JP2981340B2 - Method for producing catalyst for catalytic hydrocracking of heavy hydrocarbons - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for obtaining a cracked oil having good properties from heavy hydrocarbons such as vacuum residue, ultra-heavy oil, oil sand bitumen, or a mixture of coals and heavy hydrocarbons. The present invention relates to a catalytic hydrocracking process of heavy hydrocarbons using a catalyst.

[0002]

2. Description of the Related Art In the petroleum refining industry, the following methods are used in order to obtain cracked and refined oils having properties better than heavy hydrocarbons such as vacuum residues, ultra-heavy oils and oil sand bitumen. (1) Pyrolysis process of visbreaker, coker, etc. (2) Catalytic pyrolysis process represented by FCC (3) Catalytic hydrocracking process (4) Co-treatment for treating a mixture of coal and heavy hydrocarbons Treatment process (co-processing) (5) Coal liquefaction technology using iron-based catalyst

[0003]

The above-described techniques for catalytic hydrocracking of heavy oil hydrocarbons for the production of light oils having good properties have the following problems. (1) Pyrolysis method Since pyrolysis of hydrocarbons involves a polycondensation reaction, gas, pitch, and coke are generated frequently, and the light oil acquisition rate is low. (2) Catalytic cracking method Coke is generated on the catalyst, the activity is greatly reduced, and the catalyst is poisoned. Therefore, countermeasures are required, and there is a limit to the feed oil containing a large amount of heavy metals. (3) Hydrocracking method The catalyst used for hydrocracking involves dispersing a metal capable of hydrogenation on an inert carrier and adding a second or third metal as a measure to prevent metal agglomeration. It is normal to do
Therefore, the carrier was only a place for supporting the metal, the hydrogen consumption was large, the light oil yield was poor, and the conversion was not satisfactory. (4) Co-processing of coal and heavy hydrocarbons In addition to the problem of severely decreasing the activity of the catalyst, the light oil yield is low, and asphaltene and preasphaltene remain in the residue, so the oil content from the residue Vacuum distillation, filtration, and recovery
Separation steps such as sedimentation are required. (5) Coal liquefaction method When an iron-based catalyst is used, increasing the hydrogenation depth increases gas generation and increases hydrogen consumption. Since asphaltenes and preasphaltenes remain in the residue, vacuum distillation, solvent demineralization, pressurized leaf filtration, and the like are employed for oil recovery, but the oil recovery is poor.

[0004]

The present invention belongs to the catalytic hydrocracking process of (3), and the present invention has low production of gaseous hydrocarbons, high light and medium oil yield, It is an object of the present invention to provide a catalyst for converting all asphaltene and pre-asphalten into light and medium oils and coke, and to provide a method for catalytic hydrocracking of heavy hydrocarbons using the catalyst. A basic problem in applying a catalyst to the treatment of heavy hydrocarbons is how to hydrocrack asphaltene and preasphaltene, which are coke precursors.
The catalyst of the present invention is not a catalyst having only a conventional hydrogenation ability, but has a carbon support having a dehydrogenation ability, and hydrogen dehydrogenated from a coke precursor of asphalten or preasphaltene moves on the support, and the hydrogenation ability Utilizing the reverse spillover effect of hydrogenating hydrocarbons on metals having That is, an object of the present invention is to provide a bifunctional catalyst having dehydrogenation and hydrogenation capabilities. That is, the present invention activates carbonized coal obtained by carbonizing brown coal having an ash content of less than 3% by weight at 400 to 800 ° C. in a carbon dioxide gas atmosphere at 600 to 900 ° C. in a carbon dioxide gas or steam atmosphere. One or more metals selected from Group VIII of the Periodic Table are supported on the carbon support obtained by reduction, then reduced with hydrogen, and then subjected to sulfurization treatment to obtain catalytic hydrogenation of heavy hydrocarbons. This is a catalytic cracking method and a catalytic hydrocracking method for heavy hydrocarbons using the catalyst. The most important points of the production of a carbon support having a dehydrogenating ability and the bifunctional catalyst comprising a metal having a hydrogenating ability are in selecting the carbon support. As raw materials of the carbon support suitable for the purpose, elemental analysis values wt% (C;
O; 40 to 20), and lignite having an average number of aromatic groups in the range of 0.5 to 1.5 is used. Ash content in brown coal is 3
It is necessary to be less than the weight%, the less is desirable,
Particularly preferred is 1.5% by weight or less. In the case of lignite with high ash content, for example, Morwell, which generally contains ash
Charcoal cannot be used as a raw material of the present invention, but can be used if it is deashed and the ash content is less than 3% by weight. Particularly preferred types of brown coal include Yallourn coal and demineralized Morwell coal.

The method for producing the catalytic carbon carrier used in the present invention is as follows. Lignite is 400-800 ℃ in CO ₂ stream
The carbonized carbon obtained by carbonization under heating is further activated at 600 to 900 ° C. in a CO ₂ or steam atmosphere or in the presence of CO ₂ and steam to obtain a carbon carrier. The activation is particularly effective at a temperature of 800 to 900 ° C. in carbon dioxide gas. Next, the above carbon carrier is immersed in an aqueous solution of a metal salt selected from the group VIII of the periodic table, preferably in a 0.5 to 5 N aqueous solution, for several hours, and the metal is supported by an impregnation method. Since the carbon support is activated, it quickly adsorbs almost dissolved metal salts. In this case, the supported amount of the metal is sufficiently from 0.1% by weight to 10% by weight.

After the supported metal is dried, it is dried under N ₂ atmosphere.
It is decomposed by heating at 300-500 ° C, reduced and sulfurized before use. In addition, when the sulfur content in the raw material brown coal is large, this sulfurization may not be necessary. Examples of the Group VIII metal of the periodic table include iron, cobalt, nickel and the like, and iron is particularly preferable in terms of cost and ease of handling, and it is preferable to use nitrates and acetates thereof in terms of ease of reduction. For the reduction, H ₂ or a mixture of CO and H ₂ can be used. Reduction is preferably performed at 400 to 500 ° C. for several hours in an H ₂ atmosphere. Sulfide can be carried out in a gas containing H ₂ S. The catalyst thus obtained is a bifunctional catalyst having a hydrogen transfer phenomenon effect, and exhibits the following characteristics. The catalytic hydrocracking accompanied by this hydrogen transfer phenomenon is based on the basic reaction of thermal decomposition, hydrocracking, and transfer of hydrogen from a coke precursor to light components by a catalyst. The hydrogen mechanism phenomenon, also called the reverse spillover phenomenon, is a theory that explains the catalytic phenomenon.Hydrogen of asphaltene or preasphalten adsorbed on activated carbon is desorbed, the hydrogen moves on the activated carbon, and hydrogen on the activated carbon is removed. The transfer of the hydrogen to the raw material hydrocarbon on the metal having chemical activity can explain the catalytic hydrocracking reaction of heavy hydrocarbons. Since hydrogen of asphaltene or pre-asphalten is used for the hydrogenation reaction, there is an advantage that the amount of hydrogen required is small. At the same time, asphaltene or pre-asphalten is dehydrogenated to form coke, which is deposited on the activated carbon, so that there is no asphaltene or pre-asphalten in the product, so that the viscosity of the product is reduced and its handling is facilitated.

[0007] The catalytic hydrocracking and reforming of heavy hydrocarbons using the present catalyst involves mixing a finely divided catalyst and heavy hydrocarbons, treating the mixture in a tubular reactor, Flushing (F
After distillation of the lashing), the residue can be separated by solid-liquid separation, and the liquid can be separated by distillation together with the flashing distillate. In the present invention, the distillate is recovered by suppressing the conversion of the reaction, and the coke deposited or independently dispersed on the catalyst is not separated from the liquid phase but is dispersed in a small amount of the liquid phase. It is also possible to pull it out. It is also possible to form a catalyst and charge it in a fixed-bed / moving-bed reactor for reaction, or to apply it to a fluidized-bed reactor.

Further, examples of application of the present catalyst include, but are not limited to, the following. 1) Coal and petroleum heavy oil are mixed, this catalyst is added to make a slurry, and then heated under hydrogen pressure to liquefy coal and simultaneously reform petroleum heavy oil. 2) Coal and solvent are mixed, this catalyst is added, slurry is formed, and then heated under hydrogen pressure to liquefy coal. 3) Add a catalyst to the residual oil of coal liquefaction, make it into a slurry, and heat it under hydrogen pressure to convert it to light oil.

[0009]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 Lignite having the following composition, an average number of aromatic groups of 1.0, an aromatic ratio in carbon of 50%, and a volatile matter of 40 to 50%, was treated with an inner diameter of 50%.
The temperature was raised from room temperature to 600 ° C. at a rate of 5 ° C./min from a room temperature under a carbon dioxide gas flow in a quartz rotary kiln having a diameter of mm, and the mixture was carbonized at 600 ° C. for 60 minutes to obtain carbonized coal. Under the CO ₂ atmosphere
After the temperature was raised from 600 ° C. to 850 ° C. at 10 ° C./min, it was kept and activated for 60 minutes to obtain a carbon carrier. The carbon carrier was immersed in a 1N aqueous solution of iron nitrate for 3 hours, loaded with 5% by weight of Fe, dried, and heated at 400 ° C. for 1 hour in an N ₂ atmosphere.
After reducing at 450 ° C. for 1 hour under H ₂ atmosphere, H ₂ + H
₂ S (1: 0.25) for 30 minutes presulfided at 450 ° C. in a mixed gas. Table 1 shows the reaction conditions and the like. -Composition of raw material lignite C: 67.2, H: 4.3, N: 1.0, S: 0.2,
O: 27.2, ash: 0.6 The properties of the obtained catalyst were as follows. Specific surface area 840 m ² / g Pore volume 0.18 cm ³ / g MCH conversion 70.7% Example 2 A catalyst was prepared in the same manner as in Example 1 except that the reaction time was changed to 30 minutes.

Example 3 A catalyst was prepared in the same manner as in Example 2 except that demineralized Morwell coal was used as a raw material.

Example 4 A catalyst was prepared in the same manner as in Example 1, except that 1% by weight of Ni was supported instead of 5% by weight of Fe. Then, the decomposition reaction of Arabian heavy vacuum residue was carried out by the catalyst of the present invention using a gas flow type apparatus using an induction stirring type autoclave having an inner volume of 150 ml. After charging 40 g of reduced pressure Arabian heavy oil as a feedstock oil and 4 g of the catalyst obtained in Example 1 to an autoclave, the reaction temperature was increased.
The reaction was performed at 435 ° C., a reaction time of 60 minutes, and a hydrogen pressure of 70 kg / cm ² . The obtained gaseous hydrocarbon was analyzed by gas chromatography, and the distillate was analyzed by distillation gas chromatography. The toluene-insoluble matter was used as coke. Table 1 shows the results of the above examples.

Comparative Examples 1-3 Catalysts were prepared in the same manner as in Example 1 except that commercially available activated carbon (Comparative Example 2) and Morwell coal (Comparative Example 3) were used as raw materials. Next, these catalysts were subjected to a decomposition reaction of Arabian heavy vacuum residual oil in the same manner as in the above Examples. The results are shown in Table 1 together with the case without the catalyst (Comparative Example 1).

[0013]

[Table 1]

[0014]

As described above, the catalyst prepared according to the present invention is a bifunctional catalyst having a reverse spillover effect, so that when heavy hydrocarbons are treated, the product is a coke precursor in the product. Since no asphaltenes or pre-asphaltenes remain, the vacuum distillation, solvent extraction and CDS methods conventionally used for oil recovery are not required. In addition, when oil is recovered using the precoat filter method, the filtration rate has been rapidly reduced in the past due to unreacted asphaltenes and preasphaltenes. Liquid separation becomes possible. Because the reverse spillover phenomenon can be used,
Hydrogen consumption is about 1/10 compared to conventional catalytic hydrocracking catalyst.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C10G 1/00 C10G 1/00 A 1/06 1/06 D 47/12 47/12 (56) References JP-A-60- 58239 (JP, A) JP-A-63-260984 (JP, A) JP-A-59-93794 (JP, A) JP-A-54-90204 (JP, A) JP-B-26-875 (JP, B1) JP-B-48-43555 (JP, B1) (58) Field surveyed (Int. Cl. ⁶ , DB name) B01J 21/00-38/74 C01B 31/08 C10G 47/14

Claims (1)

(57) [Claims] Claims: 1. Lignite having an ash content of less than 3% by weight is carbonized in a carbon dioxide gas atmosphere at 400 to 800 ° C.
One or more metals selected from Group VIII of the periodic table are supported on a carbon support obtained by activation at 600 to 900 ° C. in a carbon dioxide gas or steam atmosphere, and then reduced with hydrogen. , then the heavy hydrocarbons contact manufacturing method of the hydrocracking catalyst, wherein the sulfiding process.