JP3440990B2 - How to convert hydrocarbon resources - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to gas, such as hydrogen, from hydrocarbon resources including fossil fuels such as coal, heavy oil, oil shale and natural bitumen, and organic wastes such as municipal waste, sludge and organic waste materials. The present invention relates to a method for producing oil, a water-soluble product oil.

[0002]

2. Description of the Related Art Water in a subcritical or supercritical state at high temperature and high pressure has a high diffusion capacity, a high density, a high ionic product, and a high ability to dissolve organic substances. Various processes have been developed for lightening, cleaning and detoxifying organic substances by using water. For example, by treating a fossil fuel such as coal or a polymer compound such as a vulcanized rubber with water in a subcritical or supercritical state, a fossil fuel accompanied by hydrogenolysis by a hydrogen donating action from water or a polymer compound A method of modifying and lowering the molecular weight has been proposed (Japanese Patent Laid-Open No. 9-151384).

[0003]

However, when a hydrocarbon resource is lightened in supercritical water based on the above-mentioned conventional method, a necessary and sufficient amount of hydrogen is obtained to lighten the produced oil. Is difficult. Therefore, this method has a problem that the conversion rate of hydrocarbon compounds is low and that the produced oil is often heavy. An object of the present invention is to provide a hydrocarbon resource conversion method capable of producing a gas such as hydrogen, a light oil and a water-soluble product oil from a hydrocarbon resource at a high conversion rate without requiring a complicated process.

[0004]

The invention according to claim 1 is
As shown in FIG. 1, the temperature is 380 to 500 ° C. and the pressure is 25 to 4
First reaction region 14 at 0 MPa and temperature 500 to 900 ° C.
A method for converting a hydrocarbon resource in a reactor 13 having a second reaction region 15 at a pressure of 25 to 40 MPa, wherein the hydrocarbon resource and water are reacted in the first reaction region 14 of the reactor 13 to carry out the above-mentioned carbonization. Primary decomposition of the hydrogen resource produces a water-insoluble oil and a water-soluble oil dissolved in water, and the reactor 13
In the second reaction region 15, the residue produced by the primary decomposition is reacted with water to produce a gas containing hydrogen as a main component, which is a hydrocarbon resource conversion method. The invention according to claim 2 is the invention according to claim 1, wherein the residue produced by primary decomposition in the second reaction region 15 of the reactor 13 and water are reacted with an alkali catalyst to contain hydrogen as a main component. It is a conversion method of hydrocarbon resources that generate gas.

The invention according to claim 3 is the invention according to claim 1 or 2, wherein the product mainly decomposed in the first reaction zone 14 of the reactor 13 and the hydrogen generated in the second reaction zone 15 are mainly used. The component gas is separated by a separator 17 into a gas containing hydrogen as a main component, a water-insoluble oil and a water-soluble oil dissolved in water, and the water-insoluble oil and hydrogen separated by the separator 17 are contained as main components. The generated gas together with the catalyst in the hydrogenation reactor 20.
It is a hydrocarbon resource conversion method in which the water-insoluble oil is converted to a light oil by reacting at a pressure of 10 to 30 MPa at a temperature of 00 to 500 ° C. The invention according to claim 4 is claim 3
The present invention relates to a method for converting a hydrocarbon resource in which the water-soluble oil dissolved in water separated by the separator 17 is solvent-extracted by the extractor 22 to obtain the water-soluble oil. The invention according to claim 5 is the invention according to claim 4, wherein the water from which the water-soluble oil has been removed by the extractor 22 has a temperature of 500 to 900 ° C and a pressure of 25 to 4
The second reaction region 15 of the reactor 13 is heated and pressurized to 0 MPa.
It is a method of converting hydrocarbon resources used for the reaction in. In the present specification, "supercritical state of water" or "supercritical water" means 22 to 30 MP at a temperature of 374 to 900 ° C.
The state of water at the pressure a.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of hydrocarbon resources used in the present invention include fossil fuels such as coal, heavy oil, oil shale and natural bitumen, organic wastes such as municipal solid waste, sludge and organic waste materials. Since the reaction is carried out in a supercritical state of water in the reactor, the above hydrocarbon resource is pulverized in advance to a particle size of several mm or less, preferably 300 μm or less depending on the ability of the pump, and then the interface with water. The activator is mixed and fed to the reactor in the form of a hydrocarbon slurry. Water in the hydrocarbon slurry preferably has a slurry concentration of 30 to 6
It is added to a finely pulverized product of hydrocarbon resources so as to be 0% by weight.

In the invention according to claim 1, the pressure is 2
In a single reactor having two reaction zones of 5 to 40 MPa and different temperatures, first the temperature of 380 to 50
The hydrocarbon resource is primarily decomposed by supercritical water in the first reaction zone at 0 ° C. This primary decomposition produces a water-insoluble oil and a water-soluble oil dissolved in water. Moreover, the temperature is 500 to 900.
In the second reaction region at 0 ° C., the residue produced by the primary decomposition is caused to undergo a water gasification reaction of the following formula (1) with supercritical water to produce a gas containing hydrogen as a main component. Here, a part of the ash contained in the residue is used as a catalyst, the water gasification reaction is further accelerated, and hydrogen is effectively produced. C + H ₂ O → CO + H ₂ (1) The gas containing hydrogen as a main component produced in the second reaction region quickly moves to the upper first reaction region, in which hydrogen is the first
A so-called hydrogenation reaction which reacts with the active primary decomposition product generated in the reaction region is caused to lighten the produced oil. The preferable temperature of the first reaction region is 380 to 450 ° C., and the preferable pressure is 25 to 30 MPa. The preferable temperature of the second reaction region is 600 to 700 ° C., and the preferable pressure is 25 to 30 MPa. The temperature of the first reaction zone is 38
When the temperature is less than 0 ° C. and the pressure is less than 25 MPa, the temperature of the second reaction region is less than 500 ° C., and when the pressure is less than 25 MPa, each reaction rate is slow, and the temperature of the first reaction region is 50%.
When the temperature exceeds 0 ° C., the pressure exceeds 40 MPa, the temperature of the second reaction region exceeds 900 ° C., and the pressure exceeds 40 MPa,
The reactor is overloaded and not efficient.

The gas containing hydrogen as a main component, which is produced in the second reaction region, contains methane, carbon monoxide, carbon dioxide and the like in addition to hydrogen. Examples of the water-insoluble oil produced in the first reaction region include oil (fraction containing benzene, toluene, and xylene (hereinafter referred to as BTX) as main components), asphaltene, and pre-asphaltene. Water-soluble oil dissolved in water Examples thereof include phenols, organic acids, aldehydes and the like.

According to the second aspect of the invention, the residue produced by primary decomposition in the second reaction zone of the reactor and water are reacted with an alkali catalyst to produce a gas containing hydrogen as a main component. Since water in a supercritical state has a high fluid density, when an alkali catalyst is added from the outside, the contact between the carbon particles of the residue produced by the primary decomposition and the particles of the alkali catalyst is improved. As a result, the water gasification reaction of the above formula (1) and the water gas shift reaction of the following formula (2) are performed more efficiently, and more gas containing hydrogen as a main component is produced. CO 2 + H ₂ O = CO ₂ + H ₂ (2) That is, the produced hydrogen is quickly separated from the active carbon surface of the residual particles, diffuses and dissolves in supercritical water. As a result, the active carbon surface is exposed and the activation ability of the carbon surface is quickly restored, and new hydrogen is generated based on the above reaction formula. Examples of the alkali catalyst include potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, calcium oxide, calcium carbonate, sodium oxide, potassium oxide and the like.

In the invention according to claim 3, the gas containing hydrogen as a main component in the separator is the gas containing hydrogen as a main component produced in the first reaction region of the reactor and the hydrogen produced in the second reaction region. And water-insoluble oil and water-soluble oil dissolved in water. Further, when the separated water-insoluble oil is reacted with a gas containing hydrogen as a main component together with a catalyst in the hydrogenation reactor, the water-insoluble oil is converted into a light oil. Examples of the catalyst used in the hydrogenation reaction include molybdenum oxide, molybdenum-cobalt composite oxide, molybdenum-nickel composite oxide, and the like.

In the invention according to claim 4, the water-soluble oil dissolved in water separated by the separator is solvent-extracted by the extractor to obtain water-soluble oil. Methyl isobutyl ketone, diethyl ether, N-butyl acetate, diisobutyl ether, etc. are added as a solvent to the water-soluble oil dissolved in the water in the extractor, and when the water-soluble oil is moved into the solvent and left standing, it is separated from water by the difference in specific gravity. To do. In the invention according to claim 5, the water from which the water-soluble oil has been removed in the extractor is heated to a temperature of 500 to 900 ° C. and a pressure of 25 to 40 MPa and supplied to the second reaction region of the reactor to supply water. Reuse.

FIG. 1 shows a hydrocarbon resource converter according to an embodiment of the present invention. The hydrocarbon resource is supplied to the preheater 11 in the form of a hydrocarbon slurry. An alkali catalyst is added if necessary. The hydrocarbon slurry is heated to about 100 to 150 ° C. in the preheater 11. The heated slurry is increased in pressure to 25 to 40 MPa by the pump 12 and sent to the first reaction region 14 of the reactor 13 which is maintained at a temperature of 380 to 500 ° C. First reaction area 14
Thus, the hydrocarbon resources in the slurry are primarily decomposed to produce a water-insoluble oil and a water-soluble oil dissolved in water. When the hydrocarbon resource is coal, it is considered that a hydrolysis reaction of coal, a thermal decomposition reaction of coal, and a hydrogenation reaction occur with respect to the coal slurry in a high temperature and high pressure state in the first reaction region 14. That is, in high-temperature water, non-covalent bonds such as hydrogen bonds in coal are dissociated, and coal expands. Thereby, the decomposition and liquefaction reaction of coal proceeds more effectively. In the hydrolysis reaction of coal, OH ⁻ and H ⁺ of H ₂ O are added to the hetero element portion connecting the benzene ring of coal to lower the molecular weight of coal. In the thermal decomposition reaction of coal, the coal is simply thermally decomposed into low molecular weight compounds. Further, in the hydrogenation reaction, H is added to the radicals generated during the above reaction, which stabilizes the thermally decomposed species. In addition, a reaction occurs between hydrogen and a stable molecule that is not thermally decomposed. Here, a hydrogenation reaction may occur also in a hydroxyl group and a carboxylic acid group generated by hydrolysis, but the hydrogen reaction to the above radical occurs predominantly. the above~
The reactions are not carried out individually but in parallel with each other, and the coal lightening progresses. In this way, the coal is decomposed, lightened, and converted into a water-insoluble oil and a water-soluble oil dissolved in water.

The decomposed products of the slurry produced in the first reaction zone 14 are a water-insoluble oil, a water-soluble oil dissolved in water and a residue. This residue is transferred to the second reaction region 15 of the reactor 13 provided in communication with the first reaction region 14 and maintained at a temperature of 500 to 900 ° C. 15a is a heater.
Here, the residue is thermally decomposed to generate a gas containing hydrogen as a main component, using the alkaline catalyst contained in the slurry, the inorganic matter contained in the residue and the inorganic matter contained in the ash described later as a catalyst. The gas containing hydrogen as a main component moves to the upper first reaction region 14 and is used for a slurry conversion reaction and a hydrogenation reaction in the first reaction region 14. Second reaction region 15
Part of the ash generated as a result of the reaction is used as a catalyst for the gas generation reaction, and the rest is withdrawn from the bottom of the reactor 13.

A mixture containing a gas containing hydrogen as a main component excluding a residue, a water-insoluble oil, and a water-soluble oil dissolved in water is a valve 1
6 to reach a separator 17, where it is separated into a gas containing hydrogen as a main component, a water-insoluble oil, and a water-soluble oil dissolved in water. The gas containing hydrogen as a main component separated by the separator 17 passes through the valve 18, and the water-insoluble oil is discharged through the valve 19.
And is supplied to the hydrogenation reactor 20. Hydrogenation reactor 20
A molybdenum catalyst is further added to. 400-
The water-insoluble oil is converted into an oil containing BTX or the like as a main component by reacting at a temperature of 500 ° C. and a pressure of 10 to 30 MPa. From the hydrogenation reactor 20, a gas containing hydrogen as a main component and a light oil are taken out. The water-soluble oil dissolved in water separated by the separator 17 is supplied to the extractor 22 through the valve 21. Here, a solvent such as diethyl ether or methyl isobutyl ketone is added to extract a water-soluble oil such as phenols and organic acids. The remaining water from which the water-soluble oil has been extracted by the extractor 22 is boosted to a pressure of 25 to 40 MPa by the pump 23, then supplied to the preheater 24 and heated to about 500 to 900 ° C., and then 25 to 30 MPa. 600-70 by pressure
It is fed under pressure to the second reaction region 15 of the reactor 13 which is maintained at a temperature of 0 ° C.

[0015]

As described above, according to the present invention, the hydrocarbon resource is reacted with water in the first reaction zone of the reactor having a temperature of 380 to 500 ° C. and a pressure of 25 to 40 MPa to generate the hydrocarbon resource. Water-insoluble oil and water-soluble oil dissolved in water are produced by primary decomposition, and the residue and water produced by the primary decomposition in the second reaction zone of the reactor at a temperature of 500 to 900 ° C. and a pressure of 25 to 40 MPa. It is possible to produce hydrogen, light oil, and water-soluble product oil from hydrocarbon resources at a high conversion rate without requiring a complicated process because it is made to react with and produce a gas containing hydrogen as a main component. Becomes

[Brief description of drawings]

FIG. 1 is a configuration diagram of a hydrocarbon resource conversion device of the present invention.

[Explanation of symbols]

11 Preheater 13 reactor 14 First reaction area 15 Second reaction area 17 Separator 20 Hydrogenation reactor 22 Extractor 24 Preheater

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-58-42689 (JP, A) JP-A-10-237458 (JP, A) JP-A-10-237459 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C10J 3/46 C01B 3/32 C10G 11/20

Claims (5)

(57) [Claims] 1. A pressure of 25 to 40 at a temperature of 380 to 500 ° C.
A method for converting a hydrocarbon resource in a reactor (13) having a first reaction zone (14) of MPa and a second reaction zone (15) at a temperature of 500 to 900 ° C and a pressure of 25 to 40 MPa, the reaction comprising: In the first reaction region (14) of the vessel (13), a hydrocarbon resource and water are reacted to primary decompose the hydrocarbon resource to produce a water-insoluble oil and a water-soluble oil dissolved in water, A method for converting a hydrocarbon resource, characterized in that in the second reaction zone (15) of the reactor (13), the residue produced by the primary decomposition is reacted with water to produce a gas containing hydrogen as a main component. 2. The gas containing hydrogen as a main component according to claim 1, wherein the residue produced by primary decomposition and water in the second reaction region (15) of the reactor (13) are reacted with an alkali catalyst to produce a gas containing hydrogen as a main component. Conversion method of hydrocarbon resources. 3. A separator (17) is used to produce a gas containing hydrogen as a main component, which is primarily decomposed in the first reaction zone (14) of the reactor (13) and hydrogen produced in the second reaction zone (15). Is separated into a gas containing water as a main component, a water-insoluble oil and a water-soluble oil dissolved in water, and the gas containing the water-insoluble oil and hydrogen separated by the separator (17) is hydrogenated together with a catalyst. 4 in the reactor (20)
The method for converting a hydrocarbon resource according to claim 1 or 2, wherein the water-insoluble oil is converted into a light oil by reacting at a pressure of 10 to 30 MPa at a temperature of 00 to 500 ° C. 4. The method for converting a hydrocarbon resource according to claim 3, wherein the water-soluble oil dissolved in water separated by the separator (17) is solvent-extracted by the extractor (22) to obtain a water-soluble oil. 5. The water in which water-soluble oil is removed in the extractor (22) is heated to a temperature of 500 to 900 ° C. and a pressure of 25 to 40 MPa to raise the pressure in the second reaction region (15) of the reactor (13). The method for converting a hydrocarbon resource according to claim 4, which is used in a reaction.