JP5138905B2 - Dimethyl ether reformer - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a dimethyl ether reformer and a system that generates reformed gas from dimethyl ether and burns the reformed gas to generate power, and in particular, in generating the reformed gas, the power generation exhaust heat is chemically absorbed and used. The present invention relates to a dimethyl ether reformer used in a chemical regeneration power generation system using dimethyl ether.

  Dimethyl ether (hereinafter sometimes referred to as DME having the same meaning) does not generate sulfur oxides or soot during combustion, and the amount of nitrogen oxides generated can be significantly reduced. In addition to being small, it can be produced from biomass in addition to fossil fuels, so it is attracting attention as a clean new energy, and the Ministry of Economy, Trade and Industry also supports its research and development. Among them, the power generation system using the DME reformed gas can be used by converting DME into a DME reformed gas having a higher calorific value, and can recover exhaust heat by utilizing the reforming reaction (endothermic reaction). Since this is a system and a highly efficient chemical regeneration power generation system can be constructed, it is a technology that is expected to be developed (Japanese Patent Laid-Open No. 2004-144018: Patent Document 1). In order to improve the efficiency of such a chemical regeneration power generation system, it is important to maximize the amount of chemical waste heat recovered in the reformer.

  The generation reaction of the DME reformed gas in the power generation system is an endothermic reaction in which water vapor is allowed to act on DME in the presence of a suitable catalyst to generate hydrogen and carbon monoxide. Even if the endothermic reaction is intended to increase the reaction rate, the endothermic amount increases as the reaction rate increases. Therefore, if there is not sufficient heat supply from the outside, the temperature of the reaction system decreases and the reaction rate decreases. There is a relationship to end up. That is, the production reaction of the DME reformed gas is a so-called heat transfer limited reaction in which the reaction rate depends on the amount of heat supplied from the outside. Therefore, in such a chemical regeneration power generation system, in order to efficiently generate the DME reformed gas, the heat transfer property of the reformer is increased and the reaction tube (the catalyst is filled while the DME gas and steam pass through it). It is necessary to keep the inside of the reaction tube) at a high temperature.

  As means for improving the heat transfer property of the reformer and keeping the inside of the reaction tube at a high temperature, the reaction tube of the reformer is provided with fins to increase the heat transfer area, or a heat supply medium (turbine for supplying heat to the reaction tube) However, these means have a problem that not only the cost increases but also the turbine back pressure increases. Further, with these means, even if the heat transfer property of the reformer is somewhat increased, the temperature inside the reaction tube is hardly increased.

On the other hand, the CO generated by the reforming gas generation reaction may cause a shift reaction of formula (3) described later, which is an undesirable reaction, or a methanation reaction of formula (4) described later. These two reactions are both exothermic reactions and inhibit chemical exhaust heat recovery. Therefore, it is necessary to promote an endothermic reaction in the DME reforming reaction, while suppressing an exothermic reaction.
JP 2004-144018 A

The present invention has been made in view of the above-described problems of the prior art , and converts DME into a reformed gas and uses the reforming reaction (endothermic reaction) to recover exhaust heat. The purpose is to provide a vessel.

In order to achieve such an object, the dimethyl ether reformer of the present invention uses a catalyst to convert a mixed gas obtained by mixing dimethyl ether gas and steam into a hydrogen-rich dimethyl ether reformed gas. a vessel, the part of or all the internal reformer, and the catalyst, Ri Na filled by mixing an inert filler which does not contribute to the reforming reaction, wherein said catalyst is a noble metal catalyst It is characterized by being.

A dimethyl ether reformer according to another aspect of the present invention is a reformer that converts a mixed gas obtained by mixing dimethyl ether gas and steam into hydrogen-rich dimethyl ether reformed gas using a catalyst, some of or all the internal reformer, and the filling portion of the catalyst, Ri Na repeatedly formed and filled portion of the inert filler that does not contribute to the reforming reaction, the catalyst is, is the catalyst of noble metal It is characterized by that.

  In a preferred embodiment of the dimethyl ether reformer of the present invention, the amount of the catalyst in the reformer is 20 to 70% by volume of the total amount of the catalyst and the inert packing.

  In another preferred embodiment of the dimethyl ether reformer according to the present invention, the catalyst has a heat resistant temperature exceeding 370 ° C.

  The dimethyl ether reforming system of the present invention comprises the reformer of the present invention, means for driving a prime mover by burning dimethyl ether reformed gas and / or dimethyl ether, and heat for supplying prime mover exhaust heat to the reformer. Supply means.

According to the present invention, it is possible to provide a DME reformer capable of converting DME into reformed gas and recovering exhaust heat by utilizing the reforming reaction (endothermic reaction) .

(Outline of DME reforming power generation system)
FIG. 1 is a schematic explanatory diagram showing an example of a DME reforming power generation system according to the present invention. In the reformed power generation system of the present invention, DME reformed gas 101, steam 102, and compressed air 103 are mixed and combusted in a combustor 104, and a power generation turbine 105 is rotated and exhausted. The DME reformed gas 101 is a gas obtained by evaporating the DME 106 in the DME evaporation system 107, mixing with the steam 102, and reforming in the reformer 108. The steam 102 is obtained by evaporating water 109 in the evaporator 110, and part of it is used in the reformer 108 and the other part is further heated in the superheater 111 and used in the combustor 104. . The compressed air 103 is obtained by compressing the air 113 by a compressor 112 that is linked to a power generation turbine. The turbine exhaust 114 acts as a heat supply medium, passes through the superheater 111, the water evaporator 110, the reformer 108, and the DME evaporation system 107 in order, radiates and discharges the heat.

(Outline of DME reforming reaction)
The production reaction of DME reformed gas is an endothermic reaction in which steam is allowed to act on DME in the presence of a suitable catalyst to generate hydrogen and carbon monoxide. The DME reformed gas generation reaction using a noble metal catalyst is a sequential reaction via methanol represented by the following DME hydrolysis of formula (1) and methanol decomposition of formula (2) (Idemitsu Technical Report, 2005). (January 1, 48, Vol. 1, No. 10-16).
_{C 2 H 6 O + H 2} O → 2CH 3 OH - 23.6kJ / mol-DME (1)
_{CH 3 OH → CO + 2H 2} - 90.7kJ / mol-CH 3 OH (2)

  These two reactions are endothermic reactions, and chemical exhaust heat recovery can be realized by these endothermic reactions. From the viewpoint of the reaction rate, the DME hydrolysis reaction of the formula (1) is rate-limiting among these two reactions. It is known that DME and methanol disappear almost completely in chemical equilibrium if the vapor supply molar flow rate relative to the DME supply molar flow rate, that is, S / DME is set to 3 to 9 at 370 to 530 ° C. Therefore, in order to maximize the amount of exhaust heat recovery, the temperature of the reformed gas is controlled to 370 to 530 ° C., and the supply molar flow rate of steam relative to the supply molar flow rate of DME, that is, S / DME is set to 3-9. It is desirable to control so that it does.

However, CO generated by the reforming gas generation reaction may cause a shift reaction of formula (3) or a methanation reaction of formula (4), which is an undesirable reaction.
_{CO + H 2 O → CO 2} + H 2 + 41kJ / mol-CO (3)
CO + 3H ₂ → CH ₄ + H ₂ O + 206 kJ / mol-CO (4)

  These two reactions are both exothermic reactions and inhibit chemical exhaust heat recovery. In particular, in Formula (4), even if a slight amount of methane is produced, the degree of inhibition of chemical exhaust heat recovery is large in that the calorific value is large. In the exothermic reactions such as (3) and (4), the reaction rate is further increased due to the temperature rise due to the generation of reaction heat, the temperature of the reformer rises excessively, and there is CO as a reaction raw material. As long as the chemical equilibrium is reached, there is a risk of so-called heat dissipation.

  Therefore, in order to improve the efficiency of the chemical regeneration power generation system, that is, to improve the amount of chemical exhaust heat recovery, and to prevent excessive temperature rise (heat dissipation) of the reformer, (1) and (2) It is necessary to promote the endothermic reaction of (3) and to suppress the exothermic reaction of (3) and (4).

(Suppression of exothermic reaction)
First, from the viewpoint of the effect of the reformer temperature on the reaction rate, a method for promoting an endothermic reaction and suppressing an exothermic reaction will be examined. Since the activation energy of the endothermic reaction of the formulas (1) and (2) is still high even if a catalyst is used, in order to promote the reaction, it is necessary to maintain a constant high temperature according to the Arrhenius rule. However, since the activation energy of the exothermic reaction of the formulas (3) and (4) is lower than the activation energy of the endothermic reaction of the formulas (1) and (2), if the temperature is high to promote the endothermic reaction, The rate of exothermic reaction will also increase. Therefore, it is difficult to promote the endothermic reaction and suppress the exothermic reaction by simply adjusting the temperature.

  Next, from the viewpoint of the effect of the substance concentration on the reaction rate, in the state where the reforming of DME has not yet progressed, that is, in the state where a large amount of DME or methanol exists and the amount of CO is small, the raw material for the endothermic reaction is sufficient. Since it exists at a high concentration, the endothermic reaction proceeds. On the other hand, since the concentration of CO that is a raw material for the exothermic reaction is low, the exothermic reaction hardly proceeds. However, when the reforming reaction of DME progresses and there is only a small amount of DME or methanol and the amount of CO is large, the endothermic reaction hardly proceeds because the raw material concentration of the endothermic reaction is low. Since the concentration of CO is high, an exothermic reaction will proceed. Therefore, it is desirable to stop all reactions as soon as DME reforming is completed to promote endothermic reaction and suppress exothermic reaction.

  Further, from the viewpoint of the influence of heat supply on the reaction rate, when the heat supply to the reformer decreases, the temperature of the reformer decreases, so that the endothermic reaction rate decreases (so-called heat transfer rate limiting). In the endothermic reaction, when the reaction rate decreases, the endothermic amount due to the reaction also decreases, so the temperature decrease is alleviated. Conversely, when the heat supply to the reformer increases, the endothermic reaction rate increases and the endothermic amount increases, so that the temperature rise is mitigated. As described above, the endothermic reactions of the formulas (1) and (2) act in such a direction that the temperature of the reformer falls within a certain temperature range (typically about 350 to 370 ° C.). Further, in such a heat transfer rate limiting state, the endothermic reaction speed depends on the heat supply amount, so that even if the DME inflow amount itself is changed, it does not change much. On the other hand, regarding the exothermic reaction, if the exothermic reaction proceeds in a large amount even if the heat supply to the reformer is reduced, the temperature decrease is hindered by the exothermic heat generated by the reaction. ) The rate of exothermic reaction does not necessarily decrease. As the heat supply to the reformer increases, the temperature rises and the reaction rate increases and the calorific value increases according to the Arrhenius law. It will progress until it reaches (so-called heat dissipation). Therefore, in the state where DME reforming has not yet progressed, that is, in the presence of a large amount of DME and methanol and low CO, the endothermic reaction is superior to the exothermic reaction, and the heat supply to the reformer is reduced. By doing so, the temperature of the reformer can be lowered, and not only the endothermic reaction but also the rate of the exothermic reaction can be easily reduced. On the other hand, it is not always easy to adjust the reaction rate by adjusting the heat supply to the reformer after the reforming of DME progresses. Therefore, also from this point, it is desired to stop all the reactions promptly after the modification of DME is completed to promote endothermic reaction and suppress exothermic reaction, that is, to prevent heat dissipation, DME. Therefore, it is necessary to avoid long contact with the catalyst packed bed in a state in which the reforming of the catalyst proceeds and DME and methanol are reduced.

(Operation method of reformer)
Considering the characteristics of the reaction described above, in order to promote endothermic reaction while suppressing exothermic reaction to enhance chemical exhaust heat recovery and prevent heat dissipation, the reformer is operated during the operation of the reformer. It is preferable to make the endothermic reaction proceed promptly while suppressing the exothermic reaction by setting the temperature as high as possible with the upper limit of the heat resistant temperature and exhaust heat temperature of the catalyst as the upper limit, for example, 370 to 530 ° C. Then, it is preferable to stop the reaction when the endothermic reaction ends and prevent the subsequent exothermic reaction, for example, to discharge the reformed gas from the reformer or to lower the temperature of the reformed gas.

(Reformer)
The reformer is an apparatus for converting a mixed gas obtained by mixing DME and water vapor into a hydrogen-rich reformed gas using a catalyst. Typically, a plurality of reaction tubes are filled with a catalyst, a mixed gas obtained by mixing DME and water vapor is passed through the reaction tubes, and a turbine exhaust as a heat supply medium is allowed to flow around the reaction tubes. Driven. The catalyst used in the present invention is preferably a noble metal catalyst (using platinum, ruthenium, palladium, rhodium or the like) having a heat resistant temperature exceeding 370 ° C.

  And as mentioned above, in order to make the temperature of the reformer as high as possible in order to advance the endothermic reaction while suppressing the exothermic reaction to increase the recovery of chemical exhaust heat and prevent heat dissipation, It is necessary to supply sufficient heat to the reaction tube with respect to the endothermic reaction amount in the reaction tube of the reformer. However, increasing the heat transfer property of the reaction tube is often accompanied by difficult problems. Conversely, the amount of endothermic reaction and exothermic reaction per unit length of the reaction tube is decreased, and as a result, at a higher temperature. The reformer is maintained at a temperature, specifically, for example, 390 ° C. or higher, preferably 440 ° C. or higher. Specifically, a part or all of the interior of the reformer is mixed and filled with a catalyst and an inert packing that does not contribute to the reforming reaction, or part or all of the interior of the reformer is The catalyst filling portion and the filling portion of the inert packing that does not contribute to the reforming reaction are repeatedly formed. The mixing ratio is preferably 20 to 70% by volume of the catalyst with respect to the total amount of the catalyst and the inert packing. As the inert substance, silica balls, quartz balls, α-alumina, SiC, BN, SiN, or the like can be used.

  FIG. 2 is a schematic diagram of the reformer 201. A mixed gas 202 of DME and steam enters the reformer from the upper left side and passes through a number of downward flow reaction tubes 203 from the upper side to the lower side from the upper side to the lower side. Then, the gas passes through a large number of upward flow reaction tubes 204 from half to back and exits the reformer 201 as reformed gas 205 from the top left. The reaction tube is filled with a catalyst and an inert substance, and the reforming reaction proceeds while a mixed gas of DME and steam passes through the reaction tube. Turbine exhaust, which is a heat supply medium for supplying heat to the reformer, passes around the reaction tube and supplies heat to the reaction tube, while exhausting the reformer from the exhaust inlet 206 on the left front side to the back right. Pass through exit 207.

  FIG. 3 is a schematic cross-sectional view showing a filling state of the catalyst 302 and the inert packing 303 in the reaction tube 301. In FIG. 3, the catalyst 302 and the inert filler 303 that does not contribute to the reforming reaction are mixed and filled.

  FIG. 4 is a schematic cross-sectional view showing a state of filling the catalyst 402 and the inert packing 403 in the reaction tube 401. In FIG. 4, the filling portion of the catalyst 402 and the filling portion of the inert filling 403 that does not contribute to the reforming reaction are repeatedly formed. Compared to the case of mixing, such a packing method has an advantage that the ratio of the catalyst and the inert packing can be easily adjusted, and the separation process can be easily performed when the catalyst and the inert packing are extracted for replacement. is there.

(Heat supply means)
The heat supply means in the present invention is means for supplying prime mover exhaust heat to the reformer via a heat supply medium. The heat supply medium is typically turbine exhaust, but is not limited thereto as long as it is a fluid.

(Motor)
The prime mover in the DME reformed power generation system of the present invention is typically a turbine or a gas engine, and provides power for power generation in conjunction with the power generator. The prime mover is driven by burning DME and / or DME reformed gas in a combustor. Although DME itself may be burned at the time of start-up, DME reformed gas is mainly burned during rated operation.

(Evaporator)
The evaporator in the DME reforming power generation system of the present invention preferably evaporates water by motor exhaust heat, sends at least a part of the steam generated by the evaporator to the DME reformer, and also generates the generated steam. A part may be supplied to the combustor.

(DME vaporizer)
The DME vaporizer in the DME reforming power generation system of the present invention preferably evaporates DME by the exhaust heat of the prime mover, and sends at least a part of the generated DME gas to the DME reformer. Moreover, you may supply at least one part of the produced | generated DME gas to a combustor.

Example 1
Using a reaction tube made of SUS316 having an outer diameter of 34 mm and a length of 500 mm, Pt-0.5 wt%, γ-alumina supported, 3.5 mm spherical catalyst, and 3.0 mm spherical high purity alumina ball The active charge) is mixed and charged so that the catalyst is 40% of the 100% charge. The exhaust temperature is 480 ° C.

  FIG. 5 shows the temperature distribution of the reaction tube in the reformer in which the catalyst of Example 1 and the inert packing are mixed, and the temperature distribution of the reaction tube in the reformer of the conventional catalyst only.

  In the case of filling only the conventional catalyst shown by the solid line in FIG. 5, the endothermic reaction proceeds rapidly from the inlet, and thus the temperature rapidly decreases. However, when the temperature decreases to some extent, the reaction rate decreases, and the reaction endotherm and tube The temperature is constant where the amount of heat input from the radial direction is balanced. In addition, toward the outlet, the reaction rate decreases as the amount of DME or methanol that causes endothermic reaction decreases, and the temperature gradually increases. Finally, near the outlet, the endothermic reaction raw material is depleted and the reaction amount becomes extremely small. However, since CO and hydrogen gradually increase from the inlet, the exothermic reaction using these as raw materials tends to increase, and as a result, the temperature increases. It rises rapidly. An exothermic reaction raises the temperature of the reaction gas and catalyst, causing local heat dissipation.

  In the case of Example 1 in which the catalyst and the inert packing indicated by the broken line in FIG. 5 are mixed, the reaction amount and the heat input amount can be balanced at a higher temperature than in the case of the catalyst alone. For this reason, the difference in reaction rate between the endothermic reaction and the exothermic reaction is further widened, and the endothermic reaction can be rapidly advanced while suppressing the exothermic reaction.

  According to FIG. 5, it is clear that the reaction tube of Example 1 has a higher temperature particularly near the inlet where the endothermic reaction is active, and does not become much higher near the outlet where heat dissipation due to the exothermic reaction tends to occur. It is.

  FIG. 6 shows the concentration distribution of DME, hydrogen CO, and methane in the reaction tube in the reformer in which the catalyst of Example 1 and the inert packing are mixed, and the reaction tube in the reformer with only the conventional catalyst. .

  In the case of the conventional catalyst-only filling shown by the solid line in FIG. 6, DME drops from the inlet and almost disappears near the outlet. With the disappearance of DME, the concentration of hydrogen and CO rapidly decreases near the outlet, but the concentration of methane using these as raw materials has increased.

  In the case of Example 1 in which the catalyst and the inert packing indicated by the broken line in FIG. 6 are mixed, hydrogen and CO can be kept at a high concentration even near the outlet, and the concentration of methane that inhibits exhaust heat recovery can be kept low. .

  According to FIG. 6, it is clear that the reaction tube of Example 1 produces less methane as an exothermic reaction than the conventional tube.

(Example 2)
The experiment was conducted by using the same reaction tube, catalyst, and inert packing as in Example 1, exhaust gas temperature was 480 ° C., and the catalyst and inert packing were alternately packed every 20 mm.

  FIG. 7 shows the temperature distribution of the reaction tube in the reformer with the catalyst and the inert packing of Example 2 alternately and the temperature distribution of the reaction tube in the reformer of the conventional catalyst only. FIG. 7 clearly shows that the reaction tube of Example 2 has a higher temperature.

  FIG. 8 shows the concentration distribution of DME, hydrogen, CO, and methane in the reaction tube in the reformer in which the catalyst of Example 2 and the inert packing are alternately packed, and the reaction tube in the reformer with only the conventional catalyst. Indicates. FIG. 8 clearly shows that the reaction tube of Example 2 produces less methane, which is an exothermic reaction.

(Example 3)
Using the same reformer as in Example 1 and changing the mixing ratio of the catalyst and the inert substance from 0% to 100% in increments of 10% while keeping the total amount of the catalyst and the inert substance constant An assumed simulation was performed to calculate methane production, DME conversion rate, and power generation efficiency.

  FIG. 9 is a graph showing the relationship between the change in the mixing ratio of the catalyst and the inert substance and the amount of methane produced. It can be seen that the higher the catalyst ratio, the more methane production.

  FIG. 10 is a graph showing the relationship between the change in the mixing ratio of the catalyst and the inert substance and the DME conversion rate. When the catalyst is at a low ratio, if the catalyst is increased, the conversion rate increases. However, when the catalyst ratio is about 20% or more, a high conversion rate is obtained, and when the catalyst ratio is 50% or more, the conversion rate reaches 100%.

  FIG. 11 is a graph showing the relationship between the change in the mixing ratio of the catalyst and the inert substance and the power generation efficiency. When the catalyst ratio is low and the DME conversion rate is lowered, an endothermic reaction does not occur, so the amount of exhaust heat recovery is lowered and the power generation efficiency is lowered. On the other hand, when the amount of methane generated, which is an exothermic reaction, increases, the amount of exhaust heat recovered similarly decreases and the power generation efficiency decreases. Due to the interaction between the endothermic reaction and the exothermic reaction, the power generation efficiency of the system draws a convex curve. When the catalyst filling rate is 20% or less and 70% or more, the pressure loss or the like is lower than the case without reforming. Lower due to influence. Thus, when the catalyst mixing ratio is 20 to 70% by volume, it can be confirmed that the power generation efficiency without reforming is exceeded.

It is a block diagram of the dimethyl ether reforming power generation system of the present invention. It is a sketch of a reformer. It is a schematic sectional drawing which shows the filling condition of the catalyst and inactive packing in a reaction tube. It is a schematic sectional drawing which shows the filling condition of the catalyst and inactive packing in a reaction tube. It is a graph which shows the temperature distribution of the reaction tube in the case of mixing a catalyst and an inert packing, and the case of only a catalyst. It is a graph which shows the density | concentration distribution of each substance at the time of mixing a catalyst and an inert packing, and the case of only a catalyst. It is a graph which shows the temperature distribution of the reaction tube in the case of packing with a catalyst and an inert packing alternately, and the case of only a catalyst. It is a graph which shows the density | concentration distribution of each substance in the case of filling with a catalyst and an inert packing alternately, and the case of only a catalyst. It is a graph which shows the relationship between the change of the mixing ratio of a catalyst and an inert substance, and the amount of methane production. It is a graph which shows the relationship between the change of the mixing ratio of a catalyst and an inert substance, and DME conversion rate. It is a graph which shows the relationship between the change of the mixing ratio of a catalyst and an inert substance, and power generation efficiency.

101 DME reformed gas 102 steam 103 compressed air 104 combustor 105 turbine for power generation 106 DME
107 DME evaporation system 108 reformer 109 water 110 evaporator 111 superheater 112 compressor 113 air 114 turbine exhaust 201 reformer 202 mixed gas of DME and steam 203 downward flow reaction tube 204 upward flow reaction tube 205 reformed gas 206 exhaust Inlet 207 Exhaust outlet 301 Reaction tube 302 Catalyst 303 Inactive packing 401 Reaction tube 402 Catalyst 403 Inactive packing

Claims (5)

A reformer that converts a mixed gas obtained by mixing dimethyl ether gas and water vapor into hydrogen-rich dimethyl ether reformed gas using a catalyst,
Wherein a part of or all the internal reformer, and the catalyst, Ri Na filled by mixing an inert filler which does not contribute to the reforming reaction,
A dimethyl ether reformer , wherein the catalyst is a noble metal catalyst . A reformer that converts a mixed gas obtained by mixing dimethyl ether gas and water vapor into hydrogen-rich dimethyl ether reformed gas using a catalyst,
Wherein the reformer within a portion or all, the filled portion of the catalyst, Ri Na form repeating the filling portion of the inert filler that does not contribute to the reforming reaction,
A dimethyl ether reformer , wherein the catalyst is a noble metal catalyst .   The dimethyl ether reformer according to claim 1 or 2, wherein the amount of the catalyst in the reformer is 20 to 70% by volume of the total amount of the catalyst and the inert packing.   The dimethyl ether reformer according to claim 1 or 2, wherein the catalyst has a heat resistant temperature exceeding 370 ° C. A reformer according to claim 1 or 2,
Means for driving the prime mover by burning dimethyl ether reformed gas and / or dimethyl ether;
Heat supply means for supplying prime mover exhaust heat to the reformer;
Dimethyl ether reforming system including.

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