KR20090025246A - Hydrorefining process - Google Patents

Abstract

Disclosed is a hydrorefining process involving a hydrorefining step in which an oil to be treated is contacted with a catalyst in the presence of hydrogen under the conditions of a hydrogen pressure of 2 to 13 MPa, a liquid hourly 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 to thereby produce a purified oil. The oil contains an oxygenated hydrocarbon compound. The catalyst comprises: a carrier which comprises a porous inorganic oxide having at least two elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium; and at least one metal selected from the elements belonging to Groups 6A and 8 in the periodic table, which is supported on the carrier.

Description

Hydrogenation Purification Process

The present invention relates to a hydrogenation purification method.

As prevention measures of global warming, attention is focused on the effective use of biomass energy. Among the biomass energy, since the plant-derived biomass energy can effectively use the hydrocarbon converted from carbon dioxide by photosynthesis in the process of plant growth, the so-called biomass energy does not lead to the increase of carbon dioxide in the atmosphere from the viewpoint of the life cycle. 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 a plant or animal oil can be used as the diesel fuel, it is expected to play an effective role in reducing the carbon dioxide emission due to the synergy effect with the high energy efficiency of the 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 of manufacturing fatty acid methyl ester oil, as described in the following patent document 1, it is pointed out that the process of the by-product glycerin is required, and cost and energy etc. are required for washing | generating the produced oil.

Patent Document 1: Japanese Unexamined Patent Publication No. 2005-154647

Problems to be Solved by the Invention

In order to use the oil-fat component derived from animal and vegetable oil, and the fuel manufactured using this as a raw material, besides the above-mentioned problem, there exist the following problems. That is, since the oil-and-oil component derived from animal and vegetable oil generally has oxygen atoms in the molecule, there is a concern about the adverse effects that the oxygen component has on the structural members of the engine, and it is difficult to remove the oxygen component to an extremely 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.

Then, an object of this invention is to provide the hydrogenation refinement | purification method which can obtain the hydrogenation refined oil by which oxygen content was fully reduced when the to-be-processed oil containing an oxygen containing hydrocarbon compound is used.

Means to solve 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. It provides a hydrogenation purification method through a hydrogenation purification step of contacting under a condition of a hydrogen oil ratio of 150 to 1500 NL / L, a reaction temperature of 150 to 380 ℃.

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. Moreover, although the fatty acid which comprises animal and vegetable fats and oils has a linear paraffin or a linear olefin as a hydrocarbon backbone, in the case of the conventional hydrogenation purification method which does not have this structure, the obtained paraffin powder is low temperature performance, such as cloud point. There is a concern that this cannot be said to be practical enough.

Moreover, in the hydrogenation purification method of this invention, it is preferable that content of oxygen content is 0.1-15 mass% on the basis of the whole quantity of to-be-processed oil. Moreover, even if it contains or does not contain sulfur content, it is preferable that the content is low enough, and it is preferable that content of sulfur content is 50 mass ppm or less based on the whole quantity of the to-be-processed oil. If the oxygen content and sulfur content of the to-be-processed oil are respectively in the said range, stable deoxygenation activity can be maintained for a long time.

In the hydrogenation and purification method of the present invention, the oxygen-containing hydrocarbon compound is preferably an oil or fat component derived from animal and vegetable oils in view of the effective use of biomass energy.

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

In the hydrogenation and purification method of the present invention, the ratio of isoparaffin to normal paraffin (mass of isoparaffin / normal paraffin) in paraffin powder contained in 150 to 350 ° C. fraction of the refined oil obtained from the oil to be treated. 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 and purification method of the present invention, the crystalline molecular constituting the catalyst contains a zeolite containing silicon, and the zeolite contains a ratio of silicon to constituent elements excluding oxygen and silicon (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. Thereby, while hydrodeoxygenation reaction is accelerated | stimulated, the improvement of low temperature performance, such as hydroisomerization reaction and the decomposition removal reaction of paraffin, can fully be 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.

In the hydrogenation and purification method of the present invention, the hydrogenation and purification step includes a first hydrogenation step of removing at least 70% by mass of the initial oxygen content contained in the oil to be treated to obtain a first refined oil, and the initial oxygen content. 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, when a to-be-processed oil containing an oxygen-containing hydrocarbon compound is used, a hydrogenation purification method capable of economically and very effectively obtaining a hydrogenated refined oil having sufficiently reduced oxygen content is provided.

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 an oxygen-containing hydrocarbon compound, the oil-fat component derived from animal and vegetable oil is suitable. Herein, the fat or oil component in the present invention may maintain or improve the performance of animal or vegetable fats and oils and animal oil components and / or animal oils and / or animal oils and / or components derived and produced from such fats and oils and oils and fats and oils. Ingredients added for the purpose are included.

Examples of fats and oils derived from animal and vegetable oils include tallow, rapeseed oil, soybean oil, palm oil, and the like. In the present invention, any fat or oil may be used as an oil or fat component derived from animal or vegetable oil, and waste oil after using such fat or oil may be good. However, plant fats and oils are preferable from a carbon neutral viewpoint, and rapeseed oil, soybean oil, and palm oil are more preferable from a fatty acid alkyl chain carbon number and its reactivity viewpoint. In addition, the said fats and oils may be used individually by 1 type or in mixture of 2 or more types.

Although the oil-fat component derived from animal and vegetable oil generally has a fatty acid triglyceride structure, it may contain the fat-and-oil component processed with ester bodies, such as another fatty acid and fatty acid methyl ester. 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 this invention, it is preferable that the ratio of the compound which has the triglyceride structure in the oxygen containing hydrocarbon compound contained in a to-be-processed oil is 90 mol% or more, It is more preferable that it is 92 mol% or more, It is more preferable that it is 95 mol% or more.

The oil to be treated may be an oxygen-containing hydrocarbon compound, and may contain compounds derived from chemical products such as plastics and solvents, in addition to the fats and oils derived from animal and vegetable oils described above, and are fischers based on a synthesis gas composed of carbon monoxide and hydrogen. It may also contain a synthetic oil obtained via a Fischer-Tropsch reaction.

In addition, the to-be-processed oil may contain the petroleum hydrocarbon fraction. As petroleum hydrocarbon fraction, the fraction obtained in the general petroleum refining process can be used. For example, the oil content corresponding to the predetermined boiling range obtained from an atmospheric distillation apparatus or a vacuum distillation apparatus, or obtained from a hydrodesulfurization apparatus, hydrocracking apparatus, residual oil direct desulfurization apparatus, fluid catalytic cracking apparatus, etc. You may use the oil content corresponding to a predetermined boiling range. In addition, you may use the oil obtained from each said apparatus individually by 1 type or in mixture of 2 or more types. 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 oil to be treated is preferably 0.1 to 15% by mass, more preferably 1 to 15% by mass, still more preferably 3 to 14% by mass, particularly preferably based on the total amount of the oil to be treated. Is 5-13 mass%. When content of oxygen content is less than 0.1 mass%, there exists a tendency for it to become difficult to stably maintain deoxidation activity and 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. In addition, content of oxygen content can be measured with a general element analyzer, For example, after converting a sample into carbon monoxide on platinum carbon or converting it into carbon dioxide again, it can measure using a thermal conductivity detector.

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 oil to be treated is preferably 50 mass ppm or less, more preferably 20 mass ppm or less, and more preferably 10 mass ppm or less, based on the total amount of the oil to be treated. When the content of sulfur exceeds 50 ppm by mass, it is difficult to stably maintain deoxygenation activity, and the sulfur content in hydrogenated refined oil tends to increase, and when used as a fuel such as a diesel engine. There is a fear of adverse effects on the engine exhaust gas purification device. In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "The sulfur test method" or ASTM-5453.

When the sulfur-containing hydrocarbon compound is contained in the oil to be treated, the sulfur-containing hydrocarbon compound may be mixed with the oil to be treated in advance, and the mixture may be introduced into the reactor of the hydrorefining apparatus, or when the oil to be treated is introduced into the reactor, the front end of the reactor You may supply in.

It is preferable that the to-be-processed oil used by this invention contains the oil component with a boiling point of 300 degreeC or more, and does not contain the heavy oil content exceeding boiling point 700 degreeC. When the to-be-processed oil containing no oil of boiling point 300 degreeC or more is used, it will become difficult to obtain sufficient yield by excessive decomposition. On the other hand, when the to-be-processed oil contains the heavy oil component whose boiling point exceeds 700 degreeC, precipitation of carbon in a catalyst is promoted by the heavy component, and there exists a tendency for activity to fall. In addition, the boiling point in this invention is a value measured based on the method of JISK2254 "distillation test method" or ASTM-D86.

In the hydrogenation and purification method of the present invention, a carrier comprising a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and Group 6A of the periodic table supported on the carrier 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 two or more selected from aluminum, silicon, zirconium, boron, titanium and magnesium as described above is used. The porous inorganic oxide is preferably at least two kinds selected from aluminum, silicon, zirconium, boron, titanium and magnesium in terms of further improving the deoxygenation activity and the desulfurization activity, and include aluminum and other elements. More preferred are inorganic oxides (composite oxides of aluminum oxide and other oxides).

The carrier included in the catalyst used in the present invention preferably contains crystalline molecular sieves. In order to provide sufficient hydrodeoxygenation activity and hydroisomerization activity, it is preferable that a crystalline molecular sieve contains at least silicon. Moreover, it is preferable that crystalline molecular sieve contains one or more types of aluminum, zirconium, boron, titanium, gallium, zinc, phosphorus as constituent elements other than silicon, and aluminum, zirconium, boron, titanium, It is more preferable to contain 1 or more types of phosphorus. By containing such an element, the crystalline molecular sieve can promote the hydrodeoxygenation reaction and the skeletal isomerization reaction of the hydrocarbon at the same time, and more fully achieve the low temperature performance of the refined oil. As such crystalline molecular sieve, zeolite is preferable, and zeolite containing silicon and aluminum, that is, aluminosilicate is more preferable.

Regarding elements other than oxygen among the elements constituting the crystalline molecular sieve, the ratio of silicon to the constituent elements excluding oxygen and silicon (the number of atoms of silicon / number of atoms of elements other than silicon) is 3 or more. 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. If this ratio is less than 3, there is a fear that the decomposition reaction of paraffin is promoted, resulting in 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. Although it does not specifically limit as a crystal structure of crystalline molecular sieve, FAU, AEL, MFI, MMW, TON, MTW, * BEA, MOR etc. which are mentioned by the structure prescribed | regulated by the international zeolite society are mentioned.

The method for synthesizing the crystalline molecular constituent constituting the catalyst used in the present invention is not particularly limited, and as is generally known, a hydrothermal synthesis method using a constituent raw material and an amine compound as a structural indicator can be used. have. Examples of the constituent raw materials include sodium silicate, colloidal silica, alkoxide silicate and the like 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.

In addition, 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, or the like as needed. Alternatively, the physical properties can be adjusted by combining a plurality of processes.

In the catalyst used in the present invention, examples of the constituents other than crystalline molecular weight include inorganic oxides containing an element selected from aluminum, silicon, zirconium, boron, titanium, and magnesium. These inorganic oxides are used as binders in forming crystalline molecular sieves and also function as active ingredients for promoting hydrodeoxygenation and hydroisomerization. Therefore, aluminum, silicon, zirconium, boron, It is preferable to include two or more elements selected from titanium and magnesium.

It is preferable that content of the crystalline molecular weight which occupies for the whole catalyst is 2-90 mass% on the basis of catalyst whole quantity, It is more preferable that it is 5-85 mass%, It is further more preferable that it is 10-80 mass% Do. When this content is less than 2 mass%, there exists a tendency for the hydrodeoxygenation activity and hydroisomerization activity as a catalyst to fall, and when it exceeds 90 mass%, catalyst formability will fall and the industrial manufacture of a catalyst will generate | occur | produce. There is concern.

With respect to the constituents other than the crystalline molecular sieve in the catalyst used in the present invention, the method of introducing silicon, zirconium, boron, titanium and magnesium, which are constituent elements other than aluminum, into the carrier is not particularly limited. It is good to use the solution containing an element as a raw material. For example, about silicon, such as silicic acid, water glass, silica sol, etc. about boron, about boric acid, about phosphorus, about phosphorus, about titanium, such as alkali metal salt of phosphoric acid and phosphoric acid, titanium sulfide, 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, after adding the said raw material to aluminum aqueous solution previously, you may manufacture the aluminum hydroxide gel containing such a component, and may add the said raw material with respect to the combined aluminum hydroxide gel. Alternatively, the raw material may be added to a commercially available aluminum oxide intermediate or boehmite powder by adding water or an acidic aqueous solution to kneading, but it is more preferable to coexist in the step of combining the aluminum hydroxide gel. . Effects of Carrier Components Other Than Aluminum Oxide The expression mechanism is not necessarily elucidated, but is thought to form a complex oxide state with aluminum, which affects activity by increasing the carrier surface area or interacting with active metals. I think it is crazy.

The carrier containing crystalline molecular resin is supported by at least one metal selected from elements of Groups 6A and 8 of the Periodic Table. Among these metals, it is preferable to use at least one metal selected from Pd, Pt, Rh, Ir, Au, Ni, and Mo, and more preferably use a combination of two or more metals selected from these. 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 More preferably, a combination of Pd-Pt, Pd-Ni, Pt-Ni, Pd-Ir, Pt-Ir, Pd-Pt-Ir, and Pt-Pd-Ni is more preferable.

As total content of the active metal based on a catalyst mass, 0.1-2 mass% is preferable as a metal, 0.2-1.5 mass% is more preferable, 0.5-1.3 mass% is still more preferable. If the total supported amount of the metal is less than 0.1% by mass, there is a tendency that the activity point decreases and sufficient activity cannot be 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. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of the active metal is preferably employed. Moreover, the equilibrium adsorption method, the pore-filling method, the incipient-wetness method, etc. are also preferably employed. 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. In addition, the impregnation method is not particularly limited, and can be impregnated by a suitable method depending on the amount of metal supported and 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 less than 200 ° C, the reduction of the active metal does not proceed sufficiently, and there is a fear that the hydrodeoxygenation and hydroisomerization activity cannot be sufficiently exhibited. Moreover, when reduction temperature exceeds 400 degreeC, aggregation of an active metal advances and there exists a possibility that activity may not be fully exhibited similarly.

When the active metal of the catalyst used in the present invention is in the reduced state, the carbon monoxide adsorption amount per 1 g of the catalyst is preferably 0.003 to 0.05 mmol, more preferably 0.005 to 0.04 mmol, still 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. Specifically, after reducing a certain amount of catalyst at 350 degreeC under hydrogen stream, it can cool to 50 degreeC and can obtain | require by a pulse method or a fixed method.

In addition, in the present invention, in addition to the catalyst (hydrogenation refining catalyst) described above, a guard catalyst or a desorbing agent may be used to trap scale content introduced with the oil to be treated as needed or to support the hydrogenation refining catalyst in a partition portion on the catalyst. A metal catalyst and an inert filler may be used. In addition, these can be used individually or in combination.

Conditions for contacting the oil to be treated with the catalyst in the presence of hydrogen include hydrogen pressure of 2 to 13 MPa, liquid space velocity (LHSV) of 0.1 to 3.0 h ^-1 , 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, more preferably hydrogen pressure 2.5 to 10 MPa, liquid space velocity 0.5 to 2.0 h ⁻¹ , hydrogen oil ratio 300 to 1200 NL / L, more preferably hydrogen pressure 3 to 8 MPa, liquid space velocity 0.8 to 1.8 h ⁻¹ , hydrogen oil ratio 350 to 1000NL / L. All of these conditions are factors that influence the reaction activity. For example, when the hydrogen pressure and the hydrogen oil ratio do not reach the lower limit, the reactivity tends to decrease or the activity rapidly decreases. On the other hand, when hydrogen pressure and hydrogen oil ratio exceed the said upper limit, there exists a tendency for excessive facility investment, such as a compressor, to be required. 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 said temperature is less than 150 degreeC, deoxidation activity tends to become inadequate, On the other hand, when it exceeds 380 degreeC, the to-be-processed oil will decompose | disassemble excessively and the oil (for example, the boiling point temperature 250-250) useful for manufacture of a liquid fuel The yield of oil in the range of 350 ° C. tends to be lowered.

As the type of reactor, a fixed bed system can be adopted. That is, hydrogen may employ either a countercurrent or cocurrent type with respect to the oil to be treated. Moreover, it is good also as a form which combined countercurrent and cocurrent using several reactor. As a general form, it is a downflow and the gas-liquid twin flow type can be employ | adopted. In addition, a reactor may combine single or multiple, and may employ | adopt the structure which divided the inside of one reactor into the several catalyst phase.

The hydrogenated refined oil which has been hydrogenated and purified in the reactor is fractionated into a hydrogenated refined oil containing a predetermined fraction through a gas-liquid separation process or a rectification process. For example, it is fractionated into light oil fraction or residue fraction. If necessary, the gas, naphtha fraction, and kerosene fraction may be fractionated. Hydrogen may be produced by reforming a portion of this light hydrocarbon fraction that is produced in a steam reformer. Hydrogen thus produced has the characteristics of carbon neutral in that the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the load on the environment. In addition, water, carbon monoxide, carbon dioxide, hydrogen sulfide, and the like may occur depending on the reaction of oxygen and sulfur contained in the oil to be treated, but gas-liquid separation equipment or other by-product gas removal equipment may be used between a plurality of reactors or in a product recovery process. You may install. 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. In addition, the carbon monoxide concentration contained in the gas to be recycled is preferably 0.5% by volume or less, and more preferably 0.1% by volume or less from the viewpoint of maintaining catalyst 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 introduced in this way is generally called quench hydrogen. It is preferable that it is 10-60 volume%, and, as for the ratio of quench hydrogen with respect to the hydrogen gas introduce | transduced with to-be-processed oil, it is more preferable that it is 15-50 volume%. If the ratio of quench hydrogen is less than 10% by volume, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the ratio of quench hydrogen exceeds 60% by volume, the reaction near the inlet of the reactor does not 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 It is preferable that content of sulfur content is 7 mass ppm or less, content of oxygen content is 0.3 mass% or less, it is more preferable that content of sulfur content is 3 mass ppm or less, and content of oxygen content is 0.2 mass% or less. When the sulfur content and the oxygen content exceed the above upper limit, there is a fear that the filter, the catalyst, and the engine and other components used in the exhaust gas treatment apparatus of the diesel engine are affected.

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, oil may not be able to maintain sufficient fluidity under a low temperature environment, or clogging in a fuel filtration device of a diesel engine may occur due to crystals precipitated under a low temperature environment, which may cause trouble.

The hydrogenated refined oil produced by the present invention can be suitably used particularly as a diesel diesel fuel or a heavy oil base material. The hydrogenated refined oil may be used alone or as a diesel gas oil or a heavy oil base material, but may be used as a diesel gas oil or a heavy base material mixed with components such as other base materials. As another base material, the light oil fraction and / or kerosene fraction obtained by the general petroleum refining process, and the residue fraction obtained by the hydrogenation purification method of this invention can also be mixed. In addition, a synthetic gas oil or synthetic kerosene obtained by a so-called synthesis gas composed of hydrogen and carbon monoxide as raw materials and via a Fischer Ropsch reaction can be mixed. Such synthetic light oils and synthetic kerosene contain little aromatics, have a saturated hydrocarbon as a main component, and have a high cetane number. In addition, as a manufacturing method of a synthesis gas, a well-known method can be used and it is not specifically limited.

In the present invention, the hydrorefining step of hydrorefining the oil to be treated includes a first hydrogenation step of removing 70 mass% or more of the initial oxygen content contained in the oil to be treated to obtain a first refined oil, and 95 mass of the initial oxygen content. A second hydrogenation step of removing the oxygen content remaining in the first refined oil to obtain a second refined oil so that at least% is removed, wherein the second hydrogenation process is an oil of 150 to 350 ° C. of the second refined oil. In the paraffin powder contained in, it is preferable that the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is preferably 0.2 or more. When the oxygen content removal rate in a 1st hydrogenation process does not reach 70 mass%, there exists a possibility that hydrodeoxygenation and hydroisomerization reaction in a 2nd hydrogenation process may not fully advance.

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. What is necessary is just to carry out by making the carrier containing and the catalyst containing the at least 1 sort (s) of metal selected from the elements of group 6A and 8 of the periodic table carry | supported by the said support | carrier carry out. 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 groups 6A and 8 of the periodic table supported on the porous inorganic oxide It is preferable to use a catalyst containing at least one metal (active metal) selected from the group elements. Here, as an active metal, it is more preferable that it is 1 or more types of elements chosen from Pd, Pt, Rh, Ir, Au, Ni, and Mo.

In the second hydrogenation step, a carrier containing crystalline molecular sieves, and elements of Groups 6A and 8 of the periodic table supported on the carrier (preferably elements of Group 8) are selected. Preference is given to using catalysts containing at least one metal. In addition, the catalyst used in a 2nd hydrogenation process may use one or more types, and the catalyst which has a hydrogenation activity may be filled in the back end of a 2nd hydrogenation process for the purpose of improving the stability of refined oil.

Example

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

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

(Production 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, 3000g of aluminum sulfate aqueous solution of 2.5 mass% concentration was manufactured in the other container which hold | maintained at 65 degreeC, and the aqueous solution containing said sodium aluminate was added dropwise here. At the point where the pH of the mixed solution became 7.0, the obtained slurry-like product was filtered 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 an aqueous 27% 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 kneaded while heating at 80 ° C. or higher to remove moisture to obtain a kneaded product in clay form. The resulting kneaded product was extruded into a shape of a 1.5 mm diameter cylinder by an extruder, dried at 110 ° C. for 1 hour, and then calcined at 550 ° C. to obtain a molding 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 aqueous sodium aluminate solution having a concentration of 5% by mass was placed in a container kept at 65 ° C. On the other hand, 3000 g of aluminum sulfate aqueous solution of 2.5 mass% in concentration was manufactured in the other container which hold | maintained at 65 degreeC, and the said sodium aluminate aqueous solution was added dropwise here. At the point where the pH of the mixed solution became 7.0, the obtained slurry product was filtered through a filter to obtain a cake slurry.

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 resulting kneaded product was extruded into a shape of a 1.5 mm diameter cylinder by an extruder, dried at 110 ° C. for 1 hour, and then calcined at 550 ° C. to obtain a molding carrier.

50 g of the obtained molding carrier was placed in a branched flask and degassed with a rotary evaporator, and the metal was impregnated using 35 ml of a mixed aqueous solution of dinitroammine platinum (II) and dinitroammine palladium (II). The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst B-1. The supported amounts of platinum and palladium in catalyst B-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 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. Subsequently, the reduction treatment of the catalyst was performed for 6 hours under the conditions of a catalyst bed average temperature (reaction temperature) 320 ° C., hydrogen partial pressure 5 MPa, and hydrogen gas amount 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 15 ° C density of the petroleum-based desulfurized diesel oil is 0.838 g / ml, the content of sulfur is 15 mass ppm, the super-oil point and the end point 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 was carried out in the same manner as in Example 1 except that the reaction temperature of the first and second reaction tubes was 120 ° C during the hydrogenation and purification. The results obtained are shown in Table 2.

(Comparative Example 3)

Hydrogenation was carried out in the same manner as in Example 1 except that the reaction temperature of the first and second reaction tubes was 400 ° C at the time of hydrogenation and 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]

(Production of Catalyst)

<Catalyst A-2>

In a polytetrafluoroethylene beaker, commercially available boehmite powders (cf. Shokubai Kasei Kogyo Co., Ltd.) and silica alumina powders (cf. Shokubaika Seiko Kogyo Co., Ltd.) were used so that the ratio of atoms of silicon / aluminum was 15. 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 material was extruded into the shape of the cylinder of diameter 1.5mm by the extrusion molding machine, dried at 110 degreeC for 1 hour, and then baked at 500 degreeC, and the molding support was obtained.

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

<Catalyst B-2>

In a polytetrafluoroethylene beaker, commercially available boehmite powders (cf. Shokubai Kasei Kogyo Co., Ltd.) and silica alumina powders (cf. Shokubaika Seiko Kogyo Co., Ltd.) were used so that the ratio of the number of atoms of silicon / aluminum was 15. The mixture was mixed, distilled water was added, concentrated and kneaded while heating to obtain a clay-like kneaded product. To this kneaded product, protonated ZSM-22 (a ratio of the number of atoms of silicon / aluminum: 45) synthesized as a zeolite was added so as to be 65% by mass of the total amount of the catalyst in terms of oxide, and kneaded again. The obtained kneaded product was extruded in the shape of a cylinder of 1.5 mm in diameter by an extrusion molding machine, dried at 110 ° C. for 1 hour, and calcined at 500 ° C. to obtain a molding 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 catalyst B-2 was 0.5 mass% of platinum and 0.7 mass% of palladium based on catalyst whole quantity.

<Catalyst C-2>

The mixed liquid which added 18.0 g of water glass No. 3 to 3000 g of sodium aluminate aqueous solution of 5 mass% of concentration, was added dropwise to the aluminum sulfate aqueous solution of 2.5 mass% of concentration which kept warm at 65 degreeC until 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 an aqueous 27% 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 kneaded while heating at 80 ° C. or higher to remove moisture to obtain a kneaded product in clay form. The obtained kneaded material was extruded into the shape of the cylinder of diameter 1.5mm by the extrusion molding machine, dried at 110 degreeC for 1 hour, and then baked at 550 degreeC, and the molding support was obtained. The aluminum content of the molded carrier was 90.1 mass% in terms of aluminum oxide, and the silicon content was 9.9 mass% in terms of silicic acid.

50 g of the obtained molding carrier was placed in a branch flask, and a mixed aqueous solution of tetraammine platinum (II) chloride and tetraamminepalladium (II) chloride was injected into the flask while degassing with a rotary evaporator to impregnate the metal with the molding carrier. After drying at, it was calcined at 350 ° C. to obtain a catalyst C-2. The supported amount of platinum and palladium in catalyst C-2 was 0.5 mass% of platinum and 0.7 mass% of palladium based on catalyst whole quantity.

(Example 3)

A first reaction tube (inner diameter 20 mm) filled with catalyst A-2 (50 ml) and a second reaction tube (inner diameter 20 mm) filled with catalyst A-2 (50 ml) were mounted in a fixed bed flow reactor in series. It was. Subsequently, the catalyst was reduced for 6 hours under the conditions of a catalyst bed average 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)

Catalyst C-2 (50 ml) was charged to the first reaction tube, Catalyst A-2 (50 ml) was charged to the second reaction tube, and hydrogenation and purification was carried out in the same manner as in Example 3. 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)

The catalyst C-2 was used instead of the catalyst A-2, and the hydrogenation purification was performed in the same manner as in Example 3, with the reaction temperature of the first reaction tube being 200 ° C and the reaction temperature of the second reaction tube being 310 ° C. . The results obtained are shown in Table 3.

(Evaluation of low temperature performance)

Refined oils obtained by the hydrogenation purification of Examples 3 to 5 and Comparative Example 5, after removing the oil lighter than the boiling point of 150 ℃ by distillation, and the residue (light kerosene oil), the cloud point JIS K2269 "crude oil and petroleum It was measured according to the "pouring point of the product and the petroleum product cloud point test method". In addition, with respect to the paraffin powder in the residue, the mass ratio (mass of isoparaffin / mass of normal paraffin) of isoparaffin to normal paraffin was measured. The results are shown in Table 3.

Claims (10)

In the presence of hydrogen, Periodic table 6A supported by a carrier comprising an oil to be treated containing an oxygen-containing hydrocarbon compound and a porous inorganic oxide comprising at least two elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium A catalyst containing at least one metal selected from the elements of Groups and Groups 8, A refined oil is obtained through a hydrogenation purification step of contacting under hydrogen pressure of 2 to 13 MPa, liquid space velocity of 0.1 to 3.0 h ⁻¹ , hydrogen oil ratio of 150 to 1500 NL / L, and reaction temperature of 150 to 380 ° C., Hydrogenation Purification Method. The hydrogenation purification method according to claim 1, wherein the carrier contains crystalline molecular sieves. The hydrogenation and purification method according to claim 1 or 2, wherein the content of oxygen is 0.1 to 15% by mass and the content of sulfur is 50 ppm by mass or less based on the total amount of the oil to be treated. The hydrogenation purification method according to any one of claims 1 to 3, wherein the oxygen-containing hydrocarbon compound is a fat or oil component derived from animal and vegetable oils. The hydrogenation purification method according to any one of claims 1 to 4, wherein the proportion of the compound having a triglyceride structure in the oxygen-containing hydrocarbon compound is 90 mol% or more. The paraffin powder according to any one of claims 1 to 5, wherein the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) in the paraffin powder contained in the oil of 150 to 350 ° C of refined oil. A hydrogenation purification method is performed so that it may become 0.2 or more. The ratio of silicon to constituent elements excluding oxy- and silicon, wherein the crystalline molecular weight comprises a zeolite comprising silicon, and the zeolite contains silicon (the number of atoms of silicon). The number of atoms of elements other than oxygen and silicon) is three or more, The hydrogenation purification method characterized by the above-mentioned. The hydrogenation purification method according to any one of claims 1 to 7, wherein the metal comprises at least one element selected from Pd, Pt, Rh, Ir, Au, Ni, and Mo. The hydrogenation purification method according to any one of claims 1 to 8, wherein the amount of carbon monoxide adsorbed per 1 g of the catalyst in which the metal is in the reduced state is in the range of 0.003 to 0.05 mmol. The first hydrogenation process according to any one of claims 1 to 9, wherein the hydrogenation purification step removes 70% by mass or more of the initial oxygen content contained in the oil to be treated to obtain a first refined oil, and A second hydrogenation step of removing the oxygen content remaining in the first refined oil to obtain a second refined oil such that at least 95 mass% of the initial oxygen content is removed; The second hydrogenation step is performed such that the ratio of isoparaffin to normal paraffin (mass of isoparaffin / mass of normal paraffin) is 0.2 or more in the paraffin powder contained in the oil of 150 to 350 ° C of the second refined oil. A hydrogenation purification method, characterized in that.