JPH0471577B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an additive suitable for hydrocracking heavy hydrocarbon oil, and a method for producing the same.
Furthermore, the present invention relates to a hydrocracking method for converting heavy hydrocarbon oil feedstock into light product oil using this additive. The term "additive" herein means a hydrocarbon oil suspension containing in concentrated form a catalyst or catalyst precursor for carrying out hydrocracking in a suspension catalytic process. The term "hydrocracking (method)" in this specification refers to a heavy oil portion with a high distillation boiling point contained in a hydrocarbon oil feedstock, such as a normal pressure or vacuum distillation residue oil portion,
It means the significant conversion (method) of hydrogen into distillate oils with lower distillation boiling points, such as naphtha, kerosene, gas oil, vacuum gas oil, etc., under high pressure and high temperature. In addition, by removing so-called hetero atoms such as sulfur and nitrogen contained in hydrocarbon oil raw materials, as well as heavy metals such as vanadium and nickel, and by effectively adding hydrogen to hydrocarbon compounds, It also includes (methods) for modifying the properties of hydrocarbon oil. Hydrocracking using a suspension catalyst method uses heavy oil with concentrated asphaltene, residual carbon, heavy metal compounds, ash, etc., such as vacuum distillation residue oil itself, as a raw material for heavy hydrocarbon oil. Depending on the treatment conditions adopted, hydrogen pressure alone may not be sufficient to avoid precipitation or deposition of significant carbonaceous solids due to side reactions of polycondensed compounds, or in fixed bed or fluidized bed catalyst systems. In cases where significant deterioration of the reactor or blockage of the reactor cannot be avoided,
This is particularly effective. (Conventional technology) A method classified as a suspension catalyst method among methods aimed at hydroprocessing in a broad sense, including the qualitative improvement (upgrading) of heavy hydrocarbons and conversion to light oil. The following methods have been proposed as methods to be carried out. U.S. Patent No. 4134825 and U.S. Patent No. 4285804 have been proposed as a method for hydrogenation treatment by adding transition metal compounds or catalysts obtained by decomposing them, in anticipation of the hydrogenation ability of transition metals.
No. 4,548,700, etc. U.S. Patent No. 4,299,685 uses crushed coal ash as a method for suspending solids and hydrocracking mainly by hydrogen pressure, and U.S. Pat. and so on. U.S. Patent No. 1 uses pulverized coal impregnated with metal salts as a method for suspending and hydrotreating solids impregnated or supported with metal compounds using the concept of catalysts used in fixed beds and fluidized beds. 4214977
No. 4,495,306, and US Pat. No. 4,557,822. Furthermore, as a hydrogenation treatment method in which a general-purpose metal compound having hydrogenation activity and a pulverized material or powder are independently added, US Pat. There are US Pat. No. 4,431,520 in which the powder is a by-product metal-containing dust, and JP-A-60-120791 in which the fraction is an ultrafine granular material. (Problem that the invention seeks to solve) Recently, the relationship between oil supply and demand has loosened compared to the time of the oil crisis, but from a medium to long-term perspective, oil resources will play a central role in energy and petrochemical raw materials. be. However, recently, while petroleum resources have tended to become heavier, demand for petroleum products has tended to become lighter to medium. As a countermeasure for this, we are implementing a continuous flow process that converts poor quality heavy hydrocarbon oil into higher value-added light oil at a high rate.
Specifically, for example, using vacuum distillation residue oil with a boiling point higher than 538°C as a raw material, the fraction with a boiling point lower than 538°C is 80% by weight or more, further 85% by weight or more, and even more strictly 90% by weight or more. It is strongly desired that a stable continuous flow process with high conversion rates can be realized that satisfies both technical and practical aspects. The suspension catalyst method has excellent characteristics in the hydrocracking process of heavy hydrocarbons, and in order to achieve this, there are two important functions required of the suspension catalyst. The purpose is to suppress as much as possible the production of polycondensation substances such as coke and asphaltene, which are generated due to side reactions that inevitably occur in the equipment, especially in the reaction zone. The goal is to avoid caulking development, where some of the material adheres or deposits inside the equipment. Functions that should be added include suppressing excessive gas generation, increasing the yield of light oil, and effectively adding hydrogen to hydrocracked oil (light oil) to remove heteroatoms (desulfurization, It is also desirable to have a function to perform nitrogen (e.g. nitrogen). On the other hand, the fate of suspended catalysts is that in order to achieve a simple continuous flow process, at least some of the catalysts must be used disposablely. Therefore, it is necessary to use a highly active catalyst that can sufficiently function in a small amount, while avoiding the use of catalysts that require complicated manufacturing methods or are relatively expensive. Furthermore, a problem that has been relatively overlooked in the prior art is the problem of handling oil produced during hydrocracking reactions. In other words, from a practical standpoint, a continuous distillation operation is required to separate and recover each fraction of the lightened product oil, and the processing of the resulting distillation residue complicates the process and increases operating costs. It is desirable to use the catalyst as is for fuel oil, etc., without separating or recovering the catalyst, which would lead to. However, the boiling point
Using vacuum distillation residue oil with a temperature higher than 538℃ as a raw material, 80% by weight or more, even 85% by weight or more,
More severely, when lightening is performed at a rate as high as 90% by weight, the distillation residue produced in the distillation operation with a boiling point higher than 538°C has a concentration of catalyst added to the raw material and the concentration of polycondensation substances produced in the reaction zone. , 5 times more than in raw materials and products, and even 10 times more than in raw materials and products.
It will be more than twice as concentrated. Therefore,
In order to handle such distillation residues without causing problems in so-called slurry handling, the suspended catalyst and polycondensation substances must be sufficiently fine and the solids concentration must be sufficiently low;
That is, it is customary that the content should be at most 40% by weight or less. In addition, in order to reduce the problem of combustion ash that occurs when distillation residue is burned, refractory inorganic substances that are commonly used as catalyst carriers should be minimized or not used in the suspension catalyst method. is desirable. In order to solve these problems, a lot of research has been carried out, and as mentioned above, several proposals have been made in the form of patents. Nothing has been proposed. (Means for Solving the Problems) The present inventors have solved the problem by satisfying both technical and practical aspects, and have made it possible to use heavy hydrocarbon oils such as vacuum distillation residue oil without being restricted by oil type. , has been conducting intensive research for many years on highly active catalysts suitable for highly hydrocracking using the suspension catalyst method. As a result, by mixing a particular substantially carbonaceous material powder and a particular molybdenum compound solution in a hydrocarbon oil, the powder and molybdenum compound agglomerate, respectively and with each other. It is possible to obtain a specific concentrated suspension that is uniformly and highly dispersed in hydrocarbon oil, without causing any In the reaction zone, the molybdenum compound contained in the suspension changes into finely dispersed amorphous molybdenum sulfide, which is characterized by not exhibiting crystallinity when measured by X-ray diffraction, and is then hydrogenated. It has been found that it exhibits an excellent hydrogenation activity effect in decomposition. The present invention has been made based on such novel findings. Therefore, the object of the present invention is to provide a new additive suitable for hydrocracking heavy hydrocarbon oil by a suspension catalyst method, a practical method for producing the same, and a method for producing heavy hydrocarbon oil using the additive. The object of the present invention is to provide a hydrocracking method for highly converting quality hydrocarbon oil into useful light oil. That is, in accordance with the present invention, an additive for hydrocracking heavy hydrocarbon oil comprises (1) carbonaceous material powder having an average primary particle size within the range of about 1 to 200 nm, and (2) polyester. A suspension is obtained by mixing in a hydrocarbon oil a solution obtained by dissolving at least one molybdenum compound selected from a heteropolyacid containing a molybdenum atom and a transition metal salt thereof in an oxygen-containing polar solvent. provided as an additive obtained by the method. Further, in accordance with the present invention, a method for hydrocracking heavy hydrocarbon oil is provided by adding the above-mentioned additives to a heavy hydrocarbon oil feedstock, and adding the resulting mixed oil in the presence of hydrogen or a hydrogen-containing gas. It is provided as a method consisting of thermal cracking and recovery of lightened product oil from the resulting product. Below, the features of the present invention will be explained in detail. Although the powder form of the specific carbonaceous material powder used in the present invention is not particularly defined, the average particle diameter of the primary particles is in the ultrafine region, that is, about 1 to 1.
Among primary particle powders belonging to 200 nm and secondary particle powders that are aggregates (agglomerates) of these primary particles, it is a powder that is substantially carbonaceous. Primary particles refer to the smallest unit particles constituting a powder that can exist without substantially breaking intramolecular bonds, and the primary particles in the scope of the present invention can be observed with an electron microscope. Therefore, the average primary particle diameter of primary particles is calculated from the particle size distribution of the (spherical) equivalent diameter, which is generally determined by measuring the number of about 200 to 500 particles using an electron microscope. ) It can be determined as the average primary particle diameter. The carbonaceous material referred to in the present invention is a carbonaceous material with an ash content of approximately 1% by weight or less at most, which is produced by carbonization of hydrocarbons, and which is produced under hydrocracking conditions. They are themselves substantially unreactive during use. Furthermore, carbonaceous materials belong to so-called lipophilic materials that are more easily wetted by hydrocarbon oil than fire-resistant inorganic materials. A method for efficiently obtaining carbonaceous material powder that conforms to the average primary particle diameter range of the present invention is a method using a build-up process in which particles are created by nucleation and growth from molecules, ions, and atoms, that is,
This is a method of producing carbon by carbonizing it through a gas phase, and specific substances include pyrolytic carbon and carbon black. Furthermore, among the carbonaceous material powders that are by-produced by water gasification reactions of hydrocarbons such as heavy oil and ethylene bottom oil, boiler combustion, etc., those whose average primary particle size is compatible with the present invention are also included. Available. Of course, coke and charcoal produced by carbonization in a liquid or solid state have an ash content of approximately 1.
It is also possible to apply materials that have a sufficiently low content of less than % by weight and are substantially carbonaceous. However, since these carbonaceous substances generally have a large primary particle size as they are, methods such as pulverization and classification must be adopted, and currently known pulverization and classification techniques are not practical. Although there may be a problem with the yield, any powder whose average primary particle size can be kept within the range of the present invention can be applied to the present invention. Preferred carbonaceous material powders include those collectively referred to as "carbon black." In other words, carbon black is classified into oil furnace black, gas furnace black, channel black, thermal black, etc. based on the manufacturing method, and there are many types of cheap carbon that are produced on an industrial scale. It is a powder substance. Many carbon blacks have a structure called a structure, that is, a chain structure or a chain-like structure due to connections and agglomeration between particles due to fusion or physical bonding at a portion of the primary particles, but when measured with an electron microscope, The primary particle diameter range of almost all types of industrially produced carbon black is approximately 10 to 150 nm, which is included within the average primary particle diameter range of the present invention. The smaller the average primary particle diameter of the carbonaceous material powder, the larger the external surface area per unit weight. The characteristics of a small particle size and a large external surface area based on the small particle size tend to play a role in holding or dispersing a metal (compound) having hydrogenation activity in a highly dispersed state on the surface and its vicinity. Further, the carbonaceous material powder having this characteristic can ensure high dispersibility and large free movement within the apparatus such as the reaction zone and the distillation zone. This provides a non-localized and uniform reaction field, and removes polycondensation substances attached to the carbonaceous material powder.
For example, coke precursor, coke, etc. can be easily discharged from the apparatus in a highly dispersed suspended state, resulting in favorable results such as less clogging within the apparatus. The average primary particle size is within the range of about 1 to 200 nm,
The particle size is preferably defined as being within the range of about 1 to 50 nm, more preferably within the range of about 1 to 30 nm, and the smaller the particle size is, the more preferable it is. The lower limit of the average primary particle size range, 1 nm, is not strict, but particles smaller than 1 nm can be applied as long as they are in the range of what is known as "powder". General-purpose carbon black, that is, furnace carbon black, is positioned as a non-porous material compared to ordinary bulk porous materials, and the total surface area per unit weight depends almost on the primary particle size. , i.e. approximately equal to the external surface area, approximately 50 ~
Although it is within the range of 250BET-m ² /g, when viewed microscopically, it has a complex microstructure consisting of an amorphous portion and a microcrystalline portion. Carbonaceous material powders obtained by subjecting these carbonaceous material powders to a secondary treatment, typically an oxidation treatment, to further increase the total surface area, also have an average primary particle size of about 1 to
If it is within the range of 200 nm, more preferably within the range of about 1 to 50 nm, it can be applied to the present invention. In other words, when oxidation treatment is applied, amorphous components and even microcrystalline components undergo various oxidation reactions, resulting in the formation of many micropores and roughness on the surface of the primary particles. An increase in total surface area occurs due to increased density and the creation of hollow states within the primary particles. The total surface area varies depending on the method and degree of treatment, but is approximately 200BET−m ² /
g, 1500BET−m ² /g for large surface area
reach even. Many known methods can be applied to the oxidation treatment to increase the total surface area. Typically, there is a method of oxidation treatment in a gas phase, that is, a method in which a gas phase oxidizing agent such as water vapor, carbon dioxide, oxygen, etc. is brought into uniform contact with the carbonaceous material powder under heating conditions. Further, as methods for oxidation treatment in the liquid phase, there are methods using chemicals such as nitric acid and chloric acid, and electrolytic treatment methods using various electrolytes such as acids, alkalis, and salts. Oxidation treatment often results in the introduction of functional groups such as carboxyl groups, phenolic hydroxyl groups, and ether groups as well as an increase in the total surface area, and may also increase acidity, so if necessary, Further, these functional groups may be removed by heating in an inert atmosphere, or neutralization treatment may be performed. From a practical standpoint, these secondary treatments should be conducted under appropriate conditions, taking into consideration the balance between mass reduction, surface area increase, change in average primary particle diameter, and improvement in effects based on these. select. Furthermore, even without such secondary treatment, some industrially produced carbonaceous material powders have a total surface area of 500 to
There are also porous carbonaceous material powders with a small average primary particle size, such as within the range of 1300BET-m ² /g.
These items can be used as is. It is essential for the carbonaceous material powder in the present invention to have a small average primary particle size (that is, a large external surface area depending on the particle size), but in addition, it has a large total surface area, that is, the primary particles themselves The present invention is further characterized by the synergistic effect achieved by using porous carbonaceous material powder. The specific molybdenum compound used in the present invention is selected from heteropolyacids containing molybdenum as a polyatom (hereinafter abbreviated as heteropolymolybdic acid) and transition metal salts thereof. Heteropolyacid is a general term for complex oxide acids produced by the condensation of two or more inorganic oxyacids. Heteromolybdate anions are polyatomic molybdenum oxyacids that form a group ~ group element with a central atom (heteroatom). ) and condensed, and the condensation ratio (atomic ratio of heteroatoms and polyatoms)
They are a unique group of compounds that can have a distinct single anion structure and intracrystalline arrangement. In other words, if a heteroatom is symbolized by "X", [X ⁺ⁿ Mo ₁₂ O ₄₀ ] ^-(8-
n) , [X ⁺ⁿ Mo ₁₂ O ₄₂ ] ^-(12-n) , [X ⁺⁵ ₂ Mo ₁₃ O ₆₂ ] ^-6 ,
[X ⁺⁴ Mo ₉ O ₃₂ ] ^-6 , [X ⁺ⁿ Mo ₆ O ₂₄ ] ^-(12-n) , [X ⁺ⁿ
Mo ₆ O ₂₄ H ₆ ] ^-(6-n) , etc., and [X ⁺ⁿ Mo ₁₁ O ₂₉ ] ^-(12-n) , which exist in solution as their structural decomposition products.
[X ⁺⁵ ₂ Mo ₁₇ O ₆₁ ] ^-10 etc. The acid form of these heteropolymolybutate anions can be applied to the present invention. All of the polyatoms constituting these heteropolymolybdic acids are molybdenum atoms, but in the present invention, heteropolymolybdic acids with a significantly large number of molybdenum atoms in the number of polyatoms, that is, the number of molybdenum atoms relative to the total number of polyatoms, are used. Heteropolymolybdic acids having a proportion of about 0.7 or more can also be included. That is, so-called mixed heteropolymolybdic acids in which some of the polyatoms are replaced with transition metal atoms other than molybdenum atoms can also be applied as long as the number of molybdenum atoms is within the above range. Naturally, even when using a simple mixture of a heteropolyacid having a molybdenum atom as a polyatom and a heteropolyacid having another transition metal atom as a polyatom, the number of molybdenum atoms in the total number of polyatoms is If they are used in a mixture such that the amount is about 0.7 or more, it can be included in the present invention. An example of a mixed heteropolymolybdic acid is [X ⁺ⁿ Mo _12-n W _n
O ₄₀ ] ^-(3-n) , [X ⁺ⁿ Mo _12-n V _n O ₄₀ ] ^-(3-n+m) ,
There are acid forms with the subscript m of 1 to 3. In these examples, it is not desirable to use a compound in which the number of substituted tungsten or vanadium atoms is further increased because the expected catalytic effect gradually deteriorates. As mentioned above, specific examples of representative heteropolymolybdate anions include [PMo ₁₂ O ₄₀ ] ^-3 ,
[SiMo ₁₂ O ₄₀ ] ^-4 , [GeMo ₁₂ O ₄₀ ] ^-4 ,
[P ₂ Mo ₁₈ O ₆₂ ] ^-6 , [CeMo ₁₂ O ₄₂ ] ^-3 ,
[PMo ₁₁ VO ₄₀ ] ^-4 , [SiMo ₁₁ O ₄₀ ] ^-3 ,
[GeMo ₁₁ VO ₄₀ ] ^-5 , [PMo ₁₁ WO ₄₀ ] ^-3 ,
[SiMo ₁₁ WO ₄₀ ] ^-4 , [CoMo ₆ O ₂₄ H ₆ ] ^-3 ,
Examples include [NiMo ₉ O ₂₂ ] ^-6 and [MnMo ₉ O ₃₂ ] ^-6 . On the other hand, many heteropolyacid compound groups (heteropolytungstic acid compound group) having a significant number of tungsten atoms as poly atoms are also known, but these compound groups have significantly inferior catalytic effects in the present invention. Excluded from scope. Many heteropolymolybdic acids have excellent oxidation properties, and heteropolymolybdic acids themselves having this property are easily reduced.
That is, compounds in which a heteropolymolybdate anion is reduced to 2, 4, or 6 electrons by an electrolytic reduction method or a chemical reduction method using various reducing agents, so-called "heteropolyblue" are also included in the present invention. Ru. For example, taking heteropolymolybdic acid of H ₃ ⁺³ [PMo ₁₂ O ₄₀ ] ^-3 , the two-electron reductant is H ₅ ⁺⁵ [PMo ₁₂ O ₄₀ ] ^-5 , and the four-electron reductant is H ₇ ^{+ 7}
[PMo ₁₂ O ₄₀ ] ^-7 , and the 6-electron reductant is H ₉ ⁺⁹
It is represented by [PMo ₁₂ O ₄₀ ] ^-9 , and their reduced forms can also be applied to the present invention. Furthermore, as the cation that forms a pair with the heteropolymolybdate anion, not only protons (acid type) but also transition metal cations (salt type) can be applied to the present invention. Transition metal cations that can be selected include Cu ²⁺ , Mn ²⁺ , Ni ²⁺ ,
Examples include Co ²⁺ , Fe ³⁺ , Cr ³⁺ , and Zn ²⁺ . These transition metal salts can be easily synthesized into compounds with partial or equivalent cation exchange, for example, by reacting heteropolymolybdic acid (acid type) with transition metal carbonates or transition metal nitrates in water. On the other hand, alkali metal salts containing Na ⁺ , K ⁺ , etc., alkaline earth metal salts containing Mg ²⁺ , Ca ²⁺ , etc., and ammonium salts and alkylammonium salts have significantly inferior catalytic activity and are therefore not suitable for the present invention. Not recommended for application. Based on the above description, various groups of heteropolymolybdic acid compounds in which the anion structure, partial exchange of molybdenum polyatoms, cation species, and degree of reduction of the anion are complexly changed are included as molybdenum compounds compatible with the present invention. let When at least one molybdenum compound selected from these heteropolymolybdic acids or transition metal salts thereof is used to produce the additive of the present invention, it is not in an aggregated bulk state but in a colloidal highly dispersed state. It is essential to use these molybdenum compounds in the form of a solution dissolved in a solvent in order to suspend them in a hydrocarbon oil and bring them into contact with the carbonaceous material powder. The solvent can be selected from solvents that have high solubility for these molybdenum compounds and that allow the molybdenum compound solution to become emulsified in the hydrocarbon oil. Specifically, These include water, which is an oxygen-containing polar solvent, lower alcohols, ethers, and ketones. A more preferred solvent is water, and since heteropolymolybdic acids are generally synthesized in water, the additives can be added in an aqueous solution state without isolating the crystalline solid after synthesis. Since it can be used for manufacturing, it also becomes an efficient method for manufacturing additives. The concentration of the molybdenum compound in the solution is high because it facilitates colloidal dispersion in hydrocarbon oil and reduces the amount of solvent that does not directly participate in the catalytic function in hydrocracking. Although it varies depending on the type of molybdenum compound used, it is generally used at a high concentration of 10% by weight or more in terms of molybdenum. However, solutions with such high concentrations that the solubility is exceeded and solids precipitate must be avoided, and although this will vary depending on the type of molybdenum compound and solvent used, the upper limit will generally be 40% by weight in terms of molybdenum concentration. . Additionally, if the solution of these molybdenum compounds is unstable, it must be mixed with a hydrocarbon oil and emulsified before it can be substantially decomposed into the simple acids (anions) that make up the heteropolymolybdate anion. . Of course, to stabilize the solution, e.g.
In the case of an aqueous solution of H ₃ [PMo ₁₂ O ₄₀ ], it is possible to employ known stabilization methods such as adding phosphate ions. In a method for producing a specific suspension, i.e. an additive, containing a catalyst precursor of the invention,
A method is adopted in which the carbonaceous material powder is added to a hydrocarbon oil and suspended, and a solution of the molybdenum compound is added to emulsify the mixture, and the two are thoroughly mixed. However, the order in which these two types of substances are added is not limited, and they can be added at the same time.
The hydrocarbon oil used here is defined as a broadly petroleum-derived oil containing sulfur compounds and nitrogen compounds. From the perspective of petroleum product classification, those belonging to the heavy oils specified by JIS K2205 are more preferable. Of course, the raw material oil itself to be subjected to hydrocracking can also be used. By emulsifying a solution of a molybdenum compound in hydrocarbon oil and contacting and mixing it with carbonaceous material powder, a colloidal compound having a heteromolybdate anion skeleton is formed. A unique concentrated suspension is formed in which the carbonaceous material powder is mixed together. The nature of this colloidal compound, which will essentially have a heteropolymolybdate anion backbone, which means that it is no longer in solution in the hydrocarbon oil, is not necessarily clear, but it is likely that it will interact with the carbonaceous material powder. Of course, it is a compound that is the result of
Furthermore, it is also possible that the compound is the result of an ionic reaction or interaction with nitrogen compounds in hydrocarbon oil. In the production method, it is important to sufficiently emulsify, suspend, and contact mix in hydrocarbon oil to obtain a suspension with improved dispersibility, and there are generally known means for this purpose. It is effective to use a disperser or wet pulverizer that applies high shearing force. Furthermore, if necessary, a surfactant that promotes water/oil emulsification and dispersion in oil may be used. Examples of such surfactants include petroleum sulfonates, fatty acid amides, naphthenates, alkyl sulfosuccinates, alkyl phosphate ester salts, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, glycerin resin acids. It can be selected from esters, sorbitan resin acid esters, polycarboxylic acid amine salt type polymeric surfactants, and the like. The average primary particle diameter used in the present invention is about 1 to
Carbonaceous substance powder within the range of 200 nm is industrially manufactured using the physical and chemical properties of the powder surface, rather than as a powder, in order to prevent dust and improve workability during transportation, storage, and use. It is often handled in the form of so-called granules, which are made by granulating powder in a post-processing process using mechanical or electrical agglomeration forces. Of course, such granules can also be used as carbonaceous material powder if the average primary particle diameter is within the range of the present invention, and this makes the present invention even more practical. From the viewpoint of handling as a suspension, so-called slurry handling, it is desirable to mechanically crush and suspend the granules in hydrocarbon oil. The use of a pulverizer etc. is effective. It is effective to aim for a shear rate of about 1×10 ⁴ sec ^-1 or higher, more preferably about 2×10 ⁴ sec ^-1 or higher, to generate a high shearing force.
It is assumed that the faster the shear rate is, the more preferable it is, but the practical upper limit would be about 2×10 ⁵ sec ⁻¹ . When using granules, the degree of disintegration of the granules is preferably such that most of the granules pass through a 200 mesh (74 μm) sieve, or even a 325 mesh (43 μm) sieve. The quantitative ratio of carbonaceous substance powder and molybdenum compound in the manufacturing method varies depending on the type of each type, but in general, the amount of molybdenum equivalent in the molybdenum compound is set to be smaller than the amount of carbonaceous substance powder. Use less. Furthermore, if the carbonaceous powder is used in consideration of its proportion to the total surface area, it will be used more effectively. That is, for example, per 100 parts by weight of carbonaceous material powder having a total surface area of 100BET-m ² /g, the amount of molybdenum compound in terms of molybdenum is 0.05 to 10 parts by weight, or even 0.05 parts by weight.
For example, for 100 parts by weight of carbonaceous material powder with a total surface area of 1000BET-m ² /g, which is 10 times the previous example, the upper limit of the amount of molybdenum compound in molybdenum equivalent is Approximately 10 of the precedents
It is appropriate to use 0.05 to 100 parts by weight, or even 0.05 to 20 parts by weight.
In addition, the suspension concentration of hydrocarbon oil, defined as [total amount of carbonaceous material powder and molybdenum compound amount (A)/(hydrocarbon oil amount + (A))] x 100, is In order to reduce the amount of hydrocarbon oil used and reduce the production scale, it is recommended to use a high concentration, and to maintain the fluidity of the suspension and make slurry handling easier, it is recommended to use a low concentration. Desirably, the balance between the two should be taken into consideration, and a concentration suitable for the types of carbonaceous material powder and molybdenum compound aqueous solution, their quantitative ratio, and the combination of hydrocarbon oil types should be selected. Usually about 2-20
It is preferable to select from a range of weight % concentrations to form a concentrated suspension. As for the operating temperature in the production method, it is sufficient that it is higher than the pour point of the hydrogen oxide oil used and that the suspension can maintain a fluid state during production. The temperature at which the solution is emulsified in hydrocarbon oil must not exceed the boiling point of the solvent used for the solution of the molybdenum compound, i.e., if water is used, the temperature must not exceed 100°C (normal pressure). It makes sense that there isn't one. After emulsion, when using a high shear force dispersing machine for a long time, such as when crushing granules of carbonaceous material powder, the temperature may rise due to the heat generated by the shear force. evaporation of the solvent may occur during manufacturing. In the present invention, it is not necessarily limited whether the solvent is left in the produced additive or whether the solvent is partially or substantially removed by evaporation or the like. However, it is meaningless to leave a significant amount of solvent that does not participate in the catalytic activity in hydrocracking in the additive, and it is meaningless to leave a significant amount of solvent in the additive that does not participate in the catalytic activity in hydrocracking.
In particular, it may be undesirable from the viewpoint of handling in a heated state, so actively applying external heat,
It makes practical sense to substantially remove the solvent by evaporation. The concentrated suspension of hydrocarbon oil produced by the above method can be used as is as an additive for hydrocracking, but the substances suspended in this hydrocarbon oil are positioned as so-called catalyst precursors. When used in hydrocracking, in the preheating zone or reaction zone before the start of the reaction, the molybdenum compound constituting the catalyst precursor is released into the production hydrocarbon oil or heavy hydrocarbon feedstock oil for hydrocracking. The sulfur compounds contained in the molybdenum and the hydrogen oxide gas generated from these transform into molybdenum sulfide, and the suspended solids formed as a result exhibit a catalytic effect. Therefore, to ensure this transformation into molybdenum sulfide, a concentrated suspension of hydrocarbon oil is
Furthermore, (unit) sulfur or a sulfur compound can be added as an auxiliary component. Specific examples of sulfur compounds include thiophenol, methylthiophene, dimethylthiophene, thionaphthene, diphenyl sulfide, diethyl sulfide, etc. Among the sulfur and sulfur compounds that should be added,
Sulfur is most preferred. When adding sulfur or a sulfur compound, it is sufficient if the amount is 2 gram atoms or more per gram atom of molybdenum, and there is no problem in terms of functional performance no matter how much the amount is. In consideration of what you can bring in, it is best to select from the range of gram atoms of 2 or more and 4 or less. Of course, when using a molybdenum compound containing a transition metal other than molybdenum, such as a heteropolymolybdate transition metal salt, an extra amount of sulfur or sulfur compound must be added, taking into consideration the sulfide composition of these transition metals. It is good to add. When added as sulfur, there is no particular shape, but in order to improve the suspension and dispersion properties in hydrocarbon oil and to help people understand it, from a practical point of view it is recommended to add sulfur in the form of 100 mesh (147μ) rather than lumps.
m) It is desirable to add it in the form of powder or colloid while passing through a sieve. It should be noted that during additive manufacturing, molybdenum compounds derived from heteropolymolybdic acids or their transition metal salts, such as chelating sulfur compounds such as tetraalkylthiuram disulfides and dialkyldithiocarbamates, are Reacts to form coordination compounds and complexes,
A sulfur compound that substantially decomposes the heteropolymolybdate anion skeleton should not be used because it impairs the inherent characteristics of the molybdenum compound according to the present invention. In addition, 350% additive containing catalyst precursor
At a high temperature in the range of ℃ to 500℃, or even 400℃ to 500℃, preferably in an oxygen-free atmosphere,
Furthermore, additives obtained by heat treatment, preferably in a hydrogen atmosphere, can be used in the present invention. Through this heat treatment, the molybdenum compound in the additive is thermally decomposed and reacts with sulfur or sulfur compounds in the hydrocarbon oil.
The additive that converts into amorphous molybdenum sulfide and contains this amorphous molybdenum sulfide exhibits high catalytic activity in the hydrocracking reaction. "Amorphous" as used herein means that it does not exhibit detectable crystallinity when measured by X-ray diffraction, and is an indicator of high microdispersity. In this regard, if the dispersibility of the molybdenum compound in the catalyst precursor is low, the molybdenum sulfide after heat treatment will be more crystalline in X-ray diffraction.
In such a case, the catalytic activity in the hydrocracking reaction will be significantly degraded. The mechanism by which these manufactured additives exhibit excellent effects in hydrogenolysis is not necessarily clear, but the specific carbon chamber material powder and the specific heteropolymolybdic acid compound defined in the present invention. The characteristics derived from the combination with the hydrogenation group and the method of producing concentrated suspensions in petroleum-based hydrocarbon oils achieve high dispersion of the hydrogenation-active metal species and the suspended catalyst (precursor), respectively. It is presumed that they act synergistically, resulting in an excellent catalytic effect. One of the characteristics of the heteropolymolybdate compound group is the structural specificity of the heteropolymolybdate anion. Taking the [PMo ₁₂ O ₄₀ ] ^-3 anion structure in which the hetero atom is P as an example, This anion is composed of a well-regulated condensation of 12 octahedral MoO ₈ (centered on Mo atoms) and one central tetrahedral PO ₄ (centered on P atom), and the real image of the anion is: It has a nearly spherical shape with a diameter of about 1 nm and is covered with 36 oxygen ions.
As typified by this example, heteropolymolybdate anions have a clear single anion structure and intracrystalline arrangement, and are metal oxide ions in isopolyacids such as paramolybdate and other complex oxides. It has a structure that is completely different from the infinite length crystal structure seen in metal ions such as general inorganic acid metal salts and organic acid metal salts. This is clearly distinguishable from the use of other transition metal compounds as the catalyst precursor of the present invention, and is one of the important features for increasing the dispersibility of the hydriding metal species. It is estimated that there are. In addition, based on the easy reducibility of the heteropolymolybdic acid compound group, it can be considered as one of the characteristics that it is easily converted into amorphous molybdenum sulfide, which is a hydrogenation active species. A further characteristic feature is that by manufacturing the heteropolymolybdate compound group and carbonaceous material powder in combination, the carbonaceous material powder plays the role of a so-called carrier, and the structure of the heteropolymolybdate anion is This would make it possible to maintain high dispersion of hydrogenation-active metal species based on specificity. It is presumed that not only the characteristics of the carbonaceous material powder, that is, its characteristics as ultrafine particles based on its small primary particle size, but also its specific affinity with the heteropolymolybdic acid compound are helpful. Ru. In addition, ionic reactions and interactions between nitrogen compounds in petroleum-derived hydrocarbon oils and heteropolymolybdate anions are also considered to be involved in the high dispersibility of hydrogenation-active metal species. Due to these synergistic effects, the hydrogenation-active molybdenum species, which has achieved high dispersion in hydrocarbon oil in which carbonaceous material powder with ultrafine particle characteristics is suspended, can be used for hydrocracking of heavy hydrocarbon oil. It is estimated that it shows high catalytic activity against. By using the additive according to the present invention described above, the hydrocracking method for heavy oil hydrocarbon oil can be carried out effectively. The type of heavy hydrocarbon oil used as a raw material is not limited in the present invention. Heavy hydrocarbon oils of any property can be used, such as paraffinic crude oil, naphthenic crude oil, aromatic crude oil, tar oil, shale oil, tar sand extracted oil, coal liquefied oil, etc. Normal pressure distillation residue oil, vacuum distillation residue oil, etc. can be used as the raw material oil. The amount of additives added to the feedstock depends on the type of catalyst (precursor), the type of heavy hydrocarbon feedstock, the degree of hydrocracking (i.e., the degree of lightening and property modification of the produced oil), and the hydrogen It depends on the type of chemical cracking reactor, the hydrocracking reaction system, etc.
In order to satisfy the most important catalytic functions of suppressing by-products of polycondensation compounds such as coke and asphaltene and avoiding coking within the equipment, the catalyst of the present invention must have high activity. Taking advantage of certain characteristics, the amount of molybdenum equivalent for mixed oil (mixture of additives and raw material heavy hydrocarbon oil) is usually 5 to 30 ppmW, and furthermore,
In the range of 10 to 180 ppmW, and 0.02 to 1.5% by weight as carbonaceous material powder equivalent, and even 0.05
-1% by weight. Of course, in order to further improve the properties of the produced oil by promoting effective hydrogenation to the hydrocracked oil and functions such as deheteroatomization, the usage amount of each of the above (especially , amount of molybdenum) may be further increased. The raw material oil mixed with additives is mixed with hydrogen or hydrogen-containing gas and subjected to hydrocracking treatment at high temperature and high pressure. The hydrocracking treatment conditions are:
In order to take advantage of the characteristics of the catalyst according to the present invention and to make the reactor compact and increase the unit throughput, which is of practical significance, conditions were adopted to achieve a high degree of lightness through relatively high temperature and short reaction times. can. That is, the reaction temperature is in the range of 450 to 520°C, preferably in the range of 470 to 500°C, and the reaction time is in the range of 5 minutes to 2 hours, preferably 10 minutes based on the mixed oil volume in the raw material supply state. A range of ˜1 hour is used. The hydrocracking treatment is carried out in hydrogen or a hydrogen-containing gas, and the hydrogen-containing gas includes gases other than hydrogen, such as hydrocarbon gases such as methane and ethane, and hydrogen sulfide gas.
The hydrogen or hydrogen-containing gas used has a reaction hydrogen partial pressure in the range of 100 to 300 Kg/ ^cm2 , preferably
It is supplied in a range of 100-200Kg/ ^cm2 .
In addition, the amount of hydrogen or hydrogen-containing gas used should be supplied with consideration given to the reaction equipment used to ensure sufficient gas-liquid mixing.
Approximately as the amount of hydrogen for mixed oil in raw material supply state
200-2000Nm ³ /Kl, preferably 300-1000Nm ³ /
In general, it is possible to supply hydrogen within the range of Kl, and generally replenish the amount corresponding to the amount of hydrogen consumed (chemical hydrogen consumption and hydrogen dissolved in oil consumption) and recycle it. Each of these processing conditions does not take an appropriate value independently, but they are related to each other, so the appropriate range may change, but the bottom line is:
By using additives containing the catalyst (precursor) according to the invention, it is possible to obtain, for example, a boiling point of 538 °C.
Even when a higher vacuum distillation residue oil is used as a raw material, the fraction with a boiling point lower than 538℃ contains 80% by weight or more.
Strictly more than 85% by weight, even more strictly 90% by weight
It is possible to select treatment conditions that result in conversion with a higher decomposition rate than those described above. The hydrocracking method according to the present invention can be carried out by either a batch process or a continuous flow process, but when carried out on a practical or industrial scale, it may be carried out by a continuous flow process. Makes sense. The method of carrying out the hydrocracking method according to the invention by means of a continuous flow process will therefore be explained in more detail with reference to the drawings. The main components of the reactor system shown in the drawing are a feedstock adjustment zone 3 where additives and feedstock heavy hydrocarbon oil are mixed, a reaction zone 6 where hydrocracking is carried out, and a reaction zone where reaction products are separated into gas and liquid phases. It consists of a gas-liquid separation zone 8 that separates into phases, and a distillation zone 12 that separates the separated reaction product liquid (strictly speaking, suspension) into boiling point fractions. The additive according to the present invention is introduced through pipe 1 and the heavy hydrocarbon oil as a raw material is introduced through pipe 2, respectively, and they are thoroughly mixed in a raw oil adjustment area 3. The obtained mixed oil is pressurized by a pump, and then mixed with hydrogen or hydrogen-containing gas introduced from a pipe 5 and pressurized by a compressor in a pipe 4. It is then fed to the hydrocracking zone 6. As the reactor type in the hydrocracking zone 6, any reactor type capable of carrying out a suspension catalytic reaction, such as a tube type, tower type, or tank type, can be adopted.
It usually consists of a preheating area and a reaction area. As a reactor type on an industrial scale, a tubular reaction gas type is preferred because it allows a high flow rate in the reactor and can efficiently create a flow pattern such as a bubble flow that facilitates sufficient mixing of gas/liquid/solid. Will. The effluent from the hydrocracking zone 6 is taken out through line 7 and passed through a gas-liquid separation zone 8 where the product is separated into a gas phase and a liquid phase (suspension). The separated gas phase can be taken out through a pipe 9, and after separating light oil and undesirable gas components as necessary, the hydrogen-containing gas can be circulated through a pipe 10 for reuse. The separated liquid phase (suspension) is taken out through a pipe 11, and after the high pressure is released, it passes through a distillation zone 12, where it is separated into necessary fractions based on differences in boiling point range. In the distillation zone 12, a distillation type in which a normal pressure distillation column and a vacuum distillation column are arranged in series can be conventionally adopted.
For example, it can be separated into light oil fractions (naphtha, kerosene, etc.), intermediate oil fractions (via, vacuum gas oil, etc.), and residual oil containing solids of catalysts and polycondensation substances. Distillate oils of the separated light oil fraction and intermediate oil fraction are taken out as light product oil through paths 13 and 14, respectively. The light product oil taken out from these reactor systems can be used as is or, if necessary, refined by a known hydrorefining device.
It can be used for applications such as petroleum intermediate products and petrochemical raw materials. On the other hand, the separated residual oil is
It is taken out through the path 15 and typically can be used as is as a general boiler fuel oil, etc., without separating the contained solids by solid-liquid separation or the like. A reaction system in which the entire amount of residual oil is taken out of the system is generally called a one-through reaction system. Since the catalyst according to the present invention contained in the residual oil after the one-through reaction retains sufficient catalytic activity for hydrocracking, it is further possible to use the recycling reaction system, i.e., to recycle at least a portion of the residual oil containing the catalyst. A reaction system with circulation through path 16 may also be employed. The recycling reaction system has the characteristic that the amount of unused fresh catalyst used can be significantly reduced by taking into account the amount of recycled catalyst. Furthermore, since the recycled residual oil repeatedly passes through the hydrocracking zone 3, in contrast to the one-through reaction system, in order to further increase the hydrocracking rate or obtain a predetermined hydrocracking rate, the hydrocracking zone Since the hydrocracking rate per passing amount can be lowered (that is, the hydrocracking treatment conditions can be relaxed), it will become a more practical reaction system. (Examples) Next, the present invention will be further explained by examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. The heteropolyacids and their salts used in the following Examples and Comparative Examples were synthesized and purified by known methods, and were subjected to metal content measurements using optical emission spectrometry, X-ray diffraction, and infrared spectroscopy. After identification was carried out by structural analysis using , decomposition pattern analysis and crystal water content measurement using thermal analysis, and redox potential measurement using polarographic method, it was put into use. The carbonaceous material powder used was commercially produced. Example 1 Additive production Vacuum distillation residue oil of Minas crude oil [fraction with a boiling point of 520°C or higher 94.0% by weight, S content 0.20% by weight, N content 0.31% by weight, pour point 56°C, kinematic viscosity 240cst (80%)
℃)] 400g was heated to 75℃ and kept warm. A suspension was obtained by adding and immersing 55 g of carbon black fine powder (average primary particle diameter 20 nm as determined by electron microscope, specific surface area 130 m ³ /g as determined by BET method) into this hydrocarbon oil. Separately, H ₃ [MPo ₁₂ O ₄₀ ]・
A yellow aqueous solution was prepared by adding and dissolving 4.4 g of 29H ₂ O in 4 g of deionized water. 2.1 g of this yellow aqueous solution and 0.7 g of sulfur powder passed through a 100 mesh (147μ) sieve are added to the suspension, and the fluid passes through the clearance (0.4 mm) between the turbine (turbine diameter 28 mm) and the stator. A high-speed stirring type dispersion machine that generates high shear force reduces the rotational speed.
10000rpm, circumferential speed 16m/s, turbine displacement 33
/mim, 1 under the condition of turbine power consumption 0.06KW
Stir and mix for hours. During the stirring and mixing operation, water evaporation was observed due to the heat of stirring, and the temperature of the suspension reached 135°C after the operation was completed. When the Mo content of the obtained suspension was measured by fluorescent X-ray method, it was found to be 1170ppmW.
Also, when the water content was measured by Karl Fischer method, it was less than 0.1% by weight.
The resulting suspension was mixed with a catalyst precursor having a Mo equivalent concentration of 1180 ppmW and a carbonaceous material equivalent concentration of 12.0% by weight, based on the weight of each charged material (excluding the amount of water used to create the aqueous solution). Defined as a substance-containing additive. Hydrocracking treatment A 316 stainless steel electromagnetic stirring autoclave with an internal volume of 1 and an external heating coil heater was used as the reactor, and the vacuum distillation residue of the same Minas crude oil used in the above production was used as the feedstock oil. Batch experiments were conducted using 240 g of raw oil was charged into an autoclave, and 20 g of the above additives were added. In this experiment, the catalyst precursor concentration is determined to be 91 ppmW as a concentration in terms of Mo and 0.92% by weight as a concentration in terms of carbonaceous material. The inside of the autoclave was pressurized with hydrogen to 120 kg/cm ² at room temperature, and the autoclave was sealed. For gas-liquid contact and fluid mixing, the reaction was carried out at an internal temperature of 470° C. for 35 minutes while stirring with a stirrer having a scraping type propeller blade at a rotational speed of 1000 rpm. The reaction time of 35 minutes is the time the reaction temperature is maintained at 470°C after it reaches that temperature, and the temperature is increased (temperature increase rate is approximately 6°C).
℃/min) and the time required for temperature reduction (temperature reduction rate of 15°C/min) were not taken into consideration. The entire amount of the product after the reaction, both gas and suspension, was recovered and subjected to analysis. Gas components were analyzed by gas chromatography, produced oil was analyzed by distillation using a distillation apparatus in accordance with ASTM D-1160, and polycondensation substances were analyzed by solvent extraction. The results are shown in Table 1. The extent to which the feedstock has become lighter, that is, the hydrocracking rate, is: (1 - percentage of bp520℃ ⁺ residual oil in the product/proportion of bp520℃ ⁺ residual oil in the raw material mixture) x 100% by weight It was defined as . In addition, asphaltene is defined as a polycondensation substance that is insoluble in hexane extraction and soluble in tetrahydrofuran extraction, and coke is defined as a polycondensation substance that is insoluble in tetrahydrofuran extraction by subtracting the amount of catalyst precursor or catalyst charged. Defined as a substance. To determine whether or not there is caulking, after taking out the product, check to see if there is any solid matter that is firmly attached to the autoclave inner wall, stirrer, or thermocouple protection tube for internal temperature measurement to the extent that it cannot be removed without scraping it off with mechanical force. Judgment was made by doing so. Examples 2 to 11 Additives were manufactured in the same manner as in Example 1, except that the solutions listed below were used as solutions of heteropolymolybdic acid compounds. A catalyst precursor-containing additive having a concentration of 12.0% by weight in terms of solid substance was obtained. The hydrocracking treatment was carried out in exactly the same manner as in Example 1. The results are shown in Table 1. Example 2 Example of 70% by weight aqueous solution of H ₆ [P ₂ Mo ₁₃ O ₆₂ ]・28H ₂ O Example 3 Example of 30% by weight propanol solution of H ₄ [GeMo ₁₂ O ₄₀ ]・20H ₂ O 4 Example of H ₈ [GeMo Example of a 50% by weight aqueous solution of ₁₂ O ₄₂ ]・18H ₂ O 5 Example of a 40% by weight aqueous solution of Cu ₂ [PMo ₁₂ O ₄₀ ] ₂・29H ₂ O 6 Ni ₃ [PMo ₁₂ O ₄₀ ] ₂・31H ₂ O Example of a 28% by weight aqueous solution 7 Example of a 35% by weight aqueous solution of Mn ₂ [SiMo ₁₂ O ₄₀ ]・18H ₂ O 8 Example of a 70% by weight aqueous solution of H ₄ [PMo ₁₁ VO ₄₀ ]・26H ₂ 9 H ₃ Example of a 50% by weight _aqueous solution of [PMo ₁₀ W ₂ O ₄₀ ]・18H ₂ O 10 H ₃ Example of a 40% by weight _aqueous solution of 12H ₂ O 11 _{H 4 [} SiMo ₁₂ O ₄₀ ]・30H ₂ O in 30% by weight ethanol solution

【table】

[Table] Comparative Examples 1 to 11 Additive production In Comparative Example 1, an aqueous solution of H ₃ [PMO ₁₂ O ₄₀ ]/29H ₂ O was not used, and in Comparative Example 2, carbon black fine powder was not used. Each was produced in the same manner as in Example 1. In Comparative Example 3, calcine coke powder pulverized with a jet pulverizer was used instead of the carbon black fine powder used in Example 1, and in Comparative Example 4, γ
- Alumina (specific surface area 220 m ² /g by BET method,
The powders having a pore volume of 0.43 ml/g were pulverized with a rolling ball mill and passed through a 400 mesh (37μ) sieve. The particle size distribution of the powders used was measured by centrifugal sedimentation method and is shown below. Powder used in Comparative Example 3 > 20 μm 10% 20-10 μm 23% 10-5 μm 30% 5-2 μm 25% 2 μm > 12% Powder used in Comparative Example 4 37-20 μm 30% 20-10 μm 38% 10 −5μm 26% 5μm＞6% H ₃ [PMo ₁₂ O ₄₀ ]・29H ₂ O aqueous solution and sulfur powder were added to the vacuum distillation residue of Minas crude oil at 80°C in the same weight ratio as in Example 1, and the mixture was heated at high speed. 10 with stirring type disperser
The aqueous solution was emulsified by stirring for a minute.
Add 35g of each powder to this, stir at 1000 rpm for 1 hour with a propeller type stirrer, and heat to 120°C.
heated to. The obtained suspensions were used in Comparative Examples 3 and 4.
Both contained 1230 ppm of molybdenum and 8.0% by weight of powder. Comparative Examples 5 to 8 are the same as Example 1, except that the following examples of aqueous solutions of molybdenum compounds or tungsten compounds are used so that the Mo or W equivalent concentration is 1180 ppm in the production suspension.
Manufactured in the same way. Comparative example 5 Comparative example of 8 wt% aqueous solution of (NH ₄ ) ₆ Mo ₇ O ₂₄・4H ₂ O 6 Comparative example of 50 wt % aqueous solution of H ₃ [PW ₁₂ O ₄₀ ]・31H ₂ O 7 Na ₄ [SiMo ₁₂ O Comparative example of 30% aqueous solution of ₄₀ ]・9H ₂ O 8 2% by weight of (NH ₄ ) ₂ H ₂ [SiMo ₁₂ O ₄₀ ]・15H ₂ O
Aqueous solution In Comparative Examples 9 and 10, the combination of H ₃ [PMo ₁₂ O ₄₀ ]·29H ₂ O and carbon black fine powder and the manufacturing method were the same as in Example 1, but in Comparative Example 9, H ₃
[PMo ₁₂ O ₄₀ ].29H ₂ O was added as a crystalline solid instead of an aqueous solution, and in Comparative Example 10, tetramethylthiuram disulfide 1.0 was added instead of sulfur powder.
g to produce concentrated suspensions. Hydrocracking treatment It was carried out using the same reaction apparatus and method as in Example 1. The results are shown in Table 2, along with the catalyst precursor concentrations used. In all these comparative examples,
During the hydrogenolysis reaction after the reaction temperature was reached, disturbances occurred in the charts of internal temperature records and pressure records, although there were differences in the time at which disturbances began. During observation after opening the autoclave and taking out the resulting suspension, it was found that in all comparative examples, although there were differences in degree, the inner wall of the autoclave, the stirrer, and the thermocouple protection tube, which were not observed in Examples 1 to 11, were observed. The caulking phenomenon was clearly observed. The results of the comparative examples shown in Table 2 are very different from the results of the examples according to the invention shown in Table 1. This indicates that under high cracking conditions with a hydrogenolysis rate of 80% by weight or more, the additive according to the present invention performs the basic function in the reaction zone, that is, suppressing the generation of polycondensation substances (alphaartene and coke). Furthermore, it was confirmed that the catalyst exhibited excellent catalytic activity, satisfying the function of not causing coking in the reaction zone. In addition, in Examples 1 to 11, since the generation of polycondensation substances was suppressed to a low level, the coke concentration in the 520°C ⁺ residual oil after hydrocracking was approximately 3.
The concentration is in the range of ~7% by weight, and even when asphaltene, which can be partially colloidally dispersed, is added, the concentration is in the range of approximately 12 to 22% by weight. At this level of suspension concentration, slurry handling is possible without any practical problems.

[Table] Example 12 Additive production 500g of vacuum gas oil fraction with the properties shown in Table 3 was heated to 60°C.
After heating and keeping warm, granulated porous carbonaceous material powder (average primary particle diameter 30 nm as measured by electron microscope,
Specific surface area 950m ² /g, pore volume 1.15 by BET method
ml/g, particle size distribution of granules d ₁₀ 1.65mm, d ₃₀ 1.19mm,
d ₉₀ 0.40mm) 20g and soaked in vacuum light oil.
Further, 3.7 g of sulfur powder was added to obtain a suspension.
Separately, 7.6 g of H ₃ [PMo ₁₂ O ₄₀ ].29H ₂ O was added to 5 g of deionized water, and the resulting aqueous solution was added to the suspension. This mixture was stirred and mixed under the same conditions using the same high-speed stirring type disperser as in Example 1 to obtain a hydrocarbon oil in which the suspended matter was in a highly dispersed state. Next, this material was heated in an autoclave at a temperature of 450℃ and a hydrogen partial pressure of 50Kg/ ^cm2 .
After heat treatment for an hour, the suspension was collected. The suspension obtained by collection has a Mo equivalent concentration of 7010 ppmW and a carbon material equivalent concentration of 3.76% by weight, based on the weight of each charged material (excluding the amount of water used to create the aqueous solution). Defined as a catalyst-containing additive. In addition, the produced catalyst-containing additive was heated to 325°C at 60°C.
When the mixture was passed through a mesh sieve (43 μm) and washed with tetrahydrofuran, the amount of solids remaining as residue on the sieve was just a trace.
In addition, a solid substance separated and recovered from the catalyst-containing additive through a series of operations of filtration, washing, extraction, and drying (hexane was used as the washing liquid and extracting liquid) was measured by X-ray diffraction. The X-ray diffraction device uses GEIGERFLEX RAD manufactured by Rigaku Denki Kogyo Co., Ltd., target: Cu, voltage: 40 KV, current: 30 mA, Kβ filter: Ni, slit width: 0.05 mm (divergent slit), 0.15 mm (light receiving slit). ), step width:
Measurement was carried out under the following conditions: 0.01deg, preset time: 0.4sec, angle zoom: 0.2mm/step. The measurement result is the main line of molybdenum disulfide 14.4deg (2θ)
Approximately 10~20deg (2θ) without showing a clear peak at
It showed a very wide halo extending over , suggesting that the formed molybdenum disulfide was amorphous. Hydrocracking treatment: Vacuum residual oil of Victory Crude Oil (90.2% by weight of distillate with a boiling point of 520°C or higher, S content: 1.26% by weight, N content:
0.82% by weight) as the raw material oil, 242g of this raw material oil
and using 8 g of the manufactured additive, the internal volume was 1
Batch experiments were conducted using an autoclave. In this experiment, the catalyst concentration is determined to be 224 ppmW as Mo equivalent concentration and 1200 ppmW as carbonaceous substance equivalent concentration. A hydrogen pressure of 120 Kg/cm ³ was sealed at room temperature, and the reaction was carried out at 470° C. for 25 minutes to obtain a product. The results are shown in Table 4. Comparative Example 11 Additive Production Instead of an aqueous solution obtained by adding H ₃ [PMo ₁₂ O ₄₀ ]・29H ₂ O to deionized water and dissolving it,
Example 12 was carried out using an aqueous solution obtained by adding 6.8 g of (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O to 80 g of deionized water.
Manufactured in the same way. The produced catalyst-containing suspension is
When passed through a 325 mesh (43 μm) sieve while washing with tetrahydrofuran, 21
% by weight of solids remained as sieve residue. Also,
The solid matter separated and recovered by the same operation as in Example 12 was measured by X-ray diffraction method, and it was found to be 14.4 deg.
(2θ) on the same scale as Example 12, half-width approximately
A peak of 2deg (2θ) was obtained. This peak is
The peak was significantly sharper than that of Example 12, suggesting stronger crystallinity. Hydrocracking treatment The same procedure as in Example 12 was carried out using 8 g of the obtained additive. After the reaction, the autoclave was opened, and a clear coking phenomenon was observed on the inner wall of the autoclave and the thermocouple protection tube. As a result of solvent extraction analysis, the amounts of alpha-artene and coke generated were 2.1% by weight and 4.2% by weight, respectively, and the results of S and N analysis in the produced oil were 0.73% by weight of S (desulfurization rate 42%),
The N content was 0.72% by weight (denitrification rate 12%). Example 13 Additive production and hydrocracking treatment 500 g of vacuum distillation residue oil from the same Shengri crude oil used in the hydrocracking treatment in Example 12 was heated to 80°C.
After keeping warm, the same sulfur-forming porous carbonaceous material powder used in Example 12, an aqueous solution of H ₃ [PMo ₁₂ O ₄₀ ]/29H ₂ O, and sulfur powder were added to 6 g, 8.4 g, and 2.5 g, respectively.
A suspension was prepared using the same method as in Example 1 using the following methods. Take 250g of this material and place it in an autoclave with an internal volume of 1, and heat it at 470℃.
A hydrogenolysis experiment was conducted for 25 minutes under the conditions of 140 Kg/cm ³ (hydrogen charging pressure at room temperature). In this experiment, the catalyst precursor concentration was expressed as Mo equivalent concentration.
It is calculated as 0.49% by weight and 1.17% by weight as a carbonaceous substance equivalent concentration. The results are shown in Table 4. While Examples 1 to 11 were evaluated using feedstock oils exhibiting parafinic properties, the results of Examples 12 and 13 showed that even when feedstock oils exhibiting naphthenic properties were used, the hydrocracking rate was 80% by weight. This shows that the catalyst activity according to the present invention satisfies the basic functions under the above high decomposition conditions. Example 12 uses a catalyst precursor that has been further processed to become a catalyst, and Example 13
This shows the results obtained using the raw material oil itself for hydrocracking as the hydrocarbon oil for producing additives. In addition, in both Examples 12 and 13, granules of porous carbonaceous material powder were used for additive production, but in addition to the average primary particle size being in the ultrafine region, Therefore, the primary particles themselves have a porous property. Based on this, the results of Example 12 show that even if the amount of powder used is significantly smaller than in Examples 1 to 11, the function of preventing caulking is exhibited. Furthermore, regarding the properties of the produced oil, the results of Example 12 show that a desulfurization rate of 80% by weight and a sulfur nitride rate of 26% by weight were achieved. From the results of Example 13, the amount of catalyst used,
In particular, by increasing the amount of Mo used, the desulfurization rate was improved to 97% by weight, and the denitrification rate was improved to 69% by weight.
It is clear that increasing the amount of catalyst has an effect on reforming the produced oil.

【table】

【table】

【table】

[Table] Example 14 Additive production A 200 container with an agitator and circulation piping exiting from the bottom of the container and returning to the top of the container, and a gear pump and a high-speed rotating line mill were arranged in series in the middle of the piping. Additive production was carried out using the equipment.
The line mill has two coaxial turbines with a diameter of 90 mm, and one turbine on the discharge side has a grinding mill blade structure, and the clearance between the turbine and the stator was set to 0.8 mm. . 200 containers were charged with 125 kg of heavy oil having the properties shown in Table 5, heated to 80°C and kept warm, and granulated carbon black (average primary particle diameter determined by electron microscope) was added to the container.
22nm, specific surface area 120m ² /g by BET method, particle size distribution of granules d ₁₀ 1.60mm, d ₅₀ 0.92mm, d ₉₀ 0.25mm)
22Kg was added with stirring and immersed in heavy oil.
After that, start the gear pump and line mill,
Fluid circulation amount 2m ³ /H, line mill rotation speed
It was operated for 2 hours at 3600 rpm and power consumption of 3.3KW. During the process, 20 minutes after the start of circulation, H ₄ [SiMo ₁₂ O ₄₀ ]
An aqueous solution obtained by dissolving 550 g of 30H ₂ O in 350 g of deionized water was added to 200 containers. After the circulation operation was completed, the concentration of the highly dispersed concentrated suspension was 105°C. The concentrated suspension obtained in this way has a Mo equivalent concentration of 1810 ppmW and a carbonaceous substance equivalent concentration.
It was defined as an additive containing 14.9% by weight of catalyst precursor. In addition, a part of the manufactured additive was separated and heated at 60℃.
Using a 325 mesh (43 μm) sieve,
When the sieve was washed with tetrahydrofuran, only a trace amount of solid matter remained as a sieve residue. Further, the Mo content of the additive was measured by the fluorescent X-ray method and was found to be 1800 ppmW, and the water content by the Karl Fischer method was 0.2% by weight. Hydrocracking treatment As feedstock oil, vacuum distillation residue oil of Khafji crude oil (96.6% by weight of fraction with boiling point of 520℃ or higher, S content 4.13
% by weight, N content 0.25% by weight), the prepared additive was added thereto, and the mixed oil was prepared by thoroughly mixing and stirring at a rotation speed of 500 rpm using a propeller-type three-blade stirrer. In addition, the amount of catalyst precursor contained in the mixed oil is 146 ppW in terms of Mo.
In addition, the mixing ratio of the raw material oil and the additive was determined so that the carbon black equivalent amount was 1.20% by weight. The hydrocracking process is carried out using a preheater consisting of a 1/4 inch x 5 m spiral pipe, inner diameter 21 mm, height
It consists of a set of high-pressure reaction equipment with a 2.5 m gas-liquid cocurrent upflow reactor, and a set of distillation equipment with a flatsier with an inner diameter of 36 mm and a height of 3 m that can separate fractions at a normal pressure equivalent boiling point of 520 °C by blowing nitrogen gas.
Continuous experiments were conducted using a flow device made of 316 stainless steel. The operating conditions for hydrocracking are a reaction temperature of 480°C and a residence time based on the volume of mixed oil supplied.
34 minutes, pressure 200Kg/cm ³ , hydrogen/mixed oil volume ratio
1200N/ was adopted, and continuous operation was performed for 250 hours using a one-through reaction system. driving,
Stable operation was possible without any clogging phenomenon occurring anywhere in the flow device including the reactor. Table 6 shows the results of the hydrocracking treatment based on the analysis of the obtained product. Example 14 shows the results of using a raw material oil exhibiting aromatic properties, whereas in Examples 1 to 13, raw oils exhibiting parafinic or naphthenic properties were evaluated. The results show that continuous experiments using a flow device, which are meaningful for practical use, are carried out under high decomposition conditions with a hydrolysis rate of 85% by weight or more.
This shows that it was possible to implement it stably. Comparative example 12 H ₄ [SiMo ₁₂ O ₄₀ ]・30H ₂ O instead of an aqueous solution,
Example using the (NH ₄ ) ₆ Mo ₇ O ₂₄ ·4H ₂ O aqueous solution used in Comparative Example 5, which is not within the scope of the present invention.
Hydrocracking treatment was carried out in the same manner as in Example 14 using a flow device using additives prepared in the same manner as in Example 14. After 20 hours had passed after the start of steady operation, a significant pressure difference occurred between the input and output of the reactor, and the liquid withdrawal from the high-pressure gas-liquid separator became unstable, which hindered continued operation. has been discontinued. Upon inspection after the start of the apparatus, a significant amount of solid matter stuck and remaining in the reactor and the piping to the high-pressure gas-liquid separator was found, and the total amount was 530 g.

【table】

【table】

【table】

[Table] * Amount of solids stuck to the inner wall of the reactor after operation Example 15 Additive production The same method as in Example 14 was used. Hydrocracking treatment As feedstock oil, vacuum distillation residue oil of Minas crude oil (94.0% by weight of fraction with boiling point of 520°C or higher, S content 0.20
% by weight, N content: 0.31% by weight), and the flow device described in Example 14 was used as the device to carry out continuous experiments. The quantitative ratio of the mixed oil consisting of the raw material oil and the additive was such that the amount of catalyst precursor contained in the mixed oil was 117 ppmW in terms of Mo and 0.96% by weight in terms of carbon black. The operating conditions for hydrocracking are the reaction temperature
490℃, residence time based on mixed oil volumetric feed rate 32
min, pressure 200Kg/cm ³ , hydrogen/mixed oil volume ratio 1100N
/ was adopted, and continuous operation was performed for 250 hours using a one-through reaction system. During the operation, stable operation was possible without any clogging phenomenon occurring in any part of the flow device including the reactor. The results of the hydrocracking treatment are shown in Table 7. Example 16 Additive production H ₃ [PMo ₁₂ O ₄₀ ]・29H ₂ O 55 g and deionized water 30 g
After dissolution, a four-electron reduction reaction was performed by adding ascorbic acid to create a blue aqueous solution. To 16 kg of vacuum distillation residue oil of Minas crude oil, which is the same as that used for the raw material oil for hydrocracking treatment in Example 15,
Added 30g of polybutenyl succinic acid amide.
Heat to 80℃ and keep warm, add the entire amount of the blue aqueous solution and 25g of sulfur powder passed through a 100 mesh (147μ) sieve.
added. This material is processed at a rotation speed of 8000 rpm using a high-speed stirring type disperser with a turbine diameter of 50 mm and a clearance of 0.5 mm between the turbine and the stator.
A water/oil emulsion was created by stirring at a circumferential speed of 21 m/s, a turbine discharge rate of 200/mm, and a turbine power consumption of 1.0 KW. While still stirring, granulated carbon black (average primary particle diameter using an electron microscope)
50 nm, specific surface area by BET method 58 m ² /g, particle size distribution of granules d ₁₀ 2.05 mm, d ₅₀ 1.38 mm, d ₉₀ 0.76 mm) 2.8
Kg was added and grinding and mixing was carried out for 2 hours. The resulting concentrated suspension was used as an additive with a Mo concentration of 1430 ppW and a carbon black equivalent amount of 14.8% by weight. Hydrocracking treatment Using the same vacuum distillation residue oil of Minas crude oil as used in Example 15 as the feedstock oil, the quantitative relationship between the feedstock oil and the additive was such that the Mo equivalent amount in the mixed oil was 33ppmW.
And, the carbon black equivalent amount was 0.34% by weight. For the hydrocracking treatment, continuous experiments were carried out using the distribution apparatus described in Example 14, which was equipped with a circulation process in which a part of the flasher bottom oil was mixed with the raw material mixture oil and supplied to the reactor. carried out.
The operating conditions for hydrocracking are a reaction temperature of 485℃,
Residence time based on the combined volume supply of raw mixed oil and circulating oil: 22 minutes, pressure: 180 Kg/cm ³ , hydrogen/supplied oil volume ratio: 950 N/, recycling ratio (circulated oil/raw mixed oil weight ratio): 0.34. The recycling reaction system was used for continuous operation for 300 hours. During the operation, stable operation was possible without any clogging phenomenon occurring in any part of the flow device including the reactor. The results are shown in Table 7. The results of Examples 15 and 16 show that stable continuous operation can be carried out even under high cracking conditions with a hydrocracking rate of 90% by weight and with either one-through or recycling reaction systems. The results of Example 16 showed that by adopting the recycling reaction system, the catalyst activity was not affected, and
This shows that the amount of catalyst (precursor) used can be significantly reduced compared to the one-through reaction system (Example 15). That is, it was confirmed that the catalyst according to the present invention can withstand repeated use. In addition, in the recycling reaction system according to the present invention, the hydrocracking conditions can be relaxed compared to the one-through reaction system, and based on this, hydrogen consumption and gas generation can be suppressed and a high decomposition rate can be achieved. It could be confirmed. Therefore, the recycling reaction system is a more practical reaction system.
It can be included within the scope of the present invention.

[Table] (Effects of the Invention) As is clear from the above description, the additive according to the present invention can be easily produced, and this additive can be used for hydrocracking of heavy hydrocarbon oil. It exhibits a highly active suspension catalytic effect, and even when the heaviest vacuum distillation residue obtained as a petroleum fraction is used as a raw material, it can produce more than 80% by weight of a light fraction with higher added value. , and even 85
It is possible to establish a continuous flow process that allows conversion at a high decomposition rate of more than 90% by weight, more precisely 90% by weight or more. As described above, the ability of the present invention to provide an additive for hydrocracking and a hydrocracking method using this additive that satisfies both technical and practical aspects is important in view of its role in the effective utilization of petroleum resources. , the industrial value is extremely large.

[Brief explanation of drawings]

The drawing shows, as a schematic flow sheet, one embodiment of a reactor system for carrying out the hydrocracking process within the scope of the present invention in a continuous flow process.

Claims (1)

[Scope of Claims] 1 () Carbonaceous material powder having an average primary particle size within the range of 1 to 200 nm; () At least one member selected from heteropolyacids containing molybdenum atoms as poly atoms and transition metal salts thereof. An additive for hydrocracking, characterized in that it is obtained by a method of obtaining a suspension by mixing a solution of a molybdenum compound in an oxygen-containing polar solvent in a hydrocarbon oil. 2. The additive according to claim 1, wherein the method further comprises adding and dispersing sulfur or a sulfur compound in an amount of 2 or more gram atoms per gram atom of molybdenum to the suspension. 3. The additive according to claim 1, wherein the method further comprises heat-treating the suspension in an oxygen-free atmosphere in the presence of sulfur or a sulfur compound. 4. The additive according to any one of claims 1 to 3, wherein the carbonaceous material powder is carbon black. 5. The additive according to any one of claims 1 to 3, wherein the carbonaceous material powder has an average primary particle size within a range of 1 to 50 nm. 6. Claim No. 6, wherein the molybdenum compound is at least one molybdenum compound selected from the group of compounds of heteropolyacids or transition metal salts thereof such that the ratio of the number of molybdenum atoms to the number of polyatoms is at least 0.7. The additive according to any one of Items 1 to 3. 7 A heteropolyacid and its transition metal salt are 2,
The additive according to any one of claims 1 to 3, which is a molybdenum compound reduced to 4 or 6 electrons. 8 Transition metal salts include Cu ²⁺ , Mn ²⁺ , Ni ²⁺ , Co ²⁺ ,
The additive according to any one of claims 1 to 3, which has a cation selected from the group consisting of Fe ³⁺ , Cr ³⁺ , and Zn ²⁺ . 9. The additive according to any one of claims 1 to 3, wherein the oxygen-containing polar solvent is water. 10. The additive according to any one of claims 1 to 3, wherein the method is carried out in the presence of high shear forces. 11. The additive according to any one of claims 1 to 3, wherein the method is carried out using a molybdenum equivalent amount in the molybdenum compound that is smaller than the amount of the carbonaceous material powder. 12 A process of adding additives to heavy hydrocarbon oil to obtain a mixed oil raw material. Here, the additives include () carbonaceous material powder having an average primary particle size within the range of 1 to 200 nm; and () polycarbonate. A solution obtained by dissolving at least one molybdenum compound selected from heteropolyacids and transition metal salts thereof in an oxygen-containing polar solvent if it contains a molybdenum atom is mixed in a hydrocarbon oil to obtain a suspension. The additive obtained by the method is characterized by comprising: a step of thermally decomposing the mixed oil raw material in the presence of hydrogen or a hydrogen-containing gas to obtain a product; and a step of recovering light oil and residual oil from the product. Hydrocracking method for heavy hydrocarbon oil. 13. The hydrocracking method according to claim 12, wherein the additive method is to further add and disperse sulfur or a sulfur compound to the suspension. 14. The hydrocracking method according to claim 12, wherein the additive method further comprises heat treating the suspension in an oxygen-free atmosphere in the presence of sulfur or a sulfur compound. 15. The hydrocracking method according to any one of claims 12 to 14, wherein the carbonaceous material powder is carbon black. 16. The hydrocracking method according to any one of claims 12 to 14, wherein the carbonaceous material powder has an average primary particle diameter within a range of 1 to 50 nm. 17. Claim No. 1, wherein the molybdenum compound is at least one molybdenum compound selected from the group of compounds of heteropolyacids or transition metal salts thereof such that the ratio of the number of molybdenum atoms to the number of polyatoms is at least 0.7. 12
The hydrocracking method according to any one of Items 1 to 14. 18 Heteropolyacid and its transition metal salt are
The hydrogenolysis method according to any one of claims 12 to 14, which is a molybdenum compound reduced to 2, 4 or 6 electrons. 19 Transition metal salts include Cu ²⁺ , Mn ²⁺ , Ni ²⁺ , Co ²⁺ ,
The hydrogenolysis method according to any one of claims 12 to 14, which has a cation selected from the group consisting of Fe ³⁺ , Cr ³⁺ , and Zn ²⁺ . 20. The hydrogenolysis method according to any one of claims 12 to 14, wherein the oxygen-containing polar solvent is water. 21. The hydrocracking process according to any one of claims 12 to 14, wherein the process is carried out in the presence of high shear forces. 22 Claims 12 to 1, wherein the method is carried out using a molybdenum equivalent amount in the molybdenum compound that is smaller than the amount of the carbonaceous material powder.
The hydrocracking method according to any one of Item 4. 23 The mixed oil raw material has a molybdenum content of 5 to 5
300ppmW, and contains an additive such that the amount of carbonaceous material powder is within the range of 0.02 to 1.5% by weight, according to any one of claims 12 to 14. Hydrocracking method. 24. The hydrocracking method according to any one of claims 12 to 14, wherein the heavy hydrocarbon oil is a vacuum distillation residue oil. 25. The hydrocracking method according to any one of claims 12 to 14, wherein the thermal decomposition is carried out at a temperature within the range of 450 to 520°C. 26. Any one of claims 12 to 14, characterized in that the hydrocracking method further involves recycling at least a portion of the residual oil by returning it to the step of obtaining a mixed oil raw material. Hydrocracking method described in.