 0.2 or more The hydrogenation purification method characterized by the above-mentioned.