JP4075281B2 - Method and apparatus for producing high calorie gas - Google Patents

Description

【００２０】
水の超臨界状態は表１より明らかなように３７４℃、２２．４ＭＰａ以上であるが、それより臨界温度や臨界圧の低い二酸化炭素や水素、一酸化炭素、メタン等を含む混合ガスの状態になると３７４℃、２２．４ＭＰａに達しなくとも水は超臨界状態を有するようになる。
水、水素、メタン及びＣＯ₂吸収体をそれぞれ分離する方法について説明する。
ガス化・ＣＯ₂固定化領域１４までの工程で生成した水、水素、メタン及びＣＯ₂吸収体はまずＣＯ₂吸収体を分離するため反応器１０に設けられた排出口２４より減圧弁３３を介して固気分離器３６に送られる。生成物は固気分離器３６でＣＯ₂吸収体と生成ガスとに分離される。次に生成ガスより水を水の超臨界点以下で凝縮させ水素、メタンを含む生成ガスのみにする。
【００２１】
本発明の第２の実施の形態を図２に基づいて説明する。図２において、図１と同一符号は同一構成要素を示す。この実施の形態の製造装置は、次の点が第１の実施の形態と相違する。即ち、反応器１０の他端には酸化剤２１を導入するための第１導入パイプ２３が貫通し、筒体１８の端部から僅かに筒体１８内部に入った部分燃焼領域１３まで延びて設けられる。また反応器１０の他端にはＣＯ₂吸収剤２２を導入するための第２導入パイプ４１が貫通し、筒体１８の端部から筒体１８内部に入ったガス化・ＣＯ₂固定化領域１４まで延びて設けられる。第１導入パイプ２３には、第２タンク２９に貯えられた酸化剤２１が第２ポンプ３１で圧送され、予熱器３２で加熱されて導入される。第２導入パイプ４１には、第３タンク４２に貯えられたＣＯ₂吸収剤２２が第３ポンプ４３で圧送され、予熱器４４で加熱されて導入される。上記以外の構成は第１の実施の形態と同様である。この製造装置による反応は図４に示される。
第１の実施の形態と比較して、第２の実施の形態ではガス化・ＣＯ₂固定化領域１４よりＣＯ₂吸収剤２２を添加するため、部分燃焼領域１３では高い効率でガス化反応及び部分燃焼によりＣＯ₂を発生する。
【００２２】
【発明の効果】
以上述べたように、本発明によれば、反応器内部を７〜２５ＭＰａの圧力にするとともに２００〜５００℃の原料処理領域に硫黄分を含む化石燃料と水酸化ナトリウム水溶液とガス化促進剤を混合した原料混合物を導入して化石燃料を活性化し、活性化した原料混合物を酸化剤とＣＯ₂吸収剤とともに部分燃焼領域に導入して原料混合物を部分燃焼して部分燃焼領域を８００〜１２００℃にし、１２００〜５００℃のガス化・ＣＯ₂固定化領域に部分燃焼物を導入して水素、メタン、水蒸気及び二酸化炭素を主成分とするガスを生成するとともに二酸化炭素を添加物中のＣＯ₂吸収剤で固定化し、部分燃焼領域及びガス化・ＣＯ₂固定化領域が原料処理領域への熱交換及び吸熱反応により冷却されるようにしたので、複雑なプロセスを要することなく、メタン及び水素ガスを主成分とする高カロリーガスを効率良く連続して製造することができる。また臨界点の差異を利用して分離器によりＣＯ₂を固定化し回収することができる。
【図面の簡単な説明】
【図１】本発明の第１実施の形態における高カロリーガス製造装置の構成図。
【図２】本発明の第２実施の形態における高カロリーガス製造装置の構成図。
【図３】本発明の第１実施の形態の高カロリーガスの製造工程を示す図。
【図４】本発明の第２実施の形態の高カロリーガスの製造工程を示す図。
【符号の説明】
１０ 反応器
１１ ヒータ
１２ 原料処理領域
１３ 部分燃焼領域
１４ ガス化・ＣＯ₂固定化領域
１６ 原料混合物
１７ 導入口
１８ 筒体
２１ 酸化剤
２２ ＣＯ₂吸収剤
２３ 第１導入パイプ
２４ 排出口
２７ 第１ポンプ
３１ 第２ポンプ
３３ 減圧弁
３６ 固気分離器
３９ 気液分離器
４１ 第２導入パイプ
４３ 第３ポンプ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method and apparatus for producing a high calorie gas mainly composed of hydrogen and methane from fossil fuels such as coal and heavy oil.
[0002]
[Prior art]
Coal and super heavy oil and other resources are expected to continue to play a role in petroleum alternative energy, but because of the large amount of carbon dioxide emissions per unit of calorific value and a large environmental impact, the use and efficiency are improved. Is a big issue. As a method for solving the above problems, a method of gasifying coal using a gasification furnace has been performed. Generally, when gasifying a fossil fuel typified by coal or the like, gas is produced by the following reaction formulas (1) to (3) by causing water vapor to act on carbon of the fossil fuel.
C + CO ₂ = 2CO (1)
_{C + H 2 O = CO +} H 2 ...... (2)
CO + H ₂ O = CO ₂ + H ₂ (3)
In the above formulas (1) and (2), since the reaction is an endothermic reaction, the reaction is accelerated by heating at a high temperature of 800 to 1800 ° C., and if necessary, the carbonaceous matter is completely obtained by using a catalyst. It is gasified.
[0003]
However, in the case of producing hydrogen gas by proceeding the reactions of the above formulas (1) to (3) in a gasification furnace, the water gas shift reaction based on the formula (3) does not proceed sufficiently, so that there is no unreacted product in the product. Carbon monoxide gas remains. Therefore, it is necessary to advance the reaction of the formula (3) through a shift converter using an expensive catalyst. In addition, since the raw fossil fuel contains several to ten and several percent ash, metal impurities, sulfur, nitrogen, etc., it is necessary to purify the product to remove these. Further, in the high temperature reaction, there are problems such as a part of the reaction apparatus being blocked by coke generated by the coking phenomenon, and an expensive heat-resistant material is required for the reaction apparatus. Furthermore, since carbon dioxide gas, which is a by-product, is difficult to recover, it is released into the atmosphere, which causes environmental problems.
[0004]
Therefore, a BTC method (Battelle Treated Coal method) for generating activated coal has been proposed. In this method, slurry is prepared by adding and mixing CaO and NaOH to finely pulverized coal, this slurry is treated at 250 ° C., and CaO is chemically bonded to coal through NaOH, followed by solid-liquid Separated to remove solids, which are washed and dried to produce activated coal. By using the coal produced by this BTC method as a coal gasification raw material, Ca chemically bonded to the coal acts as a catalyst to promote coal gasification and desulfurize the coal with Ca. be able to.
[0005]
[Problems to be solved by the invention]
However, since this BTC method is a batch process and is inferior in productivity, it is necessary to wash and dry the intermediate product before gasifying the coal, and the number of steps is complicated.
[0006]
An object of the present invention is to provide a method and an apparatus for efficiently and continuously producing a high calorie gas mainly composed of hydrogen and methane without requiring a complicated process.
Another object of the present invention is to provide a method for producing high-calorie gas and an apparatus therefor, in which carbon dioxide is immobilized and recovered without being released into the atmosphere.
Still another object of the present invention is to provide a continuous and small high-calorie gas production apparatus with high thermal efficiency.
[0007]
[Means for Solving the Problems]
As shown in FIG. 1, the invention according to claim 1 is a fossil fuel containing a sulfur content in a raw material processing region 12 at 200 to 500 ° C. inside the reactor 10 while the inside of the reactor 10 is set to a pressure of 7 to 25 MPa. The step of activating the fossil fuel by introducing the raw material mixture 16 in which the sodium hydroxide aqueous solution and the gasification accelerator are mixed, and the raw material mixture 16 containing the fossil fuel activated in the raw material processing region 12 are converted into the oxidant 21 and CO _2. Introducing into the partial combustion region 13 inside the reactor 10 together with the absorbent 22 to partially burn the fossil fuel to bring the partial combustion region 13 to 800-1200 ° C., and 1200 following the partial combustion region 13 inside the reactor 10 A partial combustion product is introduced into the gasification / CO ₂ fixation region 14 at ˜500 ° C. to generate a gas mainly composed of hydrogen, methane, water vapor and carbon dioxide, and carbon dioxide is contained in the additive. A step of fixing with a CO ₂ absorbent 22, a step of discharging a reaction product comprising a gas mainly composed of hydrogen, methane, and water vapor and a CO ₂ absorber from an outlet 24 of the reactor 10, and a reactor A step of separating the CO ₂ absorber from the reaction product discharged from 10 by a solid-gas separator 36 and taking out a gas mainly composed of hydrogen, methane and water vapor; A process for producing a high-calorie gas comprising a step of lowering the temperature of the gas to 50 to 150 ° C. to liquefy and separate water vapor to obtain a gas mainly composed of hydrogen and methane.
[0008]
As shown in FIG. 2, the invention according to claim 2 is a fossil fuel containing a sulfur content in the raw material processing region 12 at 200 to 500 ° C. inside the reactor 10 while making the pressure inside the reactor 10 be 7 to 25 MPa. A step of activating a fossil fuel by introducing a raw material mixture 16 in which an aqueous sodium hydroxide solution and a gasification accelerator are mixed, and a reactor containing the raw material mixture 16 containing the fossil fuel activated in the raw material processing region 12 together with an oxidant 21 10 is introduced into the partial combustion region 13 inside the reactor 10 to partially burn the fossil fuel to bring the partial combustion region 13 to 800-1200 ° C., and gasification at 1200-500 ° C. following the partial combustion region 13 inside the reactor 10. A partial combustion product is introduced into the CO ₂ fixing region 14 together with the CO ₂ absorbent 22 to generate a gas mainly composed of hydrogen, methane, and carbon dioxide, and carbon dioxide is contained in the additive. A step of fixing with a CO ₂ absorbent 22, a step of discharging a reaction product comprising a gas mainly composed of hydrogen, methane, and water vapor and a CO ₂ absorber from an outlet 24 of the reactor 10; The step of separating the CO ₂ absorber from the reaction product discharged from the solid gas separator 36 and taking out the gas mainly composed of hydrogen, methane and water vapor, and taking the extracted hydrogen, methane and water vapor as the main components A method for producing a high-calorie gas comprising a step of lowering the gas temperature to 50 to 150 ° C. to liquefy and separate water vapor to obtain a gas mainly composed of hydrogen and methane.
[0009]
In the invention according to claim 1 or 2, as shown in FIGS. 1 to 4, the raw material mixture is chemically bonded to the functional group of the raw material with the alkali metal or alkaline earth metal in the gasification accelerator in the raw material processing region. Gasification is promoted to partially burn the oxidant and the raw material mixture in the partial combustion region, and gasification reaction is performed in the gasification / CO ₂ fixation region to generate hydrogen and carbon dioxide. Carbon dioxide is absorbed and fixed with a CO ₂ absorbent and solidified. By treating the fossil fuel in these steps, CO ₂ and sulfur can be recovered as a solid, and a high calorie gas composed of hydrogen and methane can be efficiently produced.
[0010]
The invention according to claim 3 is the invention according to claim 1 or 2, and the invention according to claim 7 is the invention according to claim 5 or 6, wherein the raw material treatment region 12 is the partial combustion region 13 and In this manufacturing method, heat exchange is performed with the gasification / CO ₂ fixation region 14. The invention according to claim 3 or 7, the heat energy for heating the raw material processing region 12 the portion combustion region 13 and heat generated in the gasification · CO ₂ immobilization region 14 is transmitted to the raw material processing region 12 through the tubular body Can be reduced.
[0011]
The invention according to claim 4 is the invention according to claim 1 or 2, wherein the invention according to claim 8 is the invention according to claim 5 or 6, wherein the gasification accelerator is an alkali metal or alkaline earth. The production method is a metal oxide, alkali metal or alkaline earth metal hydroxide, or alkali metal or alkaline earth metal carbonate, or a mixture thereof.
In the invention according to claim 4 or 8, by adding a gasification accelerator to the raw material, the water gasification reaction of the formula (2) and the water gas shift reaction of the formula (3) are performed more efficiently, More gas mainly composed of hydrogen gas and carbon dioxide gas is generated.
[0012]
As shown in FIG. 1, the invention according to claim 5 includes a tubular reactor 10 that is sealed at both ends and configured to maintain a supercritical state of water, and a reactor provided on the outer periphery of the reactor 10. A heater 11 that keeps or heats 10 is provided inside the reactor 10, concentrically with the reactor 10, with the tip closely attached to one end of the reactor 10, and the other end and the base end of the reactor 10 separated from each other. A fossil fuel, a sodium hydroxide aqueous solution, and a gas are provided in a raw material processing region 12 provided at one end of the reactor 10 and surrounded by the inner surface of the reactor 10 and the outer surface of the cylinder 18. An introduction port 17 for introducing the raw material mixture 16 mixed with the chemical accelerator, a first pump 27 for feeding the raw material mixture 16 to the introduction port 17 at a pressure of 7 to 25 MPa, and a cylinder on the other end side of the reactor 10. The first extending in the partial combustion region 13 inside the body 18 is provided. The inlet pipe 23, followed by an oxidizing agent 21 and CO ₂ absorbent 22 and the second pump 31 for pumping at a pressure of 7~25MPa the first introduction pipe 23, the partial combustion region 13 provided at one end of the reactor 10 cylinder A discharge port 24 for discharging the reaction product that has passed through the gasification / CO ₂ fixation region 14 inside the body 18, a pressure reducing valve 33 for reducing the pressure of the reaction product discharged from the reactor 10, and a reaction product A solid-gas separator 36 that separates the CO ₂ absorber from the reaction product by reducing the pressure and lowering the temperature of the reaction product to extract a gas mainly composed of hydrogen, methane, and water vapor; High-calorie equipped with a gas-liquid separator 39 that lowers the temperature of the gas mainly composed of hydrogen, methane, and water vapor extracted from the gas, liquefies and separates the water vapor, and extracts the gas mainly composed of hydrogen and methane This is a gas production device.
In the invention according to claim 5, by using the production apparatus having such a structure, carbon dioxide is solidified and recovered, and high-calorie gas mainly composed of methane and hydrogen can be produced efficiently and continuously. it can.
[0013]
As shown in FIG. 2, the invention according to claim 6 includes a tubular reactor 10 that is sealed at both ends and configured to maintain a supercritical state of water, and a reactor provided on the outer periphery of the reactor 10. A heater 11 that keeps or heats 10 is provided inside the reactor 10, concentrically with the reactor 10, with the tip closely attached to one end of the reactor 10, and the other end and the base end of the reactor 10 separated from each other. A fossil fuel, a sodium hydroxide aqueous solution, and a gas are provided in a raw material processing region 12 provided at one end of the reactor 10 and surrounded by the inner surface of the reactor 10 and the outer surface of the cylinder 18. An introduction port 17 for introducing the raw material mixture 16 mixed with the chemical accelerator, a first pump 27 for feeding the raw material mixture 16 to the introduction port 17 at a pressure of 7 to 25 MPa, and a cylinder on the other end side of the reactor 10. The first extending in the partial combustion region 13 inside the body 18 is provided. The inlet pipe 23, the second introduction pipe 41 provided extending in the cylindrical body 18 inside the gasification · CO ₂ immobilization region 14 following the partial combustion region 13, 7 to the oxidizer 21 to the first introduction pipe 23 A second pump 31 that pumps at a pressure of 25 MPa, a third pump 43 that pumps the CO ₂ absorbent 22 to the second introduction pipe 41 at a pressure of 7 to 25 MPa, and a partial combustion region 13 provided at one end of the reactor 10. A discharge port 24 for discharging the reaction product that has passed through the gasification / CO ₂ fixation region 14 inside the cylinder 18, a pressure reducing valve 33 for reducing the pressure of the reaction product discharged from the reactor 10, and a reaction A solid-gas separator 36 for reducing the pressure of the product and lowering the temperature of the reaction product to separate the CO ₂ absorber from the reaction product to extract a gas mainly composed of hydrogen, methane, and water vapor; Hydrogen extracted from separator 36 and A high-calorie gas production apparatus comprising a gas-liquid separator 39 that lowers the temperature of a gas mainly composed of methane and water vapor, liquefies and separates water vapor, and takes out a gas mainly composed of hydrogen and methane. .
In the invention according to claim 6, since the CO ₂ absorbent 22 is added from the gasification / CO ₂ fixing region 14 as compared with the invention according to claim 5, the partial combustion region 13 has high efficiency in the gasification reaction and CO ₂ can be generated by partial combustion.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The fossil fuel used as a raw material in the present invention includes coal, heavy oil, coal coke obtained by pyrolyzing these, petroleum coke, or a powdery solid rich in carbon produced when coal is pyrolyzed at a high temperature. (Char). Examples of coal include grass charcoal, lignite, subbituminous coal, bituminous coal, and anthracite. The fossil fuel treated in the present invention contains a sulfur content. This fossil fuel is introduced into the reactor as a raw material mixture in which an aqueous sodium hydroxide solution and a gasification accelerator are mixed. Depending on the type of fossil fuel and its micro characteristics, the mixing of the sodium hydroxide aqueous solution and the gasification accelerator can be omitted. The addition ratio of sodium hydroxide and gasification accelerator to fossil fuel is preferably 5 to 20% by weight of sodium hydroxide and 5 to 30% by weight of gasification accelerator with respect to 100% by weight of fossil fuel. .
[0015]
Examples of the gasification accelerator include oxides, hydroxides and carbonates of alkali metals such as potassium and sodium, and oxides, hydroxides and carbonates of alkaline earth metals such as magnesium and calcium. The gasification accelerator may be a mixture thereof. When the fossil fuel is coal, the younger the coal, the more gasification promoter needs to be added. For example, in the case of subbituminous coal, 5% of the gasification promoter containing alkali metal is 100% by weight of coal. The gasification promoter containing alkaline earth metal is preferably about 5 to 20% by weight.
Examples of the oxidizing agent include oxygen and hydrogen peroxide water. Furthermore, examples of the CO ₂ absorbent include oxides and hydroxides of alkali metals such as potassium and sodium, and oxides and hydroxides of alkaline earth metals such as magnesium and calcium. These CO ₂ absorbents react with CO ₂ to form carbonates (CO ₂ absorbers).
The fossil fuel is preferably in the form of a slurry or an emulsion in order to suppress the coking phenomenon. When the fossil fuel is a solid such as coal, it is prepared into a slurry in which coal powder and water are mixed. When the fossil fuel is a liquid such as heavy oil, the heavy oil and water are mixed. Prepared into an emulsion.
[0016]
A first embodiment of the present invention will be described with reference to the drawings.
In the production apparatus of the present invention, as shown in FIG. 1, the reactor 10 is formed in a tubular shape that is sealed at both ends and configured to maintain a supercritical state of water. A heater 11 for heat insulation or heating is provided on the outer peripheral portion of the reactor 10, and a raw material processing region 12 is provided on the inner peripheral portion. A partial combustion region 13 is provided at the center of the reactor 10, and a gasification / CO ₂ fixation region 14 is provided at the center of the reactor 10 following the partial combustion region 13. One end of the reactor 10 is provided with an introduction port 17 for introducing a raw material mixture 16 leading to the raw material processing region 12. The raw material processing region 12 and the partial combustion region 13 are partitioned by a cylindrical body 18 of a heat-resistant metal made of a cylindrical heat good conductor, for example, a heat-resistant alloy of Ni—Cr. The cylindrical body 18 is in close contact with one end of the reactor 10 and is provided at a distance from the inner wall of the other end of the reactor 10. This interval constitutes a communication portion 19 that communicates the raw material treatment region 12 and the partial combustion region 13, and the fluid subjected to the heat treatment flows into the partial combustion region 13 from this portion. Since this cylindrical body 18 is exposed to high temperature and there exists a possibility that corrosion may become large, it is comprised so that replacement | exchange is possible. Further, a first introduction pipe 23 for introducing the oxidant 21 and the CO ₂ absorbent 22 into the other end of the reactor 10 passes through the other end of the reactor 10 and slightly from the end of the cylinder body 18. It extends to the partial combustion region 13 that enters the body 18. The other end of the reactor 10 is provided with a discharge port 24 for discharging a fluid composed of hydrogen, methane, a CO ₂ absorber and supercritical water converted in the gasification / CO ₂ fixing region 14. The slurry-like raw material mixture 16 stored in the first tank 26 is pumped by the first pump 27 and introduced into the introduction port 17 of the raw material mixture 16 via the preheater 28. The oxidant 21 and the CO ₂ absorbent 22 stored in the second tank 29 are pumped to the first introduction pipe 23 by the second pump 31 and heated and introduced by the preheater 32. The discharge port 24 is connected to the introduction port 36 a of the solid-gas separator 36 through the intermediate pipe 34. A pressure reducing valve 33 is provided in the middle of the intermediate pipe 34. The discharge port 36b of the solid-gas separator 36 is connected via an intermediate pipe 38 to an introduction port 39a of a gas-liquid separator 39 that separates hydrogen, methane and water. An open / close valve 37 is provided in the middle of the intermediate pipe 38. A discharge port 40 for discharging hydrogen and methane is connected to the discharge port 39b of the gas-liquid separator 39, and an open / close valve 41 is provided in the middle thereof.
[0017]
A case where coal is used as a fossil fuel for the reaction by the manufacturing apparatus configured as described above will be described with reference to FIGS.
(a) Raw material processing region A raw material mixture 16 composed of coal, sodium hydroxide aqueous solution, gasification accelerator and water is fed from the first tank 26 through the first pump 27 and the preheater 28 to the raw material processing region 12. To introduce. The raw material processing region 12 is maintained at a temperature of 200 to 500 ° C. and a pressure of 7 to 25 MPa by the pump 27, the preheater 28 and the heater 11. If it is less than 200 ° C. or less than 7 MPa, chemical bonding between the coal and the gasifying agent is not promoted, and if it exceeds 500 ° C., the coal is polymerized before chemical bonding with the gasifying agent. The temperature and pressure are preferably 200 to 300 ° C. and 15 to 25 MPa, respectively. Under the above temperature and pressure, Na of sodium hydroxide in the raw material mixture is replaced with each hydrogen atom of the OH group or COOH group which is a functional group of coal, and the coal is denatured so that the gasification rate is increased.
(b) The raw material mixture 16 processed through the partial combustion region raw material processing region 12 flows into the partial combustion region 13 through the communication portion 19. Here, the oxidant 21 and the CO ₂ absorbent 22 are introduced from the second tank 29 into the partial combustion region 13 through the second pump 31 and the preheater 32 through the first introduction pipe 23. Part of the oxidant 21 and the treated raw material mixture 16 is combusted, and the partial combustion region 13 is heated to a high temperature of 800 to 1200 ° C. by the combustion heat. As a result, the entire region 13 becomes a temperature condition that promotes gasification. The pressure is the same as the raw material processing area. This partial combustion region 13 exchanges heat with the raw material processing region 12 via the cylindrical body 18.
(c) Gasification / CO ₂ fixation region In this region 14, a gasification reaction mainly consisting of residues proceeds, and hydrogen and carbon dioxide are generated. Further, carbon dioxide generated by the partial combustion region 13 and the gasification reaction reacts with the CO ₂ absorbent 22 introduced in the partial combustion region 13, and the carbon dioxide becomes a CO ₂ absorber and is separated from the generated gas. As a result, a high calorie gas composed of hydrogen and methane is purified. For example in the case of using the CaO in CO ₂ absorbent, CaCO ₃ is obtained as a CO ₂ absorber. Since the CO ₂ absorbent also functions as a gasification accelerator, the gasification rate can be increased. Sulfur contained in the raw material is also absorbed by the CO ₂ absorbent 22 and can be recovered as a sulfur absorber in the same manner as the CO ₂ absorbent.
[0018]
The temperature of the gasification / CO ₂ fixation region 14 is cooled by heat exchange with the raw material treatment region 12 through the endothermic reaction and the cylindrical body 18, and becomes 1200 to 500 ° C. lower than that of the partial combustion region 13. The pressure is the same as the raw material processing area. If the pressure is 7 to 25 MPa, 900 ° C. or less, which is a temperature range in which the CO ₂ absorbent can react, is preferable. Under these conditions, Na becomes Na ₂ CO ₃ , Ca becomes CaCO ₃ , and CO ₂ is absorbed and immobilized. Above this temperature, the absorption of CO ₂ decreases and takes another stable chemical form. Table 1 below shows supercritical points such as carbon dioxide, hydrogen, carbon monoxide, and methane mainly existing in the reactor 10.
[0019]
[Table 1]

[0020]
As is clear from Table 1, the supercritical state of water is 374 ° C. and 22.4 MPa or more, but the state of the mixed gas containing carbon dioxide, hydrogen, carbon monoxide, methane, etc. having a lower critical temperature or critical pressure. Then, even if 374 ° C. and 22.4 MPa are not reached, water has a supercritical state.
A method for separating water, hydrogen, methane and CO ₂ absorber will be described.
The water, hydrogen, methane, and CO ₂ absorbers produced in the process up to the gasification / CO ₂ fixation region 14 are first separated from the CO ₂ absorber by a pressure reducing valve 33 from the outlet 24 provided in the reactor 10. To the solid-gas separator 36. The product is separated into a CO ₂ absorber and product gas by a solid-gas separator 36. Next, water is condensed from the product gas below the supercritical point of water so that only the product gas containing hydrogen and methane is contained.
[0021]
A second embodiment of the present invention will be described with reference to FIG. 2, the same reference numerals as those in FIG. 1 denote the same components. The manufacturing apparatus of this embodiment is different from the first embodiment in the following points. That is, the first introduction pipe 23 for introducing the oxidant 21 passes through the other end of the reactor 10, and extends from the end of the cylinder 18 to the partial combustion region 13 slightly inside the cylinder 18. Provided. Further, a second introduction pipe 41 for introducing the CO ₂ absorbent 22 passes through the other end of the reactor 10, and a gasification / CO ₂ fixation region entering the inside of the cylinder 18 from the end of the cylinder 18. 14 is provided. The oxidant 21 stored in the second tank 29 is pumped into the first introduction pipe 23 by the second pump 31 and is heated and introduced by the preheater 32. The CO ₂ absorbent 22 stored in the third tank 42 is pumped into the second introduction pipe 41 by the third pump 43 and heated and introduced by the preheater 44. The configuration other than the above is the same as that of the first embodiment. The reaction by this production apparatus is shown in FIG.
Compared to the first embodiment, in the second embodiment, since the CO ₂ absorbent 22 is added from the gasification / CO ₂ fixing region 14, the gasification reaction and the partial combustion region 13 are more efficiently performed. CO ₂ is generated by partial combustion.
[0022]
【The invention's effect】
As described above, according to the present invention, the pressure inside the reactor is set to 7 to 25 MPa, and the fossil fuel containing the sulfur content in the raw material treatment region at 200 to 500 ° C., the sodium hydroxide aqueous solution, and the gasification accelerator are added. The mixed raw material mixture is introduced to activate the fossil fuel, the activated raw material mixture is introduced into the partial combustion region together with the oxidant and the CO ₂ absorbent, and the raw material mixture is partially burned to make the partial combustion region 800 to 1200 ° C. The partial combustion product is introduced into the gasification / CO ₂ fixing region at 1200 to 500 ° C. to generate a gas mainly composed of hydrogen, methane, water vapor and carbon dioxide, and carbon dioxide is added to CO ₂ in the additive. immobilized in the absorbent, since the partial combustion region and gasification · CO ₂ immobilization region is to be cooled by the heat exchanger and endothermic reactions to material processing area, this requires a complicated process No, it is possible to produce a high-calorie gas composed mainly of methane and hydrogen gas efficiently and continuously. Further, CO ₂ can be fixed and recovered by a separator using the difference in critical points.
[Brief description of the drawings]
FIG. 1 is a configuration diagram of a high calorie gas production apparatus according to a first embodiment of the present invention.
FIG. 2 is a configuration diagram of a high calorie gas production apparatus according to a second embodiment of the present invention.
FIG. 3 is a diagram showing a production process of high calorie gas according to the first embodiment of the present invention.
FIG. 4 is a diagram showing a production process of high calorie gas according to a second embodiment of the present invention.
[Explanation of symbols]
10 reactor 11 heater 12 feed processing region 13 partial combustion zone 14 gasification · CO ₂ immobilization region 16 starting mixture 17 inlet 18 the tubular body 21 oxidizer 22 CO ₂ absorber 23 first inlet pipe 24 discharge outlet 27 first Pump 31 Second pump 33 Pressure reducing valve 36 Gas-solid separator 39 Gas-liquid separator 41 Second introduction pipe 43 Third pump

Claims (8)

Fossil fuel containing sodium content, sodium hydroxide aqueous solution, and gasification promotion in the reactor (10) with a pressure of 7 to 25 MPa and a raw material treatment region (12) of 200 to 500 ° C. inside the reactor (10) Introducing the raw material mixture (16) mixed with the agent to activate the fossil fuel; and
The raw material mixture (16) containing the fossil fuel activated in the raw material treatment region (12), together with an oxidant (21) and a CO ₂ absorbent (22), a partial combustion region (13) inside the reactor (10). And partially burning the fossil fuel to bring the partial combustion region (13) to 800 to 1200 ° C .;
Partial combustion products are introduced into a gasification / CO ₂ fixation region (14) at 1200 to 500 ° C. following the partial combustion region (13) inside the reactor (10) to mainly contain hydrogen, methane, steam and carbon dioxide. Producing a gas as a component and immobilizing the carbon dioxide with the CO ₂ absorbent (22);
Discharging a reaction product comprising a gas mainly composed of hydrogen, methane, and water vapor and a CO ₂ absorber from an outlet (24) of the reactor (10);
Separating the CO ₂ absorber from a reaction product discharged from the reactor (10) by a solid-gas separator (36) and taking out a gas mainly composed of hydrogen, methane and water vapor;
A step of reducing the temperature of the extracted hydrogen, methane and water vapor-based gas as a main component to 50 to 150 ° C., and liquefying and separating the water vapor to obtain a gas containing hydrogen and methane as main components. Gas production method. Fossil fuel containing sodium content, sodium hydroxide aqueous solution, and gasification promotion in the reactor (10) with a pressure of 7 to 25 MPa and a raw material treatment region (12) of 200 to 500 ° C. inside the reactor (10) Introducing the raw material mixture (16) mixed with the agent to activate the fossil fuel; and
The fossil fuel is introduced by introducing the raw material mixture (16) containing the fossil fuel activated in the raw material treatment region (12) into the partial combustion region (13) inside the reactor (10) together with the oxidant (21). Partial combustion to bring the partial combustion region (13) to 800-1200 ° C;
Hydrogen is obtained by introducing a partial combustion product together with a CO ₂ absorbent (22) into a gasification / CO ₂ fixation region (14) at 1200 to 500 ° C. following the partial combustion region (13) inside the reactor (10). Producing a gas mainly composed of methane and carbon dioxide and fixing the carbon dioxide with the CO ₂ absorbent (22);
Discharging a reaction product comprising a gas mainly composed of hydrogen, methane, and water vapor and a CO ₂ absorber from an outlet (24) of the reactor (10);
Separating the CO ₂ absorber from a reaction product discharged from the reactor (10) by a solid-gas separator (36) and taking out a gas mainly composed of hydrogen, methane and water vapor;
A step of reducing the temperature of the extracted hydrogen, methane and water vapor-based gas as a main component to 50 to 150 ° C., and liquefying and separating the water vapor to obtain a gas containing hydrogen and methane as main components. Gas production method. The manufacturing method according to claim 1 or 2, wherein the raw material treatment area (12) exchanges heat with the partial combustion area (13) and the gasification / CO ₂ fixation area (14). The gasification accelerator is an alkali metal or alkaline earth metal oxide, an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal carbonate, or a mixture thereof. 2. The production method according to 2. A tubular reactor (10) that is sealed at both ends and configured to maintain a supercritical state of water;
A heater (11) provided on the outer periphery of the reactor (10) for keeping or heating the reactor (10);
Provided inside the reactor (10) concentrically with the reactor (10), with the tip closely attached to one end of the reactor (10) and the other end and the base end of the reactor (10) being spaced apart A cylindrical body (18) having a good thermal conductivity and heat resistance,
A fossil fuel, an aqueous sodium hydroxide solution, and a gasification accelerator are provided in a raw material processing region (12) provided at one end of the reactor (10) and surrounded by the inner surface of the reactor (10) and the outer surface of the cylinder (18). An inlet (17) for introducing a raw material mixture (16) mixed with
A first pump (27) for pumping the raw material mixture (16) to the inlet (17) at a pressure of 7 to 25 MPa;
A first introduction pipe (23) provided extending to a partial combustion region (13) inside the cylindrical body (18) on the other end side of the reactor (10);
A second pump (31) for pumping the oxidizing agent (21) and the CO ₂ absorbent (22) to the first introduction pipe (23) at a pressure of 7 to 25 MPa;
An exhaust port for discharging reaction products that are provided at one end of the reactor (10) and that pass through the gasification / CO ₂ fixation region (14) inside the cylindrical body (18) following the partial combustion region (13) (24) and
A pressure reducing valve (33) for reducing the pressure of the reaction product discharged from the reactor (10);
A solid-gas separator that reduces the pressure of the reaction product and lowers the temperature of the reaction product to separate a CO ₂ absorber from the reaction product and extract a gas mainly composed of hydrogen, methane, and water vapor ( 36) and
Gas-liquid separation that lowers the temperature of the gas mainly composed of hydrogen, methane, and water vapor extracted from the solid-gas separator (36), liquefies and separates the water vapor, and removes the gas mainly composed of hydrogen and methane A device for producing high calorie gas comprising a vessel (39). A tubular reactor (10) that is sealed at both ends and configured to maintain a supercritical state of water;
A heater (11) provided on the outer periphery of the reactor (10) for keeping or heating the reactor (10);
Provided inside the reactor (10) concentrically with the reactor (10), with the tip closely attached to one end of the reactor (10) and the other end and the base end of the reactor (10) being spaced apart A cylindrical body (18) having a good thermal conductivity and heat resistance,
A fossil fuel, an aqueous sodium hydroxide solution, and a gasification accelerator are provided in a raw material processing region (12) provided at one end of the reactor (10) and surrounded by the inner surface of the reactor (10) and the outer surface of the cylinder (18). An inlet (17) for introducing a raw material mixture (16) mixed with
A first pump (27) for pumping the raw material mixture to the inlet (17) at a pressure of 7 to 25 MPa;
A first introduction pipe (23) provided extending to a partial combustion region (13) inside the cylindrical body (18) on the other end side of the reactor (10);
A second introduction pipe (41) provided extending to the gasification / CO ₂ fixation region (14) inside the cylindrical body (18) following the partial combustion region (13);
A second pump (31) for pumping the oxidizing agent (21) to the first introduction pipe (23) at a pressure of 7 to 25 MPa;
A third pump (43) for pumping the CO ₂ absorbent (22) to the second introduction pipe (41) at a pressure of 7 to 25 MPa;
An exhaust port for discharging reaction products that are provided at one end of the reactor (10) and that pass through the gasification / CO ₂ fixation region (14) inside the cylindrical body (18) following the partial combustion region (13) (24) and
A pressure reducing valve (33) for reducing the pressure of the reaction product discharged from the reactor (10);
A solid-gas separator that reduces the pressure of the reaction product and lowers the temperature of the reaction product to separate a CO ₂ absorber from the reaction product and extract a gas mainly composed of hydrogen, methane, and water vapor ( 36) and
Gas-liquid separation that lowers the temperature of the gas mainly composed of hydrogen, methane, and water vapor extracted from the solid-gas separator (36), liquefies and separates the water vapor, and removes the gas mainly composed of hydrogen and methane A device for producing high calorie gas comprising a vessel (39). The manufacturing apparatus according to claim 5 or 6, wherein the raw material treatment area (12) exchanges heat with the partial combustion area (13) and the gasification / CO ₂ fixation area (14). The gasification accelerator is an alkali metal or alkaline earth metal oxide, an alkali metal or alkaline earth metal hydroxide, an alkali metal or alkaline earth metal carbonate, or a mixture thereof. 6. The manufacturing apparatus according to 6.

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