JP2009298616A - Apparatus and method for reforming glycerol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus and a method for reforming glycerol capable of reforming glycerol with high energy utilization efficiency and converting into a valuable gas. <P>SOLUTION: The apparatus for reforming glycerol 1 is equipped with a reforming reactor 2 which retains a catalyst in its inside and reforms glycerol by generating a steam-reforming reaction using the catalyst between glycerol and a gas for reaction at least containing steam, a cooling-heat recovering unit 7 which collects heat from reformed gas by cooling reformed gas generated after the steam-reforming reaction and a combustor 6 for generating combustion exhaust gas by combusting fuel, and is composed to heat the inside of the reforming reactor 2 by the heat of combustion exhaust gas obtained from the combustor 6. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a glycerin reforming apparatus and a reforming method, for example, an apparatus and a method for reforming glycerin, which is a by-product when producing biodiesel fuel from vegetable oil or the like, into valuable resources.

  In recent years, a method for producing biodiesel fuel using vegetable oils such as soybean oil, rapeseed oil and sunflower oil as a raw material has been proposed. As a general production method of biodiesel fuel, methanol and an alkali catalyst are added to fats and oils to cause a transesterification reaction, and then an acid is added to neutralize the oils and separated into fatty acid methyl esters and glycerin. When the catalyst is removed from the separated fatty acid methyl ester and methanol is further removed, biodiesel fuel is obtained. Thus, in the method using an alkali catalyst, it is difficult in principle to suppress the generation of glycerin, and about 10% of glycerin of the raw material fat is by-produced.

  Glycerin is currently consumed in fields such as pharmaceuticals, cosmetics, resins, and paints, but its consumption is limited. On the other hand, it is predicted that by-product glycerin will become surplus with the increase in production of biodiesel fuel, which is expected as a countermeasure against global warming. At present, most of the by-product glycerin is heat recovered by incineration. In the background of the by-product glycerin, the surplus amount of glycerin is increasing more and the utility value of resources is reduced by incineration.

Thus, Patent Document 1 below discloses a waste treatment system including a hydrogen gas generation device that generates hydrogen gas by heating and vaporizing crude glycerin by-produced and purified glycerin obtained by further purifying the crude glycerin. According to Patent Document 1, it is described that by using this waste treatment system, biodiesel fuel can be produced, hydrogen gas can be generated from by-product glycerin, and it can be effectively used as a hydrogen fuel cell.
JP 2004-209415 A

  However, Patent Document 1 only describes a hydrogen gas generator that heats and vaporizes glycerin to generate hydrogen gas, and does not describe a specific configuration of the hydrogen gas generator. Therefore, it is desired to provide a specific apparatus and method for reforming glycerin and converting it into valuable gas.

  Furthermore, Patent Document 1 discloses a reduction in electric power by utilizing the exhaust heat of a reductive gasification melting furnace that melts the remainder of the waste containing fats and oils at a high temperature as a heat source used for heating and vaporizing glycerin in the hydrogen gas generator. It is described that it is possible. However, this is an effect obtained as a whole biodiesel fuel production system in which a reductive gasification melting furnace and a hydrogen gas generator are integrated. Therefore, provision of a device with high energy utilization efficiency is demanded even as a glycerin reforming device alone.

  The present invention has been made to solve the above-described problems, and provides a glycerin reforming apparatus and a reforming method capable of reforming glycerin with high energy utilization efficiency and capable of being converted into a valuable gas. With the goal.

  In order to achieve the above object, the glycerin reforming apparatus of the present invention has a catalyst accommodated therein, and generates a steam reforming reaction using the catalyst between glycerin and a reaction gas containing at least steam. A reforming reactor that reforms the glycerin, a cooling / heat recovery unit that cools the reformed gas generated after the steam reforming reaction and recovers heat from the reformed gas, and burns the fuel And a combustor that generates combustion exhaust gas, and the inside of the reforming reactor is heated by heat of the combustion exhaust gas obtained from the combustor.

  In the glycerin reforming apparatus of the present invention, a configuration in which air or oxygen is supplied into the reforming reactor in addition to the water vapor as the reaction gas can be employed.

  In the glycerin reforming apparatus of the present invention, a container for accommodating the reforming reactor is provided, the combustion exhaust gas is introduced into the container, and the inside of the reforming reactor is heated by the heat of the combustion exhaust gas. Can be adopted.

  In the glycerin reforming apparatus of the present invention, a configuration in which a heater for preheating the reaction gas is provided inside the container.

  In the glycerin reforming apparatus of the present invention, it is possible to employ a configuration in which water is evaporated using the heat recovered by the cooling / heat recovery device to generate the water vapor.

  In the glycerin reforming apparatus of the present invention, a configuration provided with a gas purifier for purifying hydrogen from the reformed gas cooled by the cooling / heat recovery unit can be adopted.

  In the glycerin reforming apparatus of the present invention, a configuration in which exhaust gas discharged from the gas purifier is supplied to the combustor as fuel can be employed.

  In the glycerin reforming apparatus of the present invention, a configuration in which a hydrogen separation membrane for separating hydrogen from the reformed gas is provided inside the reforming reactor.

  In the glycerin reforming apparatus according to the present invention, the cooling / heat recovery device cools the hydrogen gas separated by the hydrogen separation membrane with water, while evaporating the water by the heat of the hydrogen gas to produce the water vapor. A first cooling / heat recovery unit to be generated; and a second cooling / cooling unit that cools the reformed gas discharged from the reforming reactor with the glycerin while preheating the glycerin with heat of the reformed gas. And a heat recovery unit, and the reformed gas discharged from the second cooler can be supplied as fuel to the combustor.

  The glycerin reforming method of the present invention is for a reaction containing glycerin and at least steam while heating the inside of the reforming reactor by the heat of combustion exhaust gas obtained when fuel is burned outside the reforming reactor. A steam reforming reaction is allowed to proceed with the gas using a catalyst to reform the glycerin, cool the reformed gas generated after the steam reforming reaction, and recover heat from the reformed gas It is characterized by doing.

  According to the glycerin reforming apparatus of the present invention, a steam reforming reaction occurs between glycerin and water vapor contained in the reaction gas by the action of a catalyst in the reforming reactor. Through this reaction, glycerin is modified, and glycerin can be converted into valuable gases such as hydrogen, carbon monoxide, and carbon dioxide. By converting glycerin into valuable gas in this way, energy utilization efficiency can be increased compared to conventional glycerin treatment methods in which heat recovery by incineration is performed. And by recovering by-product glycerol as gas, such as hydrogen and carbon monoxide, these gas can be utilized as a raw material of hydrogen fuel or a chemical synthesis product. For example, by using hydrogen gas as fuel, high-efficiency power generation using a fuel cell is possible. In addition, diversion to the hydrogen utilization field is possible.

  Further, since the steam reforming reaction of glycerin is an endothermic reaction, heating in the reforming reactor is necessary to promote the reaction. Therefore, the glycerin reforming apparatus of the present invention is equipped with a combustor that combusts fuel and generates combustion exhaust gas, so that the inside of the reforming reactor can be heated by the heat of the combustion exhaust gas obtained from the combustor. It is. Since the combustor is separate from the reforming reactor and various fuels can be freely selected, the temperature in the reforming reactor can be controlled efficiently and accurately.

  Since the steam reforming reaction proceeds at a high temperature such as several hundred degrees Celsius, a considerably high-temperature reformed gas is discharged from the reforming reactor. Here, in the glycerin reforming apparatus of the present invention, the high-temperature reformed gas is cooled by using a cooling / heat recovery device, and this heat can be effectively utilized by recovering the heat. Therefore, an apparatus with high energy utilization efficiency can be realized as a glycerin reforming apparatus alone. For example, water can be evaporated using the heat recovered by the cooling / heat recovery device to generate water vapor as a reaction gas. With this configuration, external heat necessary for generating water vapor can be reduced. Alternatively, an external heat source can be eliminated.

  Further, if air or oxygen is supplied as a reaction gas into the reforming reactor, a partial oxidation reforming reaction (or complete oxidation reforming reaction) occurs in addition to the steam reforming reaction. Valuable gases such as hydrogen, carbon monoxide, and carbon dioxide are also generated by the partial oxidation reforming reaction. Since the partial oxidation reforming reaction is an exothermic reaction, the heat required for the steam reforming reaction can be covered by the heat generated during the partial oxidation reforming reaction, and less heat is supplied from the external combustor. Further, in the steam reforming reaction of glycerin, carbon is deposited on the catalyst and the catalyst is deteriorated. On the other hand, if it is the structure by which air and oxygen are supplied in a reforming reactor, precipitation of carbon can be suppressed.

  In addition, according to the configuration in which the container for storing the reforming reactor is provided and the combustion exhaust gas is introduced into the container, the reforming reactor and the container constitute one heat exchanger. In that case, heat is transmitted through the wall surface of the reforming reactor, and heating in the reforming reactor is efficiently performed. Furthermore, if the reaction gas preheating heater is provided inside the container, the heat of the combustion exhaust gas can be recovered without waste. As a result, the heat supplied from the outside for preheating the reaction gas can be reduced, and an energy efficient apparatus can be realized.

  Moreover, if it is set as the structure provided with the gas refiner which refine | purifies hydrogen from the after-reforming gas, higher purity hydrogen gas can be obtained. On the other hand, after purifying hydrogen gas, gases such as carbon monoxide and carbon dioxide are discharged from the gas purifier. By recycling the exhaust gas as fuel in the combustor, a highly energy efficient device can be realized. .

  Alternatively, according to the configuration in which the hydrogen separation membrane is provided in the reforming reactor, hydrogen is separated from the reformed gas in the reactor, so that the partial pressure of hydrogen in the reformed gas is successively reduced. The steam reforming reaction is further promoted. Further, in the case of this configuration, the reformed gas discharged from the reforming reactor is a gas such as carbon monoxide or carbon dioxide after hydrogen is separated. While these gases are cooled with glycerin, according to the configuration including the second cooling / heat recovery device that preheats glycerin with the heat of the reformed gas, the glycerin can be preheated efficiently. In addition, gas such as carbon monoxide and carbon dioxide discharged from the second cooling / heat recovery device can be recycled as fuel in the combustor.

  According to the glycerin reforming method of the present invention, as described above, glycerin can be reformed and converted into valuable gases such as hydrogen, carbon monoxide, carbon dioxide and the like. Thereby, compared with the conventional processing method of glycerin which performed heat recovery by incineration disposal, energy use efficiency can be improved.

[First embodiment]
Hereinafter, a glycerin reforming apparatus and a reforming method according to a first embodiment of the present invention will be described with reference to FIG.
FIG. 1 is a schematic configuration diagram of a glycerin reforming apparatus according to the present embodiment.

  As shown in FIG. 1, the glycerin reforming apparatus 1 of the present embodiment includes a heat exchanger 5 that houses a reforming reactor 2 and heaters 3 and 4, a combustor 6, and a cooling / heat recovery device. 7 and a gas purifier 8. The heat exchanger 5 includes a container 9 serving as a housing of the heat exchanger 5, a reforming reactor 2 and heaters 3 and 4 accommodated in the container 9. A combustion exhaust gas introduction pipe 11 for introducing combustion exhaust gas from a combustor 6 described later is connected to the top of the container 9.

  Inside the container 9, from the bottom surface of the container 9, a glycerin introduction pipe 12 for introducing glycerin into the reforming reactor 2, a steam introduction pipe 13 for introducing water vapor into the reforming reactor 2, and air are modified. Air introducing pipes 14 for introduction into the quality reactor 2 are respectively charged, and these pipes 12, 13, 14 are connected to the bottom of the reforming reactor 2. With this configuration, glycerin, and a reaction gas including water vapor and air are supplied into the reforming reactor 2. Inside the container 9, heaters 3 and 4 for preheating glycerin and water vapor (water) are respectively installed in the middle of the glycerin introduction pipe 12 and the water vapor introduction pipe 13. Here, air is introduced into the reforming reactor 2, but oxygen may be introduced instead of air.

  The glycerin introduction pipe 12 branches in the middle, one pipe 12 a is connected to the reforming reactor 2 in the heat exchanger 5, and the other pipe 12 b is connected to the combustor 6. An air introduction pipe 15 is connected to the combustor 6. Accordingly, glycerin and air are burned as fuel in the combustor 6, and high-temperature combustion exhaust gas is discharged from the combustor 6. In the present embodiment, glycerin and air are used as fuel, but city gas, LPG, hydrogen gas, or the like may be used. Moreover, it is not necessary to introduce glycerin. The installation place of the combustor 6 is not limited to the outside of the heat exchanger 5 but may be inside, for example, inside the container 9.

Inside the reforming reactor 2, the glycerol steam reforming reaction (the following reaction formula (1)), the partial oxidation reforming reaction (the following reaction formula (2)), complete with glycerin and the above reaction gas. Three types of reforming reactions of the oxidation reforming reaction (the following reaction formula (3)) occur simultaneously, and glycerin and the reaction gas are converted into a reformed gas containing hydrogen, carbon monoxide, and carbon dioxide. The reaction temperature in the reforming reactor 2 varies depending on the catalyst used, but is adjusted to 200 ° C to 900 ° C. Depending on the supply amount of air (or oxygen), only the partial oxidation reforming reaction may occur and the complete oxidation reforming reaction may not occur.
C ₃ H ₅ (OH) ₃ + H ₂ O → 5H ₂ + 2CO + CO ₂ (1)
C ₃ H ₅ (OH) ₃ + 2O ₂ → 4H ₂ O + 3CO (2)
2C ₃ H ₅ (OH) ₃ + 7O ₂ → 8H ₂ O + 6CO ₂ (3)

  However, in actuality, the amount of steam supplied is sufficiently larger than the amount of air supplied into the reforming reactor 2, and therefore the steam reforming reaction is dominant among the above three types of reforming reactions. . Since the steam reforming reaction is an endothermic reaction, heat is required to promote the steam reforming reaction. Therefore, the high-temperature combustion exhaust gas obtained by the combustor 6 is supplied into the container 9 of the heat exchanger 5 through the combustion exhaust gas introduction pipe 11. Thereby, heat exchange is made through the wall surface of the reforming reactor 2, and the temperature in the reforming reactor 2 can be raised to 200 ° C to 900 ° C. Moreover, since the partial oxidation reforming reaction that occurs slightly is an exothermic reaction, the heat from the partial oxidation reforming reaction also contributes to the temperature increase. Furthermore, carbon deposition can be suppressed by supplying air into the reforming reactor 2.

  As described above, the combustion exhaust gas flowing in the container 9 from the top to the bottom still has sufficient heat even after being deprived of heat by the reforming reactor 2 disposed on the upper part (upstream side) of the container 9. is doing. Therefore, when the combustion exhaust gas reaches the heaters 3 and 4 arranged at the lower part (downstream side) of the container 9, it is used for heating glycerin and water in the heaters 3 and 4. At this time, it is desirable that the water is evaporated to be in a steam state and supplied into the reforming reactor 2. The boiling point of glycerin is about 290 ° C., and glycerin may be supplied in a liquid state or in the state of glycerin vapor. The combustion gas after heat exchange with the heaters 3 and 4 is discharged from the exhaust pipe 16 to the outside of the heat exchanger 5.

Further, since a catalyst is necessary for the steam reforming reaction, the catalyst is accommodated in the reforming reactor 2 to form a catalyst layer. Examples of the catalyst used, can be used, for example _{Ni / Al 2 O 3, Rh} / CeO 2 / Al 2 O 3, Ni / MgO, Rh / Pt / CeO 2, Ru / Y 2 O 3. However, when performing the steam reforming reaction of glycerin, deterioration due to carbon deposition on the catalyst is a problem. Therefore, in order to prevent carbon from precipitating as much as possible, it is desirable that the steam carbon ratio (stoichiometric ratio of water vapor and carbon monoxide) be 2 to 10. Further, as a catalyst that hardly causes carbon deposition, a MgO catalyst (noble metal / MgO catalyst) supporting a noble metal such as Pt, Pd, Rh, a Ni—MgO catalyst that is a solid solution of Ni and MgO, a noble metal / MgO catalyst and Ni— It is desirable to use a physical mixed catalyst of MgO catalyst. In order to advance the catalytic reaction efficiently, it is desirable that the catalyst layer take the form of a packed bed. Alternatively, a fluidized bed can be used.

  The reforming reactor 2 and the cooling / heat recovery unit 7 are connected by a post-reforming gas transport pipe 17, and the post-reforming gas containing hydrogen, carbon monoxide, and carbon dioxide is supplied to the post-reforming gas transport pipe 17. Is discharged from the reforming reactor 2 and introduced into the cooling / heat recovery unit 7. Since the reformed gas is clean, as the form of the cooling / heat recovery unit 7, a well-known type such as a shell and tube type heat exchanger, a plate fin type heat exchanger, or the like can be used. Water is supplied to the cooling / heat recovery unit 7 as a refrigerant, and heat is exchanged between the water and the reformed gas. That is, since the reformed gas discharged from the reforming reactor 2 at 200 ° C. to 900 ° C. still maintains a considerably high temperature, the reformed gas is cooled by the cooling / heat recovery device 7 and the refrigerant Heat is recovered by the water. At this time, water evaporates to generate water vapor, which is introduced into the heater 4. Or even if not all become water vapor | steam, what is necessary is just the structure by which high temperature water is introduce | transduced into the heater 4. FIG.

  The cooling / heat recovery unit 7 and the gas purifier 8 are connected by a post-reforming gas transport pipe 17, and the post-reforming gas cooled through the cooling / heat recovery unit 7 is introduced into the gas purifier 8. . As the gas purifier 8, for example, a known one such as PSA (Pressure Swing Adsorption) can be used. For example, carbon monoxide, carbon dioxide, and the like contained in the reformed gas are adsorbed and removed by the gas purifier 8, and high-purity hydrogen gas can be obtained. Depending on the oil and fat raw material used in the production of biodiesel fuel, by-product glycerin may contain alkali, and the reformed gas may also contain alkali. In that case, if the gas purifier 8 has a function of removing alkali, an alkali-free high-purity valuable gas can be obtained. As a method for removing alkali, a filter method, a spray cleaning method, a solvent absorption method, or the like can be used. In addition, as long as gas such as carbon monoxide and carbon dioxide is discharged from the gas purifier 8, these gases may be supplied to the combustor 6 and recycled as fuel.

  According to the glycerin reforming apparatus 1 of this embodiment, in the reforming reactor 2, a steam reforming reaction between glycerin and steam and a partial oxidation reforming reaction between glycerin and oxygen are caused by the action of a catalyst. Arise. Through these reactions, glycerin is modified, and glycerin can be converted into valuable gases such as hydrogen, carbon monoxide, and carbon dioxide. Thereby, compared with the conventional processing method of glycerin which performed heat recovery by incineration disposal, energy use efficiency can be improved. In addition, by recovering glycerin as a valuable gas such as hydrogen or carbon monoxide, these gases can be used as raw materials for hydrogen fuel and chemical synthetic products (eg, FT synthetic oil, methanol, synthetic natural gas, chemical fertilizer, etc.). . For example, by using hydrogen gas as a fuel, it can be diverted to a hydrogen utilization field such as high-efficiency power generation by a fuel cell.

  Further, according to the glycerin reforming apparatus 1 of the present embodiment, the high-temperature reformed gas is cooled using the cooling / heat recovery unit 7, and the generation of water vapor, glycerin and the like by the heat recovered from the reformed gas Air can be preheated, etc., and the heat of the reformed gas can be used effectively in this device. Thereby, the external heat source for performing the preheating of the reaction gas can be reduced. In this way, a small system can be constructed, and a device with high energy utilization efficiency can be realized as a glycerin reforming device alone. Further, the inside of the reforming reactor 2 is heated by the heat of the combustion exhaust gas obtained from the combustor 6, and various fuels can be freely selected. Therefore, the temperature in the reforming reactor 2 can be efficiently and accurately controlled. It can be controlled well. In particular, in the present embodiment, since the raw material used in the reforming reaction such as glycerin or air is used as the fuel, it is not necessary to prepare another fuel.

[Second Embodiment]
Hereinafter, a second embodiment of the present invention will be described with reference to FIG.
FIG. 2 is a schematic configuration diagram of the glycerin reforming apparatus of the present embodiment.
The basic configuration of the glycerin reforming apparatus of this embodiment is the same as that of the first embodiment, and the configuration for purifying the reformed gas is only different from that of the first embodiment. Therefore, in FIG. 2, the same reference numerals are given to the same components as those in FIG. 1, and detailed description will be omitted.

  As shown in FIG. 2, the glycerin reforming apparatus 21 of this embodiment includes a catalyst housed in the reforming reactor 2 and a hydrogen separation membrane 23. The hydrogen separation membrane 23 is composed of a ceramic separation membrane, a metal separation membrane made of Pd, Pd—Ag, Pd—Cu, or the like. As described above, since the hydrogen separation membrane 23 is installed inside the reforming reactor 2, the reformed gas is separated into hydrogen, carbon monoxide, and carbon dioxide inside the reforming reactor 2. Therefore, in the present embodiment, unlike the first embodiment, a gas purifier for purifying hydrogen gas is not installed in the subsequent stage of the reforming reactor 2.

  High-temperature hydrogen gas is discharged from the hydrogen separation membrane 23 in the reforming reactor 2 through the hydrogen discharge pipe 24 and introduced into the first cooling / heat recovery unit 25. In the first cooling / heat recovery unit 25, heat exchange occurs between water and hydrogen gas, and the hydrogen gas is cooled by water, while the water is heated by the heat of the hydrogen gas to generate water vapor.

  High temperature carbon monoxide and carbon dioxide are discharged from the reforming reactor 2 through the post-reforming gas discharge pipe 26 and introduced into the second cooling / heat recovery unit 27. In the second cooling / heat recovery unit 27, heat exchange occurs between glycerin and carbon monoxide and carbon dioxide gas, and the carbon monoxide and carbon dioxide gas are cooled by glycerin, while carbon monoxide and carbon dioxide gas are cooled. Glycerin is heated by the heat. That is, glycerin is preheated by passing through the second cooling / heat recovery device 27 and then introduced into the heater 3 in the heat exchanger 28. On the other hand, the carbon monoxide and carbon dioxide gas after passing through the second cooling / heat recovery unit 27 is supplied to the combustor 6 as fuel.

  In the first embodiment shown in FIG. 1, hydrogen, carbon monoxide, and carbon dioxide are collectively discharged from the reforming reactor 2 as a reformed gas, passed through a cooling / heat recovery unit 7, and then a gas purifier. 8 was purifying hydrogen gas. On the other hand, in the present embodiment, hydrogen, carbon monoxide, and carbon dioxide are separated by the hydrogen separation membrane 23 in the reforming reactor 2, and these are taken out separately to obtain the first cooling / heat recovery unit 25, Each is supplied to the second cooling / heat recovery unit 27. The first cooling / heat recovery unit 25 effectively uses the heat of hydrogen gas to generate water vapor, and the second cooling / heat recovery unit 27 uses the heat of carbon monoxide and carbon dioxide gas to preheat glycerin. We are using. Further, carbon monoxide and carbon dioxide gas after being used for preheating glycerin in the second cooling / heat recovery unit 27 are recycled as fuel in the combustor 6. Thus, also in this embodiment, it is possible to realize a glycerin reforming apparatus with extremely high energy efficiency.

  Further, since hydrogen is sequentially separated from the reformed gas in the reforming reactor 2, hydrogen is taken into the hydrogen separation membrane while the steam reforming reaction proceeds according to the above reaction formula (1), and the reforming gas is improved. The partial pressure of hydrogen in the after-treatment gas gradually decreases. Therefore, the steam reforming reaction is more likely to proceed in the direction from the equilibrium state toward the right side of the reaction formula (1). That is, according to this structure, the effect that the steam reforming reaction is further promoted and the hydrogen generation rate is improved can be obtained.

  The technical scope of the present invention is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention. For example, in the said embodiment, it was set as the structure which introduce | transduces into a reforming reactor glycerol and the gas for reaction containing water vapor | steam and air (or oxygen). In addition to this, a configuration may be adopted in which part of the generated hydrogen gas is returned to the reforming reactor. In that case, thermal decomposition reaction of glycerin with hydrogen also takes place, and glycerin can be reformed. In addition, as a configuration for supplying the heat of combustion exhaust gas from the combustor to the reforming reactor, a container surrounding the outside of the reforming reactor is provided and the combustion exhaust gas is flowed into the container. Instead, for example, a configuration in which piping for flowing combustion exhaust gas is routed inside the reforming reactor may be employed. In addition, the specific configuration, arrangement, and the like of each element in the apparatus are not limited to the above embodiment, and can be changed as appropriate.

It is a schematic block diagram of the glycerin reforming apparatus of 1st Embodiment of this invention. It is a schematic block diagram of the glycerol reformer of 2nd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,21 ... Glycerin reformer, 2 ... Reforming reactor, 3, 4 ... Heater, 5,28 ... Heat exchanger, 6 ... Combustor, 7 ... Cooling / heat recovery device, 8 ... Gas purifier, DESCRIPTION OF SYMBOLS 9 ... Container, 23 ... Hydrogen separation membrane, 25 ... 1st cooling and heat recovery device, 27 ... 2nd cooling and heat recovery device.

Claims (10)

A reforming reactor in which a catalyst is housed, a steam reforming reaction is generated between the glycerin and a reaction gas containing at least steam using the catalyst, and the glycerin is reformed;
A cooling / heat recovery unit that cools the reformed gas generated after the steam reforming reaction and recovers heat from the reformed gas;
A combustor that generates combustion exhaust gas by burning fuel, and
The inside of the said reforming reactor is heated with the heat | fever of the said combustion exhaust gas obtained from the said combustor, The glycerol reformer characterized by the above-mentioned.   2. The glycerin reforming apparatus according to claim 1, wherein air or oxygen is supplied into the reforming reactor in addition to the water vapor as the reaction gas.   The container for accommodating the reforming reactor is provided, the combustion exhaust gas is introduced into the container, and the interior of the reforming reactor is heated by the heat of the combustion exhaust gas. Or the glycerin reforming apparatus according to 2;   The glycerin reforming apparatus according to claim 3, wherein a heater for preheating the reaction gas is provided inside the container.   The glycerin reforming apparatus according to any one of claims 1 to 4, wherein water is evaporated using heat recovered by the cooling / heat recovery unit to generate the water vapor.   The glycerin reforming apparatus according to any one of claims 1 to 5, further comprising a gas purifier that purifies hydrogen from the reformed gas cooled by the cooling / heat recovery unit.   The glycerin reforming apparatus according to claim 6, wherein the exhaust gas discharged from the gas purifier is supplied to the combustor as fuel.   The glycerol reformer according to any one of claims 1 to 5, wherein a hydrogen separation membrane for separating hydrogen from the reformed gas is provided inside the reforming reactor. The cooling / heat recovery device cools the hydrogen gas separated by the hydrogen separation membrane with water, while evaporating the water with the heat of the hydrogen gas to generate the water vapor. And a second cooling / heat recovery unit that cools the reformed gas discharged from the reforming reactor with the glycerin, while preheating the glycerin with the heat of the reformed gas,
The glycerin reforming apparatus according to claim 8, wherein the reformed gas discharged from the second cooler is supplied to the combustor as fuel.   A catalyst is used between glycerin and a reaction gas containing at least steam while heating the inside of the reforming reactor by the heat of combustion exhaust gas obtained when fuel is burned outside the reforming reactor. Proceeding with a steam reforming reaction to reform the glycerin, cooling the reformed gas generated after the steam reforming reaction, and recovering heat from the reformed gas Method.

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