JP4054934B2 - Method for producing fuel gas - Google Patents

Method for producing fuel gas Download PDF

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JP4054934B2
JP4054934B2 JP10274499A JP10274499A JP4054934B2 JP 4054934 B2 JP4054934 B2 JP 4054934B2 JP 10274499 A JP10274499 A JP 10274499A JP 10274499 A JP10274499 A JP 10274499A JP 4054934 B2 JP4054934 B2 JP 4054934B2
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liquid
step
fuel gas
method
amount
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JP2000290659A (en
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道夫 二川
吉明 原田
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大阪瓦斯株式会社
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels
    • Y02E50/14Bio-pyrolysis

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a fuel gas by treating a liquid organic material. In the present invention, the “liquid organic substance” means a liquid substance in which a liquid and / or solid organic substance is dissolved or dispersed in water.
[0002]
[Prior art and its problems]
Conventional solid organic waste (aerobic treated sludge, anaerobic treated sludge, sludge such as sewage sludge; firewood, paper, plastic, wood pieces, bamboo pieces, grass pieces, firewood, fibers, vegetable pieces, rubber, leather, food Processing waste, livestock waste, forest thinning / fallen tree, pruning waste, agriculture / forestry waste, marine product waste, etc.) and liquid organic waste (living wastewater, wastewater from food processing plants, livestock house / chicken farming) Wastewater from production sites, industrial wastewater containing components that are difficult to biologically treat; wastewater containing alcohols, carboxylic acids, aldehydes, etc.) are treated using separate technologies according to their characteristics. ing.
[0003]
In Japan, the amount of waste generated alone is about 50 million tons / year, about 75% of which is incinerated at many incineration plants. However, in these incinerators, only about 150 places effectively use waste through power recovery. Particularly in recent years, the generation of dioxins has become a major problem when incinerating various types of waste, and not only the construction of new incineration facilities but also the continued operation of some existing facilities is becoming difficult.
[0004]
More specifically, for example, sludges are incinerated after dehydration or landfilled. After the organic substance-containing wastewater is generally treated with activated sludge, the generated sludge is incinerated or landfilled as described above. Moreover, the water-containing waste containing an organic substance is dried and incinerated as it is.
[0005]
However, in recent years, the amount of solid organic waste and liquid organic waste generated has increased, and at the same time, regulations on waste are being strengthened. In the method of incinerating various kinds of waste by the conventional technology as described above, It is getting harder to deal with.
[0006]
In addition, from the viewpoint of “effective use of limited resources”, which is a major technical issue now, it is also necessary to reuse these wastes as resources.
[0007]
[Problems to be solved by the invention]
Therefore, the present invention provides a new technology for recovering and reusing solid and liquid organic wastes in a useful form such as fuel gas, electric power and thermal energy by treating them with high gasification efficiency. The main purpose is to do.
[0008]
[Means for Solving the Problems]
In light of the present state of the art as described above, the present inventor has conducted research on techniques for treating solid and liquid organic wastes, and as a result, has made these wastes wet under specific conditions in the form of liquid organic substances. It has been found that the above-mentioned problems can be almost achieved in the case of heat treatment and wet methanation treatment.
[0009]
That is, the present invention provides a method for producing fuel gas using the following liquid organic material as a raw material;
I. (1) In the first reactor, a gas containing liquid organic matter at a temperature of 100 ° C. or higher and a pressure at which at least a part of the raw material maintains a liquid phase, and containing oxygen of 0.5 times or less the theoretical oxygen amount Heating / pressurizing in the presence of
(2) Gas-liquid separation of the gas-liquid mixed phase formed in the step (1) above,
(3) In the second reactor, the separated liquid phase obtained in the step (2) is maintained at a temperature of 100 ° C. or higher and at least a pressure at which a part of the liquid phase is maintained, and metal and metal compound A process in which a gas mainly composed of methane gas is generated by catalytic cracking in the presence of a catalyst supporting at least one of the above as an active ingredient
A method for producing fuel gas, comprising:
2. Item 2. The fuel gas according to Item 1, wherein the liquid organic material is at least one of organic compound-containing water, a slurry composed of a solid organic matter crushed body and water, and a slurry composed of a solid organic matter crushed body, water and an organic compound-containing water. Manufacturing method.
3. In the step (1), the temperature in the reactor is 374 ° C. or higher, the pressure is 22 MPa · G or higher, and the liquid linear velocity (feed amount / reaction tower cross-sectional area) in the reactor is 0.01 to 0.1 cm / Item 2. The method for producing fuel gas according to Item 1, which is sec.
4). Item 2. The fuel gas production according to Item 1, wherein the amount of the oxygen-containing gas in the step (1) is 0.1 to 0.3 times the theoretical oxygen amount necessary for dissolving the organic substance and the inorganic substance in the liquid mixture. Method.
5. Item 2. The method for producing fuel gas according to Item 1, wherein the sludge and / or metal component generated in the step (1) is removed from the first reactor.
6). The fuel gas according to Item 1, wherein a part of the separated liquid phase obtained in the step (2) is circulated and mixed with the liquid organic substance in the step (1), and the remaining part of the separated liquid phase is fed to the step (3). Manufacturing method.
7. Item 7. The method for producing fuel gas according to Item 6, wherein the amount of liquid phase circulated in step (1) is at least five times the amount of liquid phase fed to step (3).
8). Item 8. The method for producing fuel gas according to Item 7, wherein the amount of liquid phase circulated in step (1) is 10 to 20 times the amount of liquid phase fed to step (3).
9. Item 2. The method for producing fuel gas according to Item 1, wherein power is recovered from the gas phase after the gas-liquid separation obtained in the step (2).
10. Item 6. The method for producing fuel gas according to Item 5, wherein the metal component is removed by subjecting the separation liquid phase fed to the step (3) to a coagulation sedimentation process in advance.
11. The catalytically active component in step (3) is at least one selected from the group consisting of Ru, Pd, Rh, Pt, Ir, Ni, Co, Mn, and Ce and water-insoluble or poorly water-soluble compounds thereof, The method for producing a fuel gas according to Item 1, wherein is at least one selected from the group consisting of titania, zirconia, titania-zirconia, alumina, silica, and alumina-silica.
12 Item 12. The method for producing fuel gas according to Item 11, wherein the amount of the catalytically active component supported is in the range of 0.01 to 10% of the carrier weight.
13. Item 13. The method for producing fuel gas according to Item 12, wherein the amount of the catalytically active component supported is in the range of 0.1 to 3% of the carrier weight.
14 In the step (3), the temperature in the reactor is 374 ° C. or higher, the pressure is 22 MPa · G or higher, and the liquid linear velocity (feed amount / reaction tower cross-sectional area) in the reactor is 0.1 to 1.0 cm / Item 2. The method for producing fuel gas according to Item 1, which is sec.
15. Item 2. The fuel gas production method according to Item 1, wherein in the step (1), the sulfur compound present in the liquid organic material is oxidized by dissolved oxygen in the liquid organic material and / or oxygen in the supply gas.
16. Item 3. The product according to Item 2, wherein the product in the step (3) is subjected to gas-liquid separation, and the obtained separated water is heat-exchanged with the liquid organic material in the step (1) and then recycled as the solid organic matter crushed slurry-containing water. A method for producing fuel gas.
17. A fuel gas characterized in that energy is recovered as heat and / or motive power from the gas mainly comprising methane and carbon dioxide obtained in the step (3) of the above item 1, and then decarboxylated and the amount of heat is adjusted. Manufacturing method.
18. Item 18. The method for producing fuel gas according to Item 17, wherein the decarboxylation is performed using PSA and / or a separation membrane and / or an alkaline solution.
19. Item 19. The fuel gas production method according to Item 18, wherein the pressure in the absorption tower for decarboxylation performed using an alkaline liquid is a high pressure exceeding atmospheric pressure, and the pressure in the regeneration tower of the alkaline liquid is equal to or lower than atmospheric pressure.
20. Item 20. The method for producing fuel gas according to Item 19, wherein power recovery is performed from a liquid feed pump to the absorption tower.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The liquid organic substance to be treated by the present invention includes all liquid substances in which at least one of a liquid and a solid organic substance is dissolved or dispersed in a liquid such as water.
[0011]
Solid organic matter as an organic source is not particularly limited, and in addition to municipal waste and other general waste, aerobic treated sludge, anaerobic treated sludge, sludge such as sewage sludge; plant, bamboo, grass, straw, fiber Solid organic matter such as corn, vegetable waste, rubber, leather, agriculture / forestry / livestock industry / poultry industry / fishery industry, bio-related waste and products (corn shaft, okara, coffee beans, straw, rice straw) , Thinned wood, fallen trees, etc .; broad biomass including giant kelp, eucalyptus, etc.); mineral products (coal, peat, etc.), various hydrocarbons, etc. These solid organic substances may be processed in a mixed state of two or more.
[0012]
Examples of liquid organic substances include domestic wastewater including straw, paper, plastics, wastewater containing organic compounds (alcohols, carboxylic acids, aldehydes, etc.), human waste, plating wastewater, food factory wastewater, paper mill wastewater, pharmaceutical factory Wastewater, photographic wastewater, printing wastewater, agricultural chemical-related wastewater, dyeing wastewater, semiconductor manufacturing plant wastewater, wastewater generated by coal liquefaction or gasification, wastewater containing organic matter such as wastewater generated by thermal decomposition of municipal waste, etc. Is exemplified.
[0013]
The above solid and liquid organic sources are usually one or more metal components such as Mg, Al, Si, P, Ca, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Cd. Is included. The method of the present invention can be carried out even if the object to be processed contains such a metal component.
[0014]
The liquid organic material to be treated by the present invention can be formed by adding a liquid such as water, if necessary, to at least one of the above solid and liquid organic sources and stirring. At this time, the solid organic material source can be pulverized to an appropriate size in advance.
[0015]
Hereinafter, the present invention will be described in detail with reference to the drawings.
[0016]
FIG. 1 is a flow sheet showing the outline of the method of the present invention.
[0017]
Solid organic matter 40 such as waste, biomass, etc. is sent to the coarse crusher 70 after being subjected to a separation treatment in the pretreatment device 50 in order to remove inorganic machine components such as metal and glass as much as possible. Together with water and / or liquid organic matter source 90, it is sent to storage tank 1 and stored as a liquid organic matter or solid organic matter slurry.
[0018]
As shown in FIG. 1, in this invention, the liquid organic substance formed as mentioned above is processed. That is, the liquid organic substance obtained in the storage tank 1 is mixed with a gas containing oxygen less than 0.5 times the theoretical oxygen amount through the line 2, the pump 3 and the line 4, as will be described later in the line 7. In response to this, after being heated to a temperature of 100 ° C. or higher by the heat exchanger 8, it is supplied to the solubilization tower 10 via the line 9. Gas required for solubilization is compressed and pressurized by a compressor 5 and then sent from line 6 to line 7 where it is mixed with liquid organic matter and solubilized along with liquid organic matter. It is supplied to the tower 10.
[0019]
As a heat source of the heat exchanger, a high-temperature treatment liquid from a catalyst-filled reactor (methanation reaction tower) described later may be circulated, or other heating means may be used. When the concentration of the component to be treated is low and the predetermined reaction temperature cannot be maintained during the solubilization reaction in winter, etc., or when it is necessary to raise the temperature to the predetermined temperature, heating is further performed by a heater (not shown). Alternatively, steam can be supplied to the solubilization tower from a steam generator (not shown). Further, in order to set the temperature in the solubilization tower to a predetermined temperature at the start-up, steam is directly fed into the solubilization tower to raise the temperature, or a heater (between the heat exchanger and the solubilization tower ( The temperature can also be raised by providing a not-shown).
[0020]
The temperature in the reaction in the solubilization tower (solubilization reaction) is usually about 100 ° C. or higher, more preferably about 150 to 370 ° C., in order to favorably progress the solubilization of the solid organic matter. The higher the temperature during the solubilization reaction, the higher the solubilization rate due to low molecular weight of the organic matter and the shorter the residence time of the object to be treated (liquid organic matter) in the solubilization tower. Therefore, the solubilization reaction temperature may be determined by comprehensively considering the pollutant concentration in the object to be processed, the operating cost, the construction cost, and the like. The pressure at the time of reaction should just be more than the pressure which can hold | maintain a liquid phase at least one part of to-be-processed object in predetermined temperature.
[0021]
In the present invention, the solubilization reaction can be performed under supercritical conditions. In this case, the temperature in the solubilization tower is preferably 374 ° C. or more, the pressure is 22 MPa · G or more, and the liquid linear velocity (feed amount / reaction tower cross-sectional area) is preferably about 0.01 to 0.1 cm / sec. . When the solubilization reaction is performed under supercritical conditions, the solubilization of the solid organic matter can be further promoted.
[0022]
The amount of gas added to the object to be treated (liquid organic material) may be the minimum amount necessary for solubilization by reducing the molecular weight of the organic material. When an oxygen-containing gas is used, a gas containing 0.5 times or less of the theoretical oxygen amount defined below is used. If the amount of oxygen is too large, the organic matter in the liquid organic matter that will eventually become the fuel component may be excessively decomposed to carbon dioxide, water, etc., and the yield of the fuel gas will be reduced. The oxygen content in the gas is more preferably about 0.1 to 0.3 times the theoretical oxygen amount.
[0023]
For example, some liquid organic substances originating from biomass-based organic substances can progress well in the solubilization of organic components even in the absence of oxygen. Therefore, in the present invention, the reaction situation “containing oxygen not more than 0.5 times the theoretical oxygen amount” includes the case where oxygen is not supplied.
[0024]
Although the embodiment using air as an oxygen source has been described, the oxygen source is not particularly limited, and additionally contains one or more of oxygen-enriched air, oxygen, hydrogen peroxide, hydrocarbons and the like. Examples include oxygen-containing waste gas.
[0025]
In the present invention, the theoretical oxygen amount is defined as “an organic substance, an inorganic substance, a nitrogen compound, etc. (an ingredient to be treated) in the article to be treated is CO 22, H2O and N2This means the amount of oxygen required to perform such a complete decomposition ”. The theoretical oxygen amount can be easily determined by analyzing the components to be treated in the liquid organic material to be treated and calculating the theoretical oxygen amount necessary for their decomposition. Practically, it is possible to find a relational expression that can approximately calculate the theoretical oxygen amount with high accuracy using several parameters based on experience and some experiments. Such a relational expression is disclosed in, for example, Japanese Patent Publication No. 58-27999.
[0026]
In the solubilization tower 10, the organic matter is solubilized and liquefied, and the concentration of the inorganic matter is relatively increased, and this is discharged out of the solubilization tower as sludge. That is, a valve between a solubilizing tower and a sludge discharging apparatus (not shown; hereinafter simply referred to as “discharging apparatus”) whose pressure has been increased to the same pressure is opened to allow sludge to settle from the solubilizing tower 10 to the discharging apparatus. . When the sludge has sufficiently settled, the above valve is closed and the temperature is lowered naturally and the pressure is lowered, and then the valve provided on the outlet side of the discharge device is opened to discharge the sludge liquid out of the system. In addition, when the solubilization process is performed under supercritical conditions, the solubility of the metal is greatly reduced, so that sludge can be efficiently removed at this stage, and the life of the catalyst used in the subsequent methanation reaction can be increased. Can be extended.
[0027]
The sludge liquid can be subjected to a known solid-liquid separation process, and the separated liquid can be circulated to the storage tank 1 for processing. The sludge generated in the solubilization tower can be extracted semi-continuously and discharged by such a lock hopper system. Further, the metal component in the solubilized solution can be removed by a known method such as coagulation precipitation. Removal of metal components in the solubilization liquid and removal of sludge and / or metal components generated in the solubilization tower suppresses the adhesion of sludge and / or metal components to the catalyst in the subsequent methanation reactor, High catalytic activity can be maintained.
[0028]
The gas-liquid mixed phase formed in the solubilizing tower 10 is separated into a gas phase from the line 11 and a liquid phase from the line 14. O2, CO2The gas phase composed of water vapor and the like is taken out of the system, the power is recovered by the expansion turbine 12, and then discharged from the line 13 to the outside of the system. The high temperature / high pressure liquid phase containing the solubilizing component is sent to the methanation reaction tower 17 via the line 14, the heat exchanger 15 and the line 16.
[0029]
A part of the liquid phase obtained by the gas-liquid separation can be circulated and mixed with the liquid organic substance in the solubilization tower 10. This achieves effects such as prevention of sedimentation of solid organic matter in the solubilization tower, promotion of solubilization by mixing with an oxygen-containing gas, oxidation of metal components, and promotion of oxidation of sulfur oxides. The circulation amount of the liquid phase is preferably 5 times or more, more preferably 10 to 20 times the amount fed to the methanation reaction tower 17.
[0030]
Even in the methanation reaction, when a predetermined reaction temperature cannot be maintained, heating can be performed by a heater (not shown). Further, in order to bring the inside of the methanation reaction tower 17 to a predetermined temperature at start-up, the temperature is raised by circulating a high-temperature liquid phase from the solubilization tower 10, or steam is directly fed into the methanation reaction tower 17. Then, the temperature can be raised, or the temperature can be raised by a heater (not shown).
[0031]
The methanation reaction tower 17 is packed with a catalyst supported on a carrier.
[0032]
Examples of the catalytically active component include Ru, Pd, Rh, Pt, Ir, Ni, Co, Mn, and Ce and water-insoluble or poorly water-soluble compounds of these metals. These metals and their compounds may be used alone or in combination of two or more. These catalytically active components are used in a state of being supported on a known metal oxide support according to a conventional method. The metal oxide carrier is not particularly limited, and those used as a known catalyst carrier can be used. As the metal oxide support, zirconia, titania, alumina, silica, composite metal oxides containing these metal oxides (titania-zirconia, alumina-silica, alumina-silica-zirconia, etc.), these metal oxides or composite metal oxidation Examples thereof include metal oxide-based carriers mainly composed of an object. Among these carriers, zirconia, titania and titania-zirconia having excellent durability are more preferable.
[0033]
The shape of the supported catalyst is not particularly limited, and examples thereof include a spherical shape, a pellet shape, a cylindrical shape, a crushed piece shape, a powder shape, and a honeycomb shape. The volume of the methanation reaction column 17 in the case of using such a supported catalyst is as follows. In the case of a fixed bed, the liquid space velocity is 0.5 to 100 hr.-1Degree, more preferably 1-60 hr-1It is good to make it to the extent. The size of the supported catalyst used in the fixed bed is usually about 3 to 50 mm, more preferably about 5 to 25 mm in the case of a spherical shape, a pellet shape, a cylindrical shape, a crushed piece shape, a powder shape and the like. In addition, as a honeycomb structure when the catalyst is supported on a honeycomb-shaped carrier, an opening having an arbitrary shape such as a square, a hexagon, or a circle is used. The area per unit volume and the aperture ratio are not particularly limited, but the area per unit volume is usually 200 to 800 m.2/ mThreeUse an aperture ratio of about 40-80%. Examples of the material of the honeycomb structure include metal oxides and metals similar to those described above, and zirconia, titania and titania-zirconia having excellent durability are more preferable.
[0034]
In the case of forming a fluidized bed in the methanation reaction tower 17, the amount by which the supported catalyst can form a fluidized bed in the reactor, that is, about 0.01 to 10%, more preferably based on the weight of the normal liquid phase. About 0.1 to 3% is suspended in the liquid phase and used. When using a fluidized bed, the supported catalyst is supplied to the methanation reaction tower in a slurry state suspended in the liquid phase, and the catalyst is settled from the liquid phase discharged outside the methane reaction tower after the reaction is completed. Separate and collect by an appropriate method such as centrifugation, and reuse. Therefore, considering the ease of separation and recovery of the catalyst from the liquid phase, the particle size of the supported catalyst used in the fluidized bed is more preferably about 0.15 to 0.5 mm. The amount of the catalytically active metal supported is not particularly limited, but is usually in the range of about 0.01 to 25%, more preferably about 0.1 to 3% of the weight of the support.
[0035]
The reaction temperature in the methanation reaction tower 17 is 100 ° C. or higher. In addition, since the sludge and / or metal components contained in the object to be treated are efficiently removed in the solubilization tower 10, the activity of the catalyst packed in the methanation reaction tower may be inhibited. , Greatly suppressed.
[0036]
In the present invention, the methanation reaction can be performed under supercritical conditions. In this case, the temperature in the methanation reaction tower 17 is 374 ° C. or higher, the pressure is 22 MPa · G or more, and the liquid linear velocity (feeding liquid amount / reaction tower cross-sectional area) is about 0.1 to 1.0 cm / sec. Is preferred. When the methanation reaction is performed under supercritical conditions, the methanation can be performed more efficiently.
[0037]
The gas-liquid mixed phase after completion of the methanation reaction is subjected to heat recovery in the heat exchanger 15 via the line 18 and then sent to the gas-liquid separator 20 via the line 19 to be a high-pressure gas mainly composed of methane. Separated into gas and liquid phase. If necessary, the obtained liquid phase is heat-recovered by the heat exchanger 8 as a heating source of the liquid organic matter via the line 36, and then SO 2 derived from the sulfur compound via the line 37 and the line 39.Four 2-It is taken out of the system in a state that contains. This liquid phase can also be used as dilution water for the solid organic matter crushed material.
[0038]
On the other hand, if necessary, the high pressure gas is recovered through the line 21 and power is recovered by the expansion turbine (or reciprocating power recovery device) 22 and the like, and then the PSA, the separation permeable membrane or the alkaline liquid is cleaned through the line 23. It is subjected to decarboxylation by means such as the tower 24 and can be recovered from the line 33 as fuel. Furthermore, SNG can be obtained by sending the gas after decarboxylation to the calorimeter 34 and adding LPG or the like to increase the heat. These power recovery, decarboxylation and heat increase can be performed by known methods.
[0039]
When decarboxylation is performed using an alkaline cleaning liquid, the alkaline liquid from the absorption tower 24 is sent to the regeneration tower 25 via the line 29, the pump 30 and the line 31, and after performing the regeneration treatment, the line 26 and the pump 27 are used. And can be circulated to the absorption tower via line 28. The carbon dioxide removed by the alkali cleaning is discharged out of the system from the line 32.
[0040]
Furthermore, the inner surfaces of the piping and equipment used in the method of the present invention are washed with an acid aqueous solution (nitric acid, ascorbic acid, etc.) and / or an alkaline aqueous solution, or air-washed as necessary or periodically. You can also.
[0041]
【The invention's effect】
According to the method of the present invention, solid organic matter (waste and biomass) and / or liquid organic matter can be converted into useful fuel gas (SNG) with high energy conversion efficiency. Reduced.
[0042]
In addition, according to the method of the present invention, it is possible to reduce the amount of fossil fuel used while contributing to diversification of SNG production sources by reusing various wastes generated in large quantities as resources. It can greatly contribute to the preservation of the global environment.
[0043]
Furthermore, according to the method of the present invention, it is possible to effectively prevent the generation of harmful substances such as dioxin, which was the biggest problem of waste treatment according to the prior art. Can be eliminated or remarkably reduced.
[0044]
Furthermore, according to the method of the present invention, electric power, thermal energy, and the like can be recovered more efficiently and in a large amount as compared with a waste disposal method mainly using conventional incineration disposal.
[0045]
Furthermore, the presence of harmful components is substantially not observed in the gas phase after the gas-liquid separation of the solubilized tower outlet product.
[0046]
Moreover, the sludge formed in the solubilizing tower has excellent sedimentation properties, and can be easily removed and handled from the apparatus.
[0047]
According to the method of the present invention, each process is carried out continuously, and the processing flow is extremely simple. Therefore, the processing cost (equipment cost, operating cost, etc.) is remarkably reduced and process management is facilitated.
[0048]
【Example】
Examples and Comparative Examples are shown below to further clarify the features of the present invention.
Example 1
In accordance with the flow shown in FIG. 1, according to the present invention, a liquid organic material (composition is shown in Table 1) composed of a mixture of soot and sludge crushed by a disposer was treated.
[0049]
[Table 1]
[0050]
In other words, liquid organic matter is space velocity 2hr-1The theoretical oxygen amount (16.1 Nm) is supplied from the compressor 5 while being supplied to the solubilizing tower 10 on an empty column basis.Three/ kl), air equivalent to 0.1 times the amount was supplied.
[0051]
In the reaction, a liquid organic substance and air are introduced into the inlet side of the heat exchanger 5 and a mixture (raw material gas) of the liquid organic substance and air at the outlet side of the heat exchanger 5 (inlet side of the solubilization tower 10). The treated gas / liquid mixed phase from the methanation reaction tower 17 was sent to the heat exchanger 15 to exchange heat with the raw material gas / liquid mixture so that the temperature of the liquid mixture) was 250 ° C., and the temperature was adjusted. In the solubilization tower 10, the liquid organic substance was maintained at a temperature of 250 ° C. and a pressure of 7 MPa · G. The liquid linear velocity in the solubilization tower 10 was 0.063 cm / sec.
[0052]
The sludge and / or metal component formed in the solubilization tower 10 opens a first valve (not shown) provided in the lower part of the solubilization tower, and the sludge liquid in the solubilization tower is discharged into a sludge discharge device (see FIG. (Not shown), the first valve was closed and cooled, and then the second valve (not shown) provided at the lower portion of the sludge discharging device was opened to discharge the sludge liquid.
[0053]
The composition of the solubilized solution obtained is shown in Table 2.
[0054]
[Table 2]
[0055]
As a result of the solubilization treatment of the liquid mixture, about 10% of the carbon in the original organic matter is decomposed, and the solubilization tower gas phase side is CO.2Migrated as.
[0056]
Next, the solubilized solution was subjected to a space velocity of 3.0 hr.-1It was supplied to the methanation reaction tower (based on an empty tower) and subjected to wet methanation in the presence of a catalyst. The methanation reaction tower is packed with a spherical catalyst (diameter 4-6mm) in which 2% of the weight of the support is supported on a titania support, and the temperature and pressure inside it are almost the same as the solubilization tower. Held on. The liquid linear velocity in the methanation reaction tower was 0.57 cm / sec.
[0057]
Table 3 shows the composition of the liquid phase after gas-liquid separation of the gas-liquid mixture produced in the methanation reaction tower.
[0058]
[Table 3]
[0059]
On the other hand, the obtained gas phase composition is CHFour78% CO221%, H21% or less.
Example 2
In accordance with the flow shown in FIG. 1, according to the present invention, the liquid organic matter (having the composition shown in Table 4) composed of a mixture of soot crushed by a disposer, paper / plastic crushed by a crusher, and sludge is treated.
[0060]
[Table 4]
[0061]
That is, the space velocity of the liquid mixture is 2.0 hr.-1The theoretical oxygen amount (31.5 Nm) from the compressor while supplying to the solubilization tower (empty standard)Three/ kl), oxygen corresponding to 0.1 times the amount was supplied.
[0062]
In the reaction, liquid organic matter and air are introduced into the inlet side of the heat exchanger 8 and the temperature of the gas-liquid mixture at the outlet side of the heat exchanger (inlet side of the solubilization tower 10) is 270 ° C. The gas-liquid mixed phase produced from the methanation reaction tower 17 was sent to the heat exchanger 5 to exchange heat with the gas-liquid mixture, and the temperature was adjusted. The inside of the solubilization tower 10 was maintained at a temperature of 270 ° C. and a pressure of 8.4 MP · G by wet oxidative decomposition of a liquid organic substance. The liquid linear velocity in the solubilization tower 10 was 0.063 cm / sec.
[0063]
Sludge and / or metal components formed in the solubilization tower were discharged in the same manner as in Example 1.
[0064]
[Table 5]
[0065]
By the solubilization treatment of the liquid organic substance in the solubilization tower 10, about 10% of the carbon in the original organic substance is decomposed, and the solubilization tower in the gas phase side of the CO2Migrated as.
[0066]
Next, the solubilization treatment solution is subjected to a space velocity of 10 hours.-1It was supplied to the methanation reaction tower 17 on the basis of an empty tower and subjected to wet methanation treatment. The methanation reaction column 17 is filled with a spherical catalyst (diameter 4 to 6 mm) in which 2% of the support weight is supported on a titania support, and the internal temperature and pressure are set to 380 ° C. and 23 MPa. Increased. The liquid linear velocity in the methanation reaction tower 17 was 0.57 cm / sec.
[0067]
Table 6 shows the composition of the liquid phase after gas-liquid separation of the gas-liquid mixture generated in the methanation reaction tower 17.
[0068]
[Table 6]
[0069]
The composition of the obtained gas phase is CHFour76.5%, CO222.1%, H21.3%.
Example 3
Woody biomass (C: 48-50%, H: 5.7-6.2%, O: 44-46%, N: 0.08-0.13%) is pulverized to a particle size of about 100 μm and then dispersed in water. A liquid organic substance having a solid concentration of about 20% was formed.
[0070]
This liquid organic matter has a space velocity of 2.0 hr.-1(Empty standard), and was supplied to the solubilization tower 10 (250 ° C., pressure 4.9 MPa) at a liquidus velocity of 0.10 cm / sec. By solubilizing the liquid organic material, about 10% of the carbon in the original organic material is decomposed, and CO2Formed.
[0071]
Next, the solubilization treatment solution is subjected to a space velocity of 5 hours.-1It was supplied to the methanation reaction tower 17 on the basis of an empty tower and subjected to wet methanation treatment. The methanation reaction tower is filled with a spherical catalyst (diameter 4 to 6 mm) in which 2% of ruthenium is supported on a titania support, and the internal temperature and pressure are adjusted to 300 ° C. and 8.8 MPa. Increased. The liquid linear velocity in the methanation reaction tower 17 was 0.57 cm / sec.
[0072]
The gas composition after the final gas-liquid separation is CHFourAnd CO2Are about 50% each, H2Was 0.5% or less.
[0073]
From biomass, 230 NmThree/ ton (wet base) CHFourIs obtained, 1.5 × 10FiveA calorie of kcal / ton (wet base) was recovered.
Example 4
A pretreated material (calorific value 1800 kcal / kg) obtained by separating and removing metal, glass, etc. from general waste was crushed to about 1 mm, and then dispersed in water to form a liquid organic substance having a solid concentration of about 30%.
[0074]
This liquid organic matter has a space velocity of 10 hours.-1While supplying to the solubilizing tower 10 (250 ° C., pressure 26 MPa) at a liquidus velocity of 0.063 cm / sec (empty standard), oxygen corresponding to 0.1 times the theoretical oxygen amount was supplied from the compressor 5. By solubilizing the liquid organic material, about 10% of the carbon in the original organic material is decomposed, and CO2Formed.
[0075]
Next, the solubilization treatment solution is subjected to a space velocity of 25 hours.-1It was supplied to the methanation reaction tower 17 on the basis of an empty tower and subjected to wet methanation treatment. The methanation reaction tower is filled with a spherical catalyst (diameter 5-6mm) with 2% ruthenium supported on the titania support, and the internal temperature and pressure are increased to 380 ° C and 25MPa. It was. The liquid linear velocity in the methanation reaction tower 17 was 0.57 cm / sec.
[0076]
The gas composition after the final gas-liquid separation is CHFourAnd CO2Are about 50% each, H2Was 0.5% or less.
[0077]
98.7Nm from waste pre-treatmentThree/ ton (wet base) CHFourIs obtained, 2.5 × 10FourA calorie of kcal / ton (wet base) was recovered.
[Brief description of the drawings]
FIG. 1 is a flow sheet showing an outline of the present invention.
[Explanation of symbols]
1 ... Storage tank
3 ... Pump
5 ... Compressor
8 ... Heat exchanger
10 ... Solubilization tower
12 ... Expansion turbine
15 ... heat exchanger
17 ... Methanation reactor
20 ... Gas-liquid separator
22 ... Expansion turbine
24 ... Absorption tower
25 ... Regeneration tower
27 ... Pump
30 ... Pump
34 ... Calorie adjuster
50. Pretreatment device
70: Coarse crusher

Claims (11)

  1. (1) In the first reactor, the liquid organic substance contains oxygen in an amount of 0.1 to 0.3 times the theoretical oxygen amount while maintaining a temperature of 100 ° C. or higher and a pressure at which at least a part of the raw material maintains a liquid phase. A step of subjecting to heat / pressure treatment in the presence of gas, (2) a step of gas-liquid separation of the gas-liquid mixed phase formed in the step of (1), and (3) in the second reactor, While maintaining the separated liquid phase obtained in the step (2) at a temperature of 100 ° C. or higher and at least a part of which maintains the liquid phase, Ru , Pd , Rh , Pt , Ir , Ni , Co , Mn and The active ingredient is at least one selected from the group consisting of Ce and its water-insoluble or poorly water-soluble compounds, and at least one selected from the group consisting of titania, zirconia, titania - zirconia, alumina, silica and alumina - silica. In the presence of a supported catalyst, Method for producing fuel gas by catalyst decomposition, characterized in that it comprises the step of generating a gas mainly composed of methane gas.
  2. 2. The fuel gas according to claim 1, wherein the liquid organic material is at least one of an organic compound-containing liquid, a slurry composed of a solid organic matter crushed body and water, and a slurry composed of a solid organic matter crushed body, water and an organic compound-containing liquid. Manufacturing method.
  3. In the step (1), the temperature in the reactor is 374 ° C. or higher, the pressure is 22 MPa · G or higher, and the liquid linear velocity (feed amount / reaction tower cross-sectional area) in the reactor is 0.01 to 0.1 cm / The method for producing a fuel gas according to claim 1, which is sec.
  4. The method for producing fuel gas according to claim 1, wherein the sludge and / or metal component produced in step (1) is removed from the first reactor.
  5. The fuel gas according to claim 1, wherein a part of the separated liquid phase obtained in the step (2) is circulated and mixed with the liquid organic substance of the step (1), and the remainder of the separated liquid phase is fed to the step (3). Manufacturing method.
  6. 6. The method for producing fuel gas according to claim 5 , wherein the amount of liquid phase circulated in step (1) is at least five times the amount of liquid phase fed to step (3).
  7. The method for producing fuel gas according to claim 6 , wherein the amount of liquid phase circulated in step (1) is 10 to 20 times the amount of liquid phase fed to step (3).
  8. The method for producing fuel gas according to claim 1, wherein power is recovered from the gas phase after gas-liquid separation obtained in step (2).
  9. The method for producing fuel gas according to claim 4 , wherein the metal component is removed by subjecting the separated liquid phase fed to the step (3) to a coagulation sedimentation process in advance.
  10. In the step (3), the temperature in the reactor is 374 ° C. or higher, the pressure is 22 MPa · G or higher, and the liquid linear velocity (feed amount / reactor cross-sectional area) in the reactor is 0.1 to 1.0 cm / The method for producing a fuel gas according to claim 1, which is sec.
  11. In step (1), the oxygen supply gas, the manufacturing method of the fuel gas according to claim 1, oxidizing the sulfur compounds present in a liquid organic material.
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