KR101785484B1

KR101785484B1 - Catalyst reactor for hydrocarbon steam reforming with excellent reaction efficiency

Info

Publication number: KR101785484B1
Application number: KR1020150117177A
Authority: KR
Inventors: 신장식; 곽인섭; 오경준; 김옥선; 조혜민
Original assignee: (주)신넥앤테크
Priority date: 2015-08-20
Filing date: 2015-08-20
Publication date: 2017-10-16
Also published as: KR20170022345A

Abstract

The present invention relates to a catalytic reactor for reforming hydrocarbon steam, which comprises a double cylindrical structure composed of an inner tube and an outer tube, and a flow path formed between the inner tube and the outer tube, At least one reforming reaction unit for generating hydrogen from the hydrocarbon-based feedstock and water vapor by means of the reforming reaction unit and at least one temperature recovery unit and inner pipe which are sequentially and repeatedly arranged in the reforming reaction unit, And a heat source supply unit for supplying reaction heat to the reforming reaction unit and the temperature recovery unit.
The hydrocarbon reactor for reforming hydrocarbon steam according to the present invention is advantageous in that a plurality of reforming reactors and a temperature recovery unit are sequentially and repeatedly arranged to uniformly distribute the temperature due to repetitive heat recovery of the raw material gas,

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a catalytic reactor for reforming hydrocarbon hydrocarbons,

The present invention relates to a catalytic reactor for hydrocarbon steam reforming, and more particularly, to a catalytic reactor for reforming hydrocarbon steam which is uniformly distributed in temperature due to repeated thermal recovery of a raw material gas, and thus has excellent catalytic reaction efficiency.

Hydrocarbon steam reforming is considered to be the cheapest method of producing hydrogen, and nearly half of the world's total hydrogen production is produced by this method. This hydrocarbon steam reforming process is a process for producing hydrogen by reacting a hydrocarbon containing methane as a main component together with steam in the presence of a catalyst. In this case, there are two reforming reactions as a main reaction and a water gas shift reaction as a side reaction. .

Scheme 1

CH ₄ + H ₂ O? CO + 3H ₂ ? 20 =? 497 kcal / mol

CO + H ₂ O? CO ₂ + H ₂ ? H = -10 kcal / mol

As shown in the above reaction scheme 1, since hydrogen is produced separately from methane and water, a high yield of hydrogen production is possible. However, since the reforming reaction is a strong endothermic reaction and the progress of the reaction is favorable under high temperature and low pressure conditions, most of the water vapor and methane are reacted in a catalytic reactor at 700-1,100 ° C under a pressure of 0-40 bar at a space velocity of 3,000-50,000 hr ^-1 To obtain hydrogen. On the other hand, the transition reaction is a mild exothermic reaction, which is advantageous at low temperature and has little effect on pressure.

As described above, since the steam reforming reaction is an endothermic reaction requiring a large amount of reaction heat, if the reaction heat is efficiently supplied to the catalyst, the reaction activity per unit catalyst is increased so that the size of the reactor can be reduced and the yield can be increased. In terms of increasing the utilization efficiency of the catalyst, a smaller particle size results in higher activity but a higher pressure loss. Therefore, a pellet type catalyst having a diameter of about 2 to 10 mm is generally used. In addition, the catalyst uses a form in which about 5 to 12% by weight of nickel, cobalt, a platinum group element or a mixture thereof is supported on a conventional heat-resistant carrier (a-alumina or calcium-aluminate). That is, the pellet type catalyst can be easily produced by immersing the heat resistant carrier in a solution containing an active metal such as nickel, cobalt, platinum group elements or a mixture thereof, and drying the resultant. If necessary, It is also said.

1A is a side cross-sectional view of a conventional catalytic reactor, and FIG. 1B is a cross-sectional view taken along line A-A of FIG. 1A. The process used for general steam reforming using a pellet type catalyst is a process in which a pellet type catalyst is filled in a tubular reactor and then a high temperature exhaust gas generated by the combustion of fuel is supplied to the outside of the tube, And the like. That is, the reactor used for hydrocarbon steam reforming is composed of a reaction part in which hydrocarbon steam reforming reaction occurs by contact with a catalyst filled with hydrocarbon and water vapor, and a flue part which transfers high-temperature reaction heat to the reaction part.

The pellet type catalyst packed in such a reactor has an advantage that the manufacturing cost is very low, but has a problem that the ratio of the exhaust gas passing through the flue gas to the reaction heat is very small.

Accordingly, as shown in FIGS. 1A and 1B, a structure in which a high-temperature reaction heat is transferred to the inside of a double tube structure is proposed. However, since the contact area between the pellet type catalyst packed in the reactor is very small, The temperature of the pellet-type catalyst far from the portion where the fuel exhaust gas is injected due to the endothermic reaction is very low, the sufficient heat source necessary for the hydrogen-hydrogen reforming reaction is not supplied and the reaction yield is remarkably decreased, .

In order to solve this problem, a method of coating a catalyst on a metal support as a method of improving the thermal conductivity of the catalyst itself and increasing the heat transfer property has been disclosed. Korean Patent Publication No. 2003-55252 and Korean Patent Publication No. 2006-78943 disclose a metal monolith catalyst in which a honeycomb-shaped metal monolith is formed of a thin metal plate and coated with an active metal such as nickel. In this case, So that the temperature of the monolithic metal catalyst can be uniformly maintained and an excellent reaction yield can be obtained. Methane conversion of about 97% can be obtained by using only pellet type catalyst, but very high methane conversion of about 99% can be obtained by using metal monolith catalyst. However, metal monolith catalysts have a disadvantage that they are not only expensive to produce, but also are not easy to produce, resulting in poor productivity.

As described above, the pellet type catalyst is superior to the metal monolith catalyst in productivity and the production cost is low. However, since the pellet type catalyst can not overcome the problem of low reaction yield, it is gradually replaced with a metal monolith catalyst having high production cost and low productivity In fact. Therefore, there is a need for a technology for a hydrocarbon reactor for reforming hydrocarbon steam, which is excellent in reaction efficiency while lowering the manufacturing cost by using a conventional pellet type catalyst.

1. Korean Patent Publication No. 10-2008-0060871

It is an object of the present invention to provide a catalytic reactor for reforming hydrocarbon steam, which is uniformly distributed in temperature due to repeated thermal recovery of a raw material gas and is excellent in catalytic reaction efficiency.

The catalytic reactor for reforming hydrocarbon steam with excellent reaction efficiency according to the present invention is a catalytic reactor for reforming hydrocarbon steam having a double cylindrical structure composed of an inner tube and an outer tube and having a flow path formed between the inner tube and the outer tube At least one reforming reaction part which is filled with a catalyst in a part of the flow path to generate hydrogen from a hydrocarbon-based feedstock and steam by a reforming reaction, and a reforming reaction part which is arranged repeatedly in succession from the reforming reaction part in the flow path, And a heat source supply unit for supplying a high temperature gas to the inner tube to transfer the reaction heat to the reforming reaction unit and the temperature recovery unit.

In one embodiment of the present invention, the flow path may be formed in a zigzag shape by disposing at least one partition plate between the inner tube and the outer tube.

In an embodiment of the present invention, the partition plate of the flow path may be vertically arranged so that the raw material moves downward in the reforming reaction unit and moves upward in the temperature recovery unit.

According to an embodiment of the present invention, the flow paths are stacked as one or more layers, but are connected to each other, so that the raw materials can move along the flow path.

According to an embodiment of the present invention, a raw material supply passage, which is disposed in contact with the upper surface of the double cylindrical structure and has a screw shape, is provided, and a part or all of the injected liquid raw material is vaporized by the heat source of the heat source supply portion, And a raw material supply unit for supplying the raw material supply unit.

According to an embodiment of the present invention, the raw material supply unit may calculate the amount of raw materials consumed in the reforming reaction and sequentially introduce the raw materials.

According to an embodiment of the present invention, the heat source supply unit includes a heat source gas distribution plate disposed in contact with a lower surface of the double cylindrical structure and distributing the introduced high temperature gas uniformly, And a heat source gas flow pipe connected to the inside of the gas source gas flow pipe and spaced apart from the inside of the inner tube of the double cylindrical structure, It may be moved upwards at an interval between the inner tube and the heat source gas flow tube and then moved downward within the heat source gas flow tube and discharged through the heat source gas outlet.

In an embodiment of the present invention, the gas of the heat source supply unit may use a high-temperature gas generated in a closed combustion reaction.

In one embodiment of the present invention, the raw materials can be prepared by mixing 2 to 5 moles of water vapor per mole of hydrocarbon.

In one embodiment of the present invention, the catalyst may be prepared by impregnating the heat-resistant support with 5-12 wt% of an active metal selected from nickel, cobalt, platinum group elements or a mixture thereof.

According to an embodiment of the present invention, the temperature recovery unit may further include a honeycomb type heat exchange unit using a metal selected from iron, stainless steel or an iron-chromium alloy.

The hydrocarbon reactor for reforming steam reforming according to the present invention is advantageous in that a plurality of reforming reactors and a temperature recovery unit are sequentially and repeatedly arranged to uniformly distribute the temperature due to repetitive heat recovery of the raw material gas,

In addition, it is possible to maximize the reaction efficiency as well as increase the hydrogen productivity in comparison with the use of the metal monolith catalyst by supplying the reaction heat smoothly.

1A is a side cross-sectional view of a conventional catalytic reactor.
1B is a cross-sectional view taken along the line AA in Fig. 1A.
2A is a perspective view of a catalytic reactor according to an embodiment of the present invention.
2B is a side cross-sectional view of a catalytic reactor according to an embodiment of the present invention.
3A is a perspective view of a reforming reaction unit and a temperature recovery unit of a catalytic reactor according to an embodiment of the present invention.
Figure 3B is a developed view of fluid flow in Figure 3A.
4A is a perspective view of a reforming reaction unit and a temperature recovery unit formed of two layers of a catalytic reactor according to an embodiment of the present invention.
FIG. 4B is a developed view of the fluid flow in FIG. 4A. FIG.
5 is a perspective view of a raw material supply portion of a catalytic reactor according to an embodiment of the present invention.
6 is a perspective view of a heat source supply unit of a catalytic reactor according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. The drawings illustrate only the essential features for the sake of clarity of the invention and are not to be construed as limiting the drawings.

FIG. 2 is a view showing a catalytic reactor according to an embodiment of the present invention, and FIG. 3 is a view showing a reforming reaction unit and a temperature recovery unit of a catalytic reactor.

The catalytic reactor 1 for reforming hydrocarbon steam according to the present invention is provided with a double cylindrical structure 200 composed of an inner tube 220 and an outer tube 210 and is provided between the inner tube 220 and the outer tube 210 And includes a reforming reaction unit 232, a temperature recovery unit 233, and a heat source supply unit 300. As the inner tube 220 and the outer tube 211, a known quartz tube or a metal such as stainless steel or iron-chrome alloy may be used as a heat resistant and oxidation resistant material.

The reforming reaction part 232 may include at least one of the hydrocarbon-based feedstock and the steam generated by the reforming reaction by filling a part of the channel 230 with a catalyst.

The raw materials can be prepared by mixing 2 to 5 moles of water vapor per mole of hydrocarbon. The hydrocarbons and water vapor supplied are brought into contact with the catalyst to cause a hydrocarbon steam reforming reaction. Hydrocarbons and water vapor can be mixed and supplied in a known range, and hydrocarbons having methane as a main component can also be used as is well known.

For example, when the reforming reaction part 232 is supplied at a space velocity of about 3,000 to about 50,000 ^{hr -1} under a pressure of ⁰ to ⁴⁰ bar while mixing and supplying the reforming reaction part at a ratio of 2 to 5 mol of steam per 1 mol of methane, Hydrogen is produced by a reforming reaction.

The catalyst may be prepared by impregnating the heat-resistant support with 5 to 12 wt% of an active metal selected from nickel, cobalt, platinum group elements or a mixture thereof. For example, the heat-resistant support may be selected from? -Alumina calcium-aluminate. The support metal may be contained in an amount of 5 to 12% by weight and may have a diameter of 2 to 10 mm. However, the present invention is not limited thereto, and it is possible to vary the content and the diameter of the carrier and the active metal, if necessary.

The temperature recovery unit 233 may be sequentially and repeatedly arranged in the flow path 230 with the reforming reaction unit 232 and may include at least one catalyst without being charged. The reforming reaction unit 232 and the temperature recovery unit 233 are sequentially and repeatedly arranged so that a sufficient heat source necessary for the hydrocarbon steam reforming reaction is smoothly supplied to the reforming reaction unit 232 to increase the reaction efficiency and increase the hydrogen productivity .

The temperature recovery unit 233 may further include a honeycomb type heat exchange unit using a metal selected from iron, stainless steel, and iron-chrome alloy. And a honeycomb type heat exchanging unit using the selected metal. Particularly, a honeycomb type that is manufactured to have 200 to 1,200 parallel fine gas flow channels per square inch of area using a metal selected from iron, stainless steel or iron-chrome alloy can be used. The heat exchanging part may be formed between the reforming reaction parts 232 filled with the catalyst to catalyze a sufficient heat source. Heat resistant and oxidation resistant metals may be used and honeycomb type gas flow passages may be used to allow movement of products including hydrocarbon, steam, and hydrogen.

The heat source supply unit 300 may supply a high temperature gas to the inner tube 220 to transfer the reaction heat to the reforming reaction unit 232 and the temperature recovery unit 233. The high temperature gas is supplied to the inside of the catalytic reactor 1 to adjust the temperature of the high temperature gas and the heat source can be located inside to have the effect of reducing heat loss compared to the heating jacket.

At this time, the gas of the heat source supply unit 300 may use a high-temperature gas generated in the closed combustion reaction. This makes it possible to produce high-temperature gas using less fuel. Considering that the optimum reaction temperature of the reforming reaction part 232 is 600 to 900 占 폚, the exhaust gas flows at a high temperature of 700 to 1,100 占 폚 as is well known.

FIG. 2A is a perspective view of a catalytic reactor according to an embodiment of the present invention, and FIG. 2B is a side cross-sectional view of a catalytic reactor according to an embodiment of the present invention.

FIG. 3A is a perspective view of a reforming reaction unit and a temperature recovery unit of a catalytic reactor according to an embodiment of the present invention, and FIG. 3B is an exploded view illustrating fluid flow in FIG. 3A.

The passage 230 may be formed in a zigzag shape by dividing the inner tube 220 and the outer tube 210 into at least one partition plate. The reforming reaction part 232 and the temperature recovery part 233 may be sequentially and repeatedly arranged in the flow path 230 partitioned by the partition plate.

The partition plate of the flow path 230 may be vertically arranged so that the raw material moves downward in the reforming reaction unit 232 and moves upward in the temperature recovery unit 233. [

FIG. 4A is a perspective view of a reforming reaction unit and a temperature recovery unit formed as two layers of a catalytic reactor according to an embodiment of the present invention, and FIG. 4B is a development view showing a fluid flow in FIG. 4A. The flow paths 230 may be stacked as one or more layers and connected to each other so that the raw materials can move along the flow path 230.

5 is a perspective view of a raw material supply portion of a catalytic reactor according to an embodiment of the present invention. The catalytic reactor (1) for reforming hydrocarbon steam according to the present invention may further include a raw material supply unit (100). The raw material supply part 100 is disposed in contact with the upper surface of the double cylindrical structure 200 and includes a screw-shaped raw material supply passage 120. A part or all of the injected liquid raw material is supplied to the heat source supply part 300, And supplies the reformed gas to the reforming reaction unit 232. In addition, the raw material supply unit 100 may calculate the amount of the raw materials consumed in the reforming reaction and sequentially flow the raw materials. The retention time can be controlled through the screw-shaped raw material supply passage 120, and the liquid fuel can be rapidly vaporized by the heat source supply unit 100.

6 is a perspective view of a heat source supply unit of a catalytic reactor according to an embodiment of the present invention. The heat source supply unit 300 may include a heat source gas distribution plate 320, a heat source gas flow pipe 330, and a heat source gas outlet 340.

The heat source gas distribution plate 320 is disposed in contact with the lower surface of the double cylindrical structure 200 to uniformly distribute the introduced high temperature gas and the heat source gas flow tube 330 has a cylindrical shape, And is inserted into the inner tube 220 of the double cylindrical structure 200 so as to be spaced apart from the inner tube 220.

The heat source gas outlet 340 is connected to the inside of the heat source gas flow pipe 330 so that the high temperature gas introduced into the heat source gas distribution plate 320 flows through the inner tube 220 and the heat source gas flow The gas can be discharged through the heat source gas outlet 340 by moving downward in the heat source gas flow pipe 330 after moving upward by an interval between the pipes 330.

As described above, the heat source supply unit 300 is formed in a structure in which a high temperature is supplied to the inside of the catalytic reactor 1 to minimize the heat loss and maximize the thermal efficiency.

As described above, in the hydrocarbon / steam reforming catalytic reactor (1) of the present invention, a plurality of reforming reaction parts (232) and a temperature recovery part (233) are sequentially and repeatedly arranged, And the catalytic reaction efficiency is excellent.

The dual cylindrical structure 200 including the raw material supply part 100, the reforming reaction part 232 and the temperature recovery part 233 and the heat source supply part 300 are separately manufactured and used in combination, There is an advantage in that it can be increased.

In order to confirm the effect of the catalytic reactor 1 according to the present invention, the following manufacturing examples are shown, but it is suggested to facilitate the understanding of the present invention, and thus the present invention is not limited thereto.

In a double cylindrical structure 200 comprising an inner tube 220 made of stainless steel having a thickness of 1 mm and an inner diameter of 23 mm and an outer tube 230 made of stainless steel having a thickness of 3 mm and an inner diameter of 39 mm, A reforming reaction part 232 in which a catalyst is filled in a flow path 230 formed between the outer pipe 230 and the outer pipe 230 and a temperature recovery part 233 in which no catalyst is filled are sequentially arranged, 233) produced two, three and four sections of the catalytic reactor (1).

The catalyst was packed using a catalyst having a diameter of 2.5 mm and 0.5 mm, which was supported on alumina so that nickel was 5% by weight.

Then, the mixed gas of 1.8 L of methane per minute and 18 L of air per minute was supplied to the burner, and the exhaust gas was supplied to the lower portion of the inner tube 220. At the same time, methane and water vapor were mixed at a molar ratio of 1: 3 and supplied at a space velocity of 9,000 hr ^{-1 to} the raw material inlet portion 100.

&Lt; Production Comparative Example &

The catalytic reactor 1 was manufactured in the same manner as in the production example except that the reforming reaction part 232 was used only between the inner pipe 220 and the outer pipe 230 without the temperature recovery part 233 .

Thereafter, the mixed gas of 1.8 L of methane per minute and 18 L of air per minute was supplied to the burner, and the exhaust gas was supplied to the lower portion of the inner tube 220, as in the manufacturing example. At the same time, methane and water vapor were mixed at a molar ratio of 1: 3 and supplied at a space velocity of 9,000 hr ^{-1 to} the raw material inlet portion 100.

The methane conversion rate was calculated based on the amount of methane in the raw material inlet 100 by measuring the amount of methane in the reformed gas outlet 234 of each of the catalytic reactors 1 manufactured in the production example, and the hydrogen yield was confirmed. The results are shown in Table 1 below.

Temperature recovery interval Conv. of NG [%] H2 yield [H2 mol / C-mol] Example 3 4 sections 99.91 3.54 Example 2 3 sections 97.28 3.27 Example 1 2 sections 85.24 2.97 Comparative Example none 73.24 2.57

As shown in Table 1, compared with the catalytic reactor of the comparative example in which the temperature recovery section of four sections was repeatedly arranged in sequence with the reforming section, the methane conversion of the catalytic reactor of the present invention was 99.92% High reaction efficiency. This methane conversion rate is equivalent to the 99% obtained using the conventional monolithic metal catalyst. Therefore, the present invention can expect a remarkably enhanced reaction efficiency while using a low-cost pellet type catalyst, and it can be confirmed that excellent hydrogen yield can be obtained even when using a pellet type catalyst which is inexpensive.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention as defined in the appended claims. It will be possible.

1: Catalytic reactor 100: Feedstock
110: feedstock feeder 120: feedstock feeder
130: Material outlet 200: Double cylindrical structure
210: outer tube 220: inner tube
230: EURO 231: Raw material inlet
232: reforming reaction unit 233: temperature recovery unit
234: reformed gas outlet 300: heat source supply part
310: heat source gas inlet 320: heat source gas distribution plate
330: heat source gas flow tube 340: heat source gas outlet

Claims

1. A catalytic reactor for reforming hydrocarbon steam, which is installed in a double cylindrical structure composed of an inner tube and an outer tube and has a flow path formed between the inner tube and the outer tube,
One or more reforming reaction units which are filled with a catalyst in a part of the flow path to generate hydrogen from hydrocarbon-based raw materials and steam by a reforming reaction;
At least one temperature recovery unit disposed in the flow path in sequence with the reforming reaction unit and not being filled with the catalyst; And
And a heat source supply unit for supplying a high temperature gas to the inner tube to transfer reaction heat to the reforming reaction unit and the temperature recovery unit,
Wherein the flow path is formed in a staggered configuration with at least one partition plate interposed between the inner tube and the outer tube and stacked with one another and connected to each other so that the raw material moves along the flow path.

delete

The method according to claim 1,
Wherein a partition plate of the flow path is vertically arranged so that the raw material moves downward in the reforming reaction unit and moves upward in the temperature recovery unit.

delete

The method according to claim 1,
A raw material supply portion which is disposed in contact with the upper surface of the double cylindrical structure and has a screw-shaped raw material supply passage and in which a part or all of the injected liquid raw material is vaporized by the heat source of the heat source supply portion and supplied to the reforming reaction portion Further comprising a catalytic reactor for reforming hydrocarbon hydrocarbons.

6. The method of claim 5,
Wherein the raw material supply unit estimates the amount of the raw material required for the reforming reaction and sequentially flows the raw material into the hydrocarbon reforming reactor.

The heat pump according to claim 1,
A heat source gas distribution plate disposed in contact with a lower surface of the double cylindrical structure and distributing the introduced high temperature gas uniformly;
A heat source gas flow pipe connected to the heat source gas distribution plate in a cylindrical shape and inserted and installed inside the inner tube of the double cylindrical structure; And
And a heat source gas outlet connected to the inside of the heat source gas flow pipe,
The gas introduced into the heat source gas distribution plate is moved upward at an interval between the inner tube and the heat source gas flow tube and then flows downward in the heat source gas flow tube and is discharged through the heat source gas outlet. Catalytic reactor.

The method according to claim 1,
Wherein the gas in the heat source supply unit uses a high-temperature gas generated in a closed-type combustion reaction.

The method according to claim 1,
Wherein the raw material is prepared by mixing 2 to 5 mol of steam per 1 mol of hydrocarbon.

The method according to claim 1,
Wherein the catalyst is supported on a heat-resistant support so as to contain 5 to 12 wt% of an active metal selected from nickel, cobalt, platinum group elements or a mixture thereof.

The method according to claim 1,
Wherein the temperature recovery section further comprises a honeycomb type heat exchange section using a metal selected from iron, stainless steel or an iron-chromium alloy.