JP2018162195A - Hydrogen production equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen production apparatus that can reduce power for operating the hydrogen production apparatus, compared with the case where a chiller is used to separate water vapor included in a reformed gas.SOLUTION: A separation film of a separation part allows the passage of at least water vapor out of a reformed gas produced from a reformer, to separate it. A hydrogen purifier separates the reformed gas from which water vapor is separated, into impurities and hydrogen, to purify hydrogen.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen production apparatus.

  As a hydrogen production apparatus for obtaining hydrogen, an apparatus for reforming raw material hydrocarbons into reformed gas by a reformer and then supplying the reformed gas to a PSA (Pressure Swing Adsorption) apparatus is known (for example, Patent Document 1). reference).

  There is also known a hydrogen production apparatus that boosts the reformed gas after reforming and supplies the reformed gas to a PSA apparatus (see, for example, Patent Document 2).

JP-A-8-225302 JP 2003-335502 A

  Conventionally, in a hydrogen production apparatus, a chiller is used to cool and dehumidify the reformed gas in order to separate water vapor from the reformed gas. Power for operating the chiller is large, and thus power for operating the hydrogen production apparatus has also been increased.

  The subject of this invention is reducing the motive power for operating a hydrogen production apparatus compared with the case where a chiller is used in order to isolate | separate the water vapor | steam contained in reformed gas.

  In the first aspect, by reforming the hydrocarbon raw material to generate a reformed gas mainly composed of hydrogen, and by passing at least steam from the reformed gas discharged from the reformer, A separation unit having a separation membrane for separation, and a hydrogen purifier that separates the reformed gas from which water vapor has been separated into impurities and hydrogen to purify hydrogen are provided.

  According to this configuration, the separation membrane is separated from the reformed gas generated by the reformer by passing water vapor. For this reason, compared with the case where a chiller is used in order to isolate | separate the water vapor | steam contained in reformed gas, the motive power for operating a hydrogen production apparatus can be reduced.

  In a second aspect, the apparatus includes a compressor that compresses the reformed gas from which water vapor has been separated, and the hydrogen purifier separates the reformed gas compressed by the compressor into impurities and hydrogen. .

  In the third aspect, the separation membrane is separated from the reformed gas by passing carbon dioxide.

  According to this configuration, the separation membrane that separates the water vapor from the reformed gas generated by the reformer is separated from the reformed gas by passing carbon dioxide. For this reason, compared with the case where the carbon dioxide contained in reformed gas is not isolate | separated, a hydrogen purifier can be reduced in size.

  In a fourth aspect, the reformer includes a flow path pipe that generates reformed gas from a hydrocarbon raw material by a steam reforming reaction, and returns the steam separated by the separation membrane to the reformer as reforming water. It is characterized by providing.

  According to this configuration, the water vapor separated by the separation membrane flows through the flow path pipe and is returned to the reformer as reforming water. Thus, the water vapor separated by the separation membrane can be used as the reforming water.

  In the fifth aspect, a hydrocarbon raw material supplied to the reformer is used as a sweep gas that flows to the water vapor passage side of the separation membrane.

  According to this configuration, since a small amount of hydrogen enters the sweep gas from the reformed gas through the separation membrane, the sulfur content contained in the hydrocarbon raw material can be reduced by hydrodesulfurization.

  In a sixth aspect, combustion air supplied to the reformer is used as a sweep gas that flows to the water vapor passage side of the separation membrane.

  According to this configuration, by using combustion air having a large flow rate in the gas used in the hydrogen production apparatus as the sweep gas, the water vapor separation performance is improved, and the membrane area of the separation membrane can be reduced.

  In this aspect, power for operating the hydrogen production apparatus can be reduced as compared with the case where a chiller is used to separate water vapor contained in the reformed gas.

It is the schematic block diagram which showed the hydrogen production apparatus which concerns on 1st Embodiment of this invention. It is sectional drawing which showed the multiple cylinder type reformer of the hydrogen production apparatus which concerns on 1st Embodiment of this invention. It is the schematic block diagram which showed the hydrogen production apparatus which concerns on 2nd Embodiment of this invention. It is sectional drawing which showed the multiple cylinder type reformer of the hydrogen production apparatus which concerns on 2nd Embodiment of this invention. It is the schematic block diagram which showed the hydrogen production apparatus which concerns on 3rd Embodiment of this invention. It is sectional drawing which showed the multiple cylinder type reformer of the hydrogen production apparatus which concerns on 3rd Embodiment of this invention.

<First Embodiment>
An example of the hydrogen production apparatus according to the first embodiment of the present invention will be described with reference to FIGS.

  As shown in FIG. 1, the hydrogen production apparatus 10 according to the first embodiment supplies a multi-cylinder reformer 12, a reforming water supply unit 30 that supplies reforming water, and combustion air. And an air supply unit 18. Furthermore, the hydrogen production apparatus 10 includes a separation unit 50 having a separation membrane 14, a compressor 80 that compresses reformed gas, and a hydrogen purifier 90 that purifies hydrogen. This hydrogen production apparatus 10 produces hydrogen from a hydrocarbon raw material. In the first embodiment, a case where city gas is used as an example of a hydrocarbon raw material will be described.

(Multiple cylinder reformer 12)
As shown in FIG. 2, the multiple cylinder reformer 12 has a plurality of cylindrical walls 21, 22, 23, and 24 arranged in multiple. The plurality of cylindrical walls 21, 22, 23, 24 are formed in, for example, a cylindrical shape or an elliptical cylindrical shape. A combustion chamber 25 is formed inside the first cylindrical wall 21 from the inside out of the plurality of cylindrical walls 21, 22, 23, 24, and a burner 26 faces downward at the upper part of the combustion chamber 25. Is arranged. The burner 26 is supplied with the off gas of the hydrogen production apparatus 10 from the supply pipe 38 as fuel. The multiple cylinder reformer 12 is an example of a reformer. Further, an air supply pipe 40 for supplying combustion air from the air supply unit 18 (see FIG. 1) is connected to the upper end of the combustion chamber 25.

  A flue gas flow path 27 is formed between the first cylindrical wall 21 and the second cylindrical wall 22. A lower end portion of the combustion exhaust gas passage 27 communicates with the combustion chamber 25, and a gas exhaust pipe 28 for discharging gas is connected to the upper end portion of the combustion exhaust gas passage 27. The flue gas discharged from the combustion chamber 25 flows from the lower side to the upper side through the flue gas passage 27 and is discharged to the outside through the gas discharge pipe 28.

  A first flow path 31 is formed between the second cylindrical wall 22 and the third cylindrical wall 23. The upper portion of the first flow path 31 is formed as a preheating flow path 32, and a raw material supply for supplying city gas that has passed through the separation section 50 (see FIG. 1) is provided at the upper end of the preheating flow path 32. A pipe 33 is connected to a reforming water supply pipe 34 for supplying reforming water from the reforming water supply unit 30 (see FIG. 1). Further, a spiral member 35 is provided between the second cylindrical wall 22 and the third cylindrical wall 23, and the preheating channel 32 is formed in a spiral shape by the spiral member 35. Yes. The raw material supply pipe 33 is an example of a flow path pipe.

  The preheating channel 32 is supplied with the city gas that has passed through the separation unit 50 (see FIG. 1) from the raw material supply pipe 33, and the reforming water in the reforming water supply unit 30 (see FIG. 1) is the reforming water. It is supplied from the supply pipe 34. The city gas and the reforming water flow from the upper side to the lower side through the preheating channel 32, and heat exchange with the combustion exhaust gas is performed through the second cylindrical wall 22 to vaporize the water. In the preheating channel 32, the mixed gas is generated by mixing the city gas and the reforming water (steam) in the gas phase.

  The reforming catalyst layer 36 is provided below the preheating channel 32 in the first channel 31, and the mixed gas generated in the preheating channel 32 is supplied to the reforming catalyst layer 36. . In the reforming catalyst layer 36, the mixed gas receives heat from the combustion exhaust gas flowing through the combustion exhaust gas channel 27, and the mixed gas generates a reformed gas containing hydrogen as a main component by a steam reforming reaction.

  Further, a second flow path 42 is formed between the third cylindrical wall 23 and the fourth cylindrical wall 24. The lower end of the second flow path 42 is in communication with the lower end of the first flow path 31. A lower portion of the second flow path 42 is formed as a reformed gas flow path 43, and a reformed gas discharge pipe 44 is connected to an upper end portion of the second flow path 42.

  Further, a CO shift catalyst layer 45 is provided above the reformed gas channel 43 in the second channel 42, and the reformed gas generated in the reformed catalyst layer 36 is converted into the reformed gas flow. After passing through the passage 43, it is supplied to the CO shift catalyst layer 45. In the CO conversion catalyst layer 45, carbon monoxide and water vapor contained in the reformed gas react to be converted into hydrogen and carbon dioxide, and carbon monoxide is reduced.

  Further, an oxidant gas supply pipe 46 is connected to the upper side of the CO shift catalyst layer 45, and a CO selective oxidation catalyst layer 47 is provided above the CO shift catalyst layer 45 in the second flow path 42. ing. The oxidant gas introduced through the oxidant gas supply pipe 46 and the reformed gas that has passed through the CO shift catalyst layer 45 are supplied to the CO selective oxidation catalyst layer 47. In the CO selective oxidation catalyst layer 47, for example, carbon monoxide reacts with oxygen on a noble metal catalyst such as platinum or ruthenium to be converted into carbon dioxide, and carbon monoxide is removed. The reformed gas from which carbon monoxide has been removed by the CO shift catalyst layer 45 and the CO selective oxidation catalyst layer 47 is discharged through the reformed gas discharge pipe 44.

  As shown in FIG. 1, the reformed gas generated in the multi-cylinder reformer 12 flows through the separator 50, the compressor 80, and the hydrogen purifier 90 in this order. That is, the multi-cylinder reformer 12, the separator 50, the compressor 80, and the hydrogen purifier 90 are arranged in this order from the upstream side to the downstream side in the gas flow direction.

(Separation unit 50)
As shown in FIG. 1, the separation unit 50 includes a separation membrane 14 that allows water vapor to pass (permeates), a supply chamber 52 and a permeation chamber 54 that are partitioned by the separation membrane 14. Connected to the supply chamber 52 are a reformed gas discharge pipe 44 through which the reformed gas from the multi-cylinder reformer 12 flows and a communication channel pipe 56 through which the reformed gas supplied to the compressor 80 flows. Yes. Then, the water vapor contained in the reformed gas supplied to the supply chamber 52 through the reformed gas discharge pipe 44 passes through the separation membrane 14 and flows from the supply chamber 52 to the permeation chamber 54. The reformed gas from which the water vapor has been separated flows through the communication channel pipe 56 and is supplied to the compressor 80.

  On the other hand, a gas supply pipe 58 to which city gas as a sweep gas is supplied and a raw material supply pipe 33 through which the city gas supplied to the multi-cylinder reformer 12 flows are connected to the permeation chamber 54. The city gas supplied as the sweep gas to the permeation chamber 54 includes water vapor that has passed through the separation membrane 14, flows through the raw material supply pipe 33, and is supplied to the multiple cylinder reformer 12.

Examples of the water vapor separation membrane include an organic polymer membrane, an inorganic material membrane, an organic polymer-inorganic material composite membrane, and a liquid membrane (compressor 80).
Connected to the compressor 80 are a communication channel pipe 56 through which the reformed gas from the supply chamber 52 flows and a communication channel pipe 68 through which the reformed gas supplied to the hydrogen purifier 90 flows. The compressor 80 compresses the atmospheric reformed gas supplied from the separation unit 50 with a pump, and supplies the compressed gas to the hydrogen purifier 90.

(Hydrogen purifier 90)
Connected to the hydrogen purifier 90 are a communication channel pipe 68 through which the reformed gas from the compressor 80 flows and a replenishment pipe 38 through which the off-gas of the hydrogen purifier 90 supplied to the multiple cylinder reformer 12 flows. ing. As an example, a PSA apparatus is used for the hydrogen purifier 90. The hydrogen purifier 90 separates the reformed gas into impurities and hydrogen, thereby purifying hydrogen.

  On the other hand, the off-gas of the hydrogen purifier 90 flows through the supply pipe 38 and is supplied as fuel to the burner 26 (see FIG. 2) of the multiple cylinder reformer 12.

(Function)
Next, the operation of the hydrogen production apparatus 10 will be described.

  As shown in FIG. 1, the city gas flows through the gas supply pipe 58, passes through the permeation chamber 54 of the separation unit 50, flows through the raw material supply pipe 33, and is supplied to the multiple cylinder reformer 12.

  The city gas supplied to the multiple cylinder reformer 12 is generated into the reformed gas by the multiple cylinder reformer 12. The reformed gas flows through the reformed gas discharge pipe 44 and is supplied to the supply chamber 52 of the separation unit 50. The water vapor contained in the reformed gas supplied to the supply chamber 52 passes through the separation membrane 14 and flows from the supply chamber 52 to the permeation chamber 54. The city gas supplied as the sweep gas to the permeation chamber 54 includes the water vapor that has passed through the separation membrane 14, flows through the raw material supply pipe 33, and is supplied to the multiple cylinder reformer 12.

  On the other hand, the reformed gas from which the water vapor has been separated by the separation membrane 14 flows through the connecting flow path pipe 56, is supplied to the compressor 80, and is compressed by the compressor 80. The compressed reformed gas flows through the communication channel pipe 68 and is supplied to the hydrogen purifier 90.

  Hydrogen (pure hydrogen) is purified by separating the reformed gas supplied to the hydrogen purifier 90 into impurities and hydrogen.

  On the other hand, the off-gas of the hydrogen purifier 90 flows through the supply pipe 38 and is supplied as fuel to the burner 26 (see FIG. 2) of the multiple cylinder reformer 12.

(Summary)
As described above, in the hydrogen production apparatus 10, the separation membrane 14 is used to separate water vapor contained in the reformed gas. For this reason, compared with the case where a chiller is used in order to isolate | separate the water vapor | steam contained in reformed gas, the motive power for operating the hydrogen production apparatus 10 can be reduced.

  The city gas supplied to the permeation chamber 54 includes water vapor that has passed through the separation membrane 14, flows through the raw material supply pipe 33, and is supplied to the multiple cylinder reformer 12. For this reason, the water vapor separated by the separation membrane 14 can be used as water for the steam reforming reaction. In addition, the amount of reforming water supplied from the reforming water supply unit 30 can be reduced. Furthermore, since a small amount of hydrogen enters the sweep gas from the reformed gas through the separation membrane, the sulfur content contained in the city gas can be reduced by hydrodesulfurization.

  Further, the reformed gas supplied to the compressor 80 is separated from water vapor by the separation unit 50. As described above, since the reformed gas from which the water vapor is separated is supplied to the compressor 80, the reformed gas is improved as compared with the case where the reformed gas from which the water vapor is not separated (including water vapor) is supplied. By reducing the volume of the quality gas, the reformed gas can be effectively compressed.

Second Embodiment
An example of the hydrogen production apparatus 110 according to the second embodiment of the present invention will be described with reference to FIGS. In addition, about 2nd Embodiment, a different part from 1st Embodiment is mainly demonstrated.

(Constitution)
As shown in FIG. 4, a raw material supply pipe 133 is connected to the upper end portion of the preheating channel 32 of the multiple cylinder reformer 112 of the hydrogen production apparatus 110. As shown in FIG. 3, the city gas is directly supplied from the raw material supply pipe 133 to the multiple cylinder reformer 112. The multi-cylinder reformer 112 is an example of a reformer.

  The separation membrane 14 of the separation unit 50 separates water vapor and carbon dioxide from the reformed gas by allowing water vapor and carbon dioxide to pass (permeate).

  As a separation membrane for separating carbon dioxide and water vapor, for example, “Zi Tong et al., 'Water vapor and CO2 transporting through amine-contaminating transported membrane members”, Reactive circa 20 Also good.

  Further, a carbon dioxide separation membrane and a water vapor separation membrane may be combined as a separation membrane for separating carbon dioxide and water vapor.

  Carbon dioxide separation membranes include organic polymer membranes (rubber-like polymer membranes, ion exchange resin membranes, etc.), inorganic material membranes, organic polymer-inorganic material composite membranes, liquid membranes (amine aqueous solution membranes, ionic liquid membranes, etc.) Etc.

  The permeation chamber 54 of the separation unit 50 includes an air transport pipe 158 through which combustion air from the air supply unit 18 flows, and an air supply pipe 40 through which combustion air supplied to the multi-cylinder reformer 112 flows. Is connected. Combustion air supplied as a sweep gas to the permeation chamber 54 includes water vapor and carbon dioxide that have passed through the separation membrane 14, flows through the air supply pipe 40, and is supplied to the multi-cylinder reformer 112. The carbon dioxide is discharged from the gas discharge pipe 28.

(Function)
Next, the operation of the hydrogen production apparatus 110 will be described.

  As shown in FIG. 3, the city gas flows through the raw material supply pipe 133 and is supplied to the multiple cylinder reformer 112. The city gas supplied to the multi-cylinder reformer 112 is generated as reformed gas by the multi-cylinder reformer 112. The reformed gas flows through the separator 50, the compressor 80, and the hydrogen purifier 90 in this order, and the hydrogen is purified.

  The combustion air supplied as the sweep gas to the permeation chamber 54 includes water vapor and carbon dioxide that have passed through the separation membrane 14, flows through the air supply pipe 40, and is supplied to the multi-cylinder reformer 112.

  In the hydrogen production apparatus 110, carbon dioxide contained in the reformed gas is separated by using the separation membrane 14. For this reason, since the carbon dioxide is removed, the compression power is reduced, and the flow rate of the sweep gas is large, so that the size and performance of the separation membrane can be reduced. And compared with the case where the carbon dioxide contained in reformed gas is not isolate | separated by the separation membrane 14, the hydrogen purifier 90 can be reduced in size.

  Further, compared to the case where carbon dioxide contained in the reformed gas is not separated by the separation membrane 14, the hydrogen recovery rate by the hydrogen purifier 90 can be improved when the hydrogen purifier 90 is not downsized. .

  In addition, combustion air supplied to the multi-cylinder reformer 112 is used as the sweep gas. As described above, by using combustion air having a large flow rate in the gas used in the hydrogen production apparatus 110 as the sweep gas, the separation performance of water vapor and carbon dioxide is improved, and the membrane area of the separation membrane 14 is reduced. Can do.

  In addition, about another effect | action of 2nd Embodiment, the city gas containing water vapor | steam is the same as the effect | action of 1st Embodiment except flowing through the raw material supply pipe | tube 33 and supplying to the multi-cylinder reformer 112. is there.

<Third Embodiment>
An example of the hydrogen production apparatus 210 according to the third embodiment of the present invention will be described with reference to FIGS. In addition, about 3rd Embodiment, a different part from 1st Embodiment is mainly demonstrated.

(Constitution)
As shown in FIG. 6, a raw material supply pipe 133 is connected to the upper end portion of the preheating channel 32 of the multiple cylinder reformer 212 of the hydrogen production apparatus 210. The city gas is supplied directly from the raw material supply pipe 133 to the multiple cylinder reformer 212. The multi-cylinder reformer 212 is an example of a reformer.

  The separation membrane 14 of the separation unit 50 separates water vapor and carbon dioxide from the reformed gas by allowing water vapor and carbon dioxide to pass (permeate).

  In addition, in the permeation chamber 54 of the separation unit 50, as shown in FIG. 5, a communication channel pipe 260 through which the off-gas of the hydrogen purifier 90 flows, and the burner 26 of the multi-cylinder reformer 212 (see FIG. 6). The replenishment pipe 38 through which the off-gas of the hydrogen purifier 90 supplied to the gas flows is connected. The off-gas of the hydrogen purifier 90 supplied to the permeation chamber 54 as a sweep gas contains water vapor and carbon dioxide that have passed through the separation membrane 14 and is supplied as fuel to the burner 26 (see FIG. 6) of the multi-cylinder reformer 212. Is done.

(Function)
Next, the operation of the hydrogen production apparatus 210 will be described.

  As shown in FIG. 5, the city gas flows through the raw material supply pipe 133 and is supplied to the multiple cylinder reformer 212. The city gas supplied to the multiple cylinder reformer 212 is generated as reformed gas by the multiple cylinder reformer 212. The reformed gas flows through the separator 50, the compressor 80, and the hydrogen purifier 90 in this order, and the hydrogen is purified.

  Further, the off-gas of the hydrogen purifier 90 as a sweep gas flows through the communication channel pipe 260, passes through the permeation chamber 54, and is supplied as fuel to the burner 26 (see FIG. 6) of the multi-tubular reformer 212.

  In the hydrogen production apparatus 210, carbon dioxide contained in the reformed gas is separated by using the separation membrane 14. For this reason, compared with the case where the carbon dioxide contained in the reformed gas is not separated by the separation membrane 14, the hydrogen purifier 90 can be downsized.

  Further, compared to the case where carbon dioxide contained in the reformed gas is not separated by the separation membrane 14, the hydrogen recovery rate by the hydrogen purifier 90 can be improved when the hydrogen purifier 90 is not downsized. .

  The other actions of the third embodiment are the same as the actions of the first embodiment except that the city gas containing water vapor flows through the raw material supply pipe 33 and is supplied to the multi-cylinder reformer 212.

  Although the present invention has been described in detail with respect to specific embodiments, the present invention is not limited to such embodiments, and various other embodiments are possible within the scope of the present invention. It is clear to the contractor. For example, although the separation membrane 14 also separated carbon dioxide from the reformed gas, it is not necessary to separate carbon dioxide. In this case, the effect of separating carbon dioxide from the reformed gas is not achieved.

  Moreover, in the said embodiment, although city gas is used as an example of a hydrocarbon raw material, hydrocarbon raw materials other than the city gas which has methane as a main component, for example, gas which has hydrocarbons, such as propane as a main component, A hydrocarbon-based liquid may be used.

  Although not particularly described in the above embodiment, when a hydrocarbon raw material other than city gas is used, the multi-cylinder reformers 12, 112, and 212 have a structure other than the above (the hydrocarbon used) The structure may be changed to a structure suitable for the raw material.

  In the above embodiment, the hydrogen production apparatuses 10, 110, and 210 include one multi-cylinder reformer 12, 112, 212. However, the hydrogen production apparatus includes a plurality of multi-cylinder reformers 12. 112, 212 may be provided.

  Moreover, although the hydrogen production apparatuses 10, 110, and 210 according to the present embodiment are suitably used for the fuel cell system, they may be used for devices and systems other than the fuel cell system.

10 Hydrogen production equipment 12 Multiple cylinder type reformer (an example of reformer)
14 Separation membrane 33 Raw material supply pipe (an example of a flow pipe)
50 Separation unit 90 Hydrogen purifier 110 Hydrogen production device 112 Multiple cylinder reformer (an example of reformer)
210 Hydrogen production device 212 Multiple cylinder type reformer (an example of a reformer)

Claims (6)

A reformer that reforms a hydrocarbon raw material to generate a reformed gas mainly composed of hydrogen;
A separation unit having a separation membrane for separating the reformed gas discharged from the reformer by passing at least water vapor;
A hydrogen purifier for purifying hydrogen by separating the reformed gas from which water vapor has been separated into impurities and hydrogen;
A hydrogen production apparatus comprising: A compressor for compressing the reformed gas from which water vapor is separated;
The hydrogen production apparatus according to claim 1, wherein the hydrogen purifier separates the reformed gas compressed by the compressor into impurities and hydrogen.   The hydrogen production apparatus according to claim 1, wherein the separation membrane is separated from the reformed gas by passing carbon dioxide. The reformer generates a reformed gas from a hydrocarbon raw material by a steam reforming reaction,
The hydrogen production apparatus according to claim 1, further comprising a flow path pipe that returns the water vapor separated by the separation membrane to the reformer as reforming water.   The hydrogen production apparatus according to any one of claims 1 to 4, wherein a hydrocarbon raw material supplied to the reformer is used as a sweep gas that flows to the water vapor passage side of the separation membrane. The hydrogen production apparatus according to any one of claims 1 to 4, wherein combustion air supplied to the reformer is used as a sweep gas that flows to the water vapor passage side of the separation membrane.