KR102381423B1 - An apparatus for producing hydrogen and a method for producing hydrogen - Google Patents

Abstract

The present invention is an incubator in which a culture solution for culturing hydrogen-producing microorganisms that produce hydrogen using carbon monoxide is accommodated therein; and a mixer in which one side and the other side are connected to the incubator from the outside of the incubator, and a fixed fractionation part is formed therein, and the transfer culture solution, which is at least a part of the culture solution, is transferred from the incubator to the mixer and flows into one side of the mixer and the carbon monoxide flows toward the dividing unit from the front end of the dividing unit to form a gas-liquid fluid that flows toward the other side of the mixer together with the transfer culture solution, and at least a portion of the gas-liquid fluid is classified by the dividing unit and then again It joins and moves to the incubator through the other side of the mixer, and provides a hydrogen production device in which the carbon monoxide and the transfer culture solution are mixed by the classification. Also provided is a method for producing hydrogen. The present invention has the advantage that hydrogen can be effectively produced by effectively utilizing carbon monoxide.

Description

An apparatus for producing hydrogen and a method for producing hydrogen

The present invention relates to a hydrogen production apparatus for producing hydrogen and a hydrogen production method for producing hydrogen by using a hydrogen-producing microorganism, and more particularly, to a hydrogen-producing microorganism that is easy to scale-up and uses the hydrogen-producing microorganism It relates to a hydrogen production device and a hydrogen production method that can effectively produce hydrogen.

Hydrogen energy is attracting attention as a future alternative energy as a clean energy. Currently, as a hydrogen production technology, a technology for producing hydrogen using hydrogen-producing microorganisms is known. Specifically, there is known an example in which a gas bubble generator is applied to effectively deliver gaseous carbon monoxide to hydrogen-producing microorganisms that produce hydrogen from carbon monoxide (refer to Korean Patent Publication Nos. 10-1190842 and 10-1401559).

Hydrogen can be effectively produced using such a gas bubble generator, but since it is a method using rotational force or high-pressure injection force, it is not easy to increase the carbon monoxide supply in accordance with an increase in the total device capacity, so there is a limit to scale-up. In addition, it was also necessary to reduce the amount of power consumed for the operation of the gas bubble generator itself.

Republic of Korea Patent Publication No. 10-1190842, (October 15, 2012), claims Republic of Korea Patent Publication No. 10-1401559, (2014. 06. 11), claims

One problem to be solved by the present invention is to provide a hydrogen production device that is easy to scale-up and can effectively produce hydrogen compared to power consumption.

In addition, another problem to be solved by the present invention is to provide a hydrogen production method capable of easily supplying carbon monoxide in response to scale-up and effectively producing hydrogen relative to power consumption.

The problems to be solved by the present invention are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

The present invention is an incubator in which a culture solution for culturing hydrogen-producing microorganisms that produce hydrogen using carbon monoxide is accommodated therein; and a mixer in which one side and the other side are connected to the incubator from the outside of the incubator, and a fixed fractionation part is formed therein, wherein the transfer culture solution, which is at least a part of the culture solution, is transferred from the incubator to the mixer introduced to one side, and the carbon monoxide flows toward the dividing unit from the front end of the dividing unit to form a gas-liquid fluid flowing toward the other side of the mixer together with the transfer culture solution, and at least a portion of the gas-liquid fluid is classified by the dividing unit After being joined again, it moves to the incubator through the other side of the mixer, and provides a hydrogen production device in which the carbon monoxide and the transfer culture solution are mixed by the classification.

The classification unit may include a mixing unit having one or more shapes selected from protrusions or plate shapes.

The mixing unit is plural, each mixing unit is formed in a plate shape, and the other mixing unit connected to one mixing unit is connected in series, and may be coupled to each other in a twisted state.

Each of the mixing units may be formed in a shape twisted with respect to the flow direction as a reference axis.

The mixing may occur while additionally undergoing a process of conversion or reverse change of the flow of the gas-liquid fluid.

A plurality of mixers may be disposed, and one mixer may be disposed in parallel with at least another mixer.

The one mixer and the other mixer may be connected to different pumps.

The different pumps may be connected to the front end of each of the one mixer and the other mixer, respectively.

The other side of the mixer may be connected to the incubator by a fluid discharge connection pipe, and the one mixer and the other mixer may be connected to different fluid discharge connection pipes.

The hydrogen production device may further include a collecting unit for collecting the hydrogen produced by the hydrogen producing microorganism.

The hydrogen production apparatus may further include a culture medium transfer unit connecting one side of the mixer and the incubator.

A carbon monoxide supply unit may be connected to one side of the culture medium transfer unit.

The culture medium transfer unit may include a pump, a suction pipe for transferring the transfer culture liquid from the incubator to the pump, and a transfer tube for transferring the transfer culture liquid from the pump to the mixer.

The one mixer and the other mixer may be connected to different culture medium transfer units.

The different culture medium transfer unit may share at least a portion of the suction tube.

The mixer includes a tubular housing, a fluid inlet portion formed on one side of the housing and into which the carbon monoxide and the transfer culture solution are introduced, and a fluid discharge part formed on the other side of the housing and mixed with the carbon monoxide and the transfer culture liquid to be discharged can be included.

The classification part may be fixed to the inside of the housing by a fixing part, and the fixing part may be formed on one side of the classification part.

The fixing part may be coupled to one side of the fluid inlet part.

A step may be formed on one side of the fluid inlet, and the fixing part may be coupled to the step by fitting.

The fixing part may be fixed in close contact with the fluid inlet by the pressure of the transfer culture solution.

A cross-sectional area of the fluid inlet portion may be formed so as not to be greater than a cross-sectional area of the fluid discharge portion.

The hydrogen-producing microorganisms may be uniform in the genus Thermococcus.

The thermococcus genus may be Thermococcus onnurineus.

In addition, the present invention is (A) using carbon monoxide in a culture medium for cultivating hydrogen-producing microorganisms that produce hydrogen in an incubator for accommodating therein, at least a portion of the culture medium as a transfer culture medium, and a fractionation unit fixed therein an inflow step of introducing the formed mixer to one side and introducing the carbon monoxide from the front end of the dividing unit toward the dividing unit; (B) the introduced transfer culture solution and the introduced carbon monoxide flow together toward the other side of the mixer to form a gas-liquid fluid, and at least a portion of the gas-liquid fluid is classified by the dividing unit, so that the carbon monoxide and the transferred culture solution are mixed a mixing step of forming a mixture; (C) generating hydrogen by moving the mixture into the incubator through the other side of the mixer, culturing the hydrogen-producing microorganisms to generate hydrogen; And (D) provides a hydrogen production method comprising a hydrogen capture step of collecting the hydrogen produced by the hydrogen-producing microorganisms using the carbon monoxide.

The culturing in step (C) may be carried out under pressure.

According to the present invention, scale-up is easy, and hydrogen can be effectively produced relative to power consumption. In addition, according to the present invention, it is possible to stably increase the carbon monoxide supply according to an increase in the volume of the culture medium for hydrogen production, so it is possible to easily supply carbon monoxide in response to scale-up, and there is an effect that hydrogen productivity is excellent compared to power consumption. .

1 is a schematic diagram showing an embodiment of the hydrogen production apparatus of the present invention.
FIG. 2 is an exploded perspective view showing an example of a mixer included in the embodiment of FIG. 1 .
3 is a partially cut-away perspective view illustrating an example of a mixer included in the embodiment of FIG. 1 .
4 is a diagram illustrating a connection method of the mixer of FIG. 3 .
FIG. 5 is a diagram for explaining a mixing method of a classification unit included in the embodiment of FIG. 1 .
6 is a schematic diagram showing another embodiment of the hydrogen production apparatus of the present invention.
7 is a flowchart for explaining an embodiment of the hydrogen production method of the present invention.
8 is a graph showing the experimental results of Specific Example 1.
9 is a graph showing the experimental results of Example 1.
10 is a graph showing the experimental results of Example 1.
11 is a schematic diagram of a hydrogen production apparatus to which the gas bubble generator of Reference Example 1 is applied.
12 is a perspective view of the gas bubble generator of FIG. 11 .
13 is a graph showing the experimental results of Experimental Example 2.

Hereinafter, the advantages and features of the present invention, and a method of achieving them will become apparent with reference to the embodiments described below in detail in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only these embodiments allow the disclosure of the present invention to be complete, and common knowledge in the art to which the present invention pertains It is provided to fully inform those who have the scope of the invention, and the present invention is only defined by the scope of the claims.

Like reference numerals refer to like elements throughout. Also, “and/or” includes each and every combination of one or more of the recited elements.

The terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, "comprises" and/or "comprising" refers to the presence of one or more other components, steps, operations and/or elements mentioned. or addition is not excluded.

In this specification, 'front end' and 'rear end' may be divided based on the flow direction of a fluid (gas, liquid, or gas-liquid fluid). The 'front end' may refer to a side through which the fluid flows or a portion connected thereto, and the 'rear end' may refer to a side through which the fluid is discharged or a portion connected thereto. For example, an inlet side or a portion connected thereto of a device, a component, a conduit through which a fluid flows can be expressed as a front end of the device, a component, a conduit, etc., and an outlet side or a portion connected thereto is the device, a component , can be expressed as the rear end of the pipe. Disposed or connected to the front end means to be disposed or connected to the inlet side, disposed or connected to the rear end may mean to be disposed or connected to the outlet side.

The hydrogen-producing microorganism may be a microorganism capable of producing hydrogen, preferably a microorganism capable of producing hydrogen using carbon monoxide as a carbon source. For example, it may be a hydrogen-producing anaerobic microorganism such as Thermococcus genus. The genus Thermococcus is an anaerobic microorganism belonging to the genus Thermococcus and capable of hydrogen production, and is meant to include a strain of the genus Thermococcus (cell line). Although not limited thereto, a preferred example of the genus Thermococcus may be Thermococcus onnurineus, and more preferably a variant of the Thermococcus onnurinews NA1 and/or Thermococcus onnurineus NA1 strain. can

Carbon monoxide as a carbon source may be in the form of carbon monoxide alone or mixed with other types of gas.

Unless otherwise stated, culture medium means a culture medium capable of culturing conventional hydrogen-producing microorganisms, and may be a known culture medium capable of culturing Thermococcus genus bacteria. The culture medium uses carbon monoxide and water, including water, so that hydrogen-producing microorganisms can produce hydrogen. At this time, the culture medium may contain hydrogen-producing microorganisms.

Hereinafter, with reference to FIGS. 1 to 5, an embodiment of the hydrogen production apparatus of the present invention will be described in more detail.

1 is a schematic diagram showing an embodiment of a hydrogen production apparatus of the present invention, FIG. 2 is an exploded perspective view showing an example of a mixer included in the embodiment of FIG. 1, and FIG. 3 is an embodiment of FIG. It is a partial cut-away perspective view showing an example of the included mixer, FIG. 4 is a diagram showing a connection method of the mixer of FIG. 3, and FIG. 5 is a diagram for explaining the mixing method of the classification unit included in the embodiment of FIG. am.

As shown in FIG. 1 , the hydrogen production device 1 includes an incubator 100 , and a mixer 200 . In addition, the hydrogen production device 1 may further include a collecting unit 500 .

The incubator 100 accommodates therein a culture solution for culturing hydrogen-producing microorganisms that produce hydrogen using carbon monoxide. The incubator 100 refers to a vessel in which hydrogen production mainly occurs by hydrogen-producing microorganisms. The incubator may be an anaerobic incubator, and the incubator 100 may be a well-known incubator of a closed structure that can keep the interior of the incubator anaerobic. The incubator 100 is equipped with a window such as an observation window (not shown) so that the inside of the incubator 100 can be checked from the outside. Alternatively, it may have a structure in which a pH adjusting agent supply means including a pH adjusting agent supply pipe or the like is mounted, and may be commercially available.

In addition, a pedestal (not shown) for supporting the incubator 100 may be installed, and a culture medium transfer unit 300 may be further installed on one side of the incubator 100 . In addition, an inlet for introducing the culture solution and an outlet for discharging the culture solution may be formed in the incubator. A new culture solution may be added by such an inlet and an outlet, and the used culture solution may be discharged. The culture medium is a culture medium capable of culturing hydrogen-producing microorganisms, and the culture medium may contain hydrogen-producing microorganisms.

The culture medium transfer unit 300 serves as a conduit for transferring the transfer culture medium from the incubator 100 to the mixer 200 by using at least a portion of the culture medium as a transfer culture medium. The culture medium transfer unit 300 includes a pump 350 , a suction pipe 370 for transferring the transfer culture liquid from the incubator 100 to the pump 350 , and a transfer pipe for transferring the culture liquid from the pump 350 to the mixer 200 . 330 may be included. In addition, the culture medium transfer unit 300 connects one side of the mixer 200 and the incubator 100 , and the carbon monoxide supply unit 400 may be connected to one side of the culture medium transfer unit 300 . With such a configuration, at least a portion of the culture medium inside the incubator 100 is transferred to the mixer 200 as a transfer culture liquid, and carbon monoxide can be supplied to the transfer culture liquid being transferred, and the transfer culture liquid supplied with carbon monoxide is mixed with a mixer (200) can be introduced.

The carbon monoxide supply unit 400 includes a carbon monoxide supply source 410 and a gas supply pipe 430 , and may adjust the flow rate of the carbon monoxide gas by a flow rate controller 450 such as a Mass Flow Controller (MFC).

The carbon monoxide source 410 may be a tube or a cylinder filled with carbon monoxide, the end of which is connected to a carbon monoxide emission source (not shown).

One side and the other side of the mixer 200 are connected to the incubator 100 from the outside of the incubator 100 , and a fixed classification unit (see 240 in FIG. 2 ) is formed therein. The transfer culture medium, which is at least a part of the culture medium, is transferred from the incubator 100 to the mixer 200 and flows into one side of the mixer 200, and carbon monoxide flows from the front end of the classification unit 240 toward the division unit 240. Together, the gas-liquid fluid flows toward the other side of the mixer 200, and at least a portion of the gas-liquid fluid is classified by the classification unit 240 and then rejoins and moves to the incubator 100 through the other side of the mixer 200, By sorting, carbon monoxide and the transfer medium are mixed.

Hereinafter, the mixer will be described in more detail with reference to FIGS. 2 and 3 .

The mixer 200 includes a tubular housing 210, a fluid inlet 220 formed on one side of the housing and into which carbon monoxide and a transfer culture solution are introduced, and a fluid discharge that is formed on the other side of the housing and discharges the mixed carbon monoxide and transfer culture solution. The unit 230 may be included.

A fixed classification unit 240 is formed inside the mixer 200 . The classifying unit 240 may include a mixing unit 241 having one or more shapes selected from protrusions or plate shapes, and the mixing unit 241 may be formed in plurality, and each mixing unit 241 is a plate. The shape is made, and the other mixing unit connected to one mixing unit is connected in series, and may be coupled to each other in a twisted state.

That is, each mixing unit is connected in series along the flow direction of the gas-liquid fluid, so that the gas-liquid fluid can be repeatedly classified. For example, as shown in the enlarged part of the mixing unit of FIG. 2, each mixing unit is coupled to each other in a twisted state, so whenever it passes through one mixing unit, it is classified into two flows, 2 ⁿ (n may go through a process of being classified into the number of mixing units).

As shown in FIG. 2 , a fixing part 250 may be formed on one side of the classification part 240 . The classification unit 240 is fixed inside the housing 210 by the fixing unit 250 . At this time, a stepped 221 may be formed on one side of the fluid inlet 220 formed on one side of the housing 210 , and the fixing unit 250 may be coupled to the stepped 221 by fitting. That is, as shown in FIG. 3 , the classification unit 240 may be fixed to the inside of the housing by the fixing unit 250 . The fixing part 250 can be completely fixed to the fluid inlet 220 by the pressure of the transported culture fluid generated when the transported culture fluid flows into the housing, so that the dividing part 240 is firmly attached to the inside of the housing 210 . can be fixed firmly. With such a structure, the classification unit 240 is firmly fixed inside the housing 210 , and at the same time, the classification unit 240 may be easily disassembled from the housing 210 if necessary. The fixing part 250 may include a body part 251 that is accommodated in a step, and a flow hole 252 through which one or more selected from a transfer culture solution or carbon monoxide can pass is formed on one side, and the other side. The flow hole 252, one side of the mixing unit 241 extends into the flow hole 252, and may be formed in a form in which the flow hole 252 is divided by the mixing unit 241, the transfer culture solution or At least one selected from among carbon monoxide may be classified as it passes through the flow hole 252 .

The mixer 200 is located outside the incubator 100 and receives from the incubator at least a portion of the culture solution accommodated in the incubator 100 as a transfer culture solution. Since the mixer 200 can be located outside, there is no restriction on the size of the mixer, and the mixer 200 itself can be extended according to circumstances and conditions, such as arranging in parallel or in series, so it is easy to scale-up . Therefore, in response to a change in the capacity of the culture medium, stable and sufficient hydrogen production is possible.

The mixer is a fixed-type mixer in a tube capable of mixing a gas phase and a liquid phase, and may be one commonly used in an industrial field, and may be a static mixer for mixing a gas phase and a liquid phase.

As shown in FIG. 4 , the mixer 200 may be connected to the incubator (see 100 in FIG. 1 ) through the culture medium transfer unit 300 . The culture medium transfer unit 300 may be connected to a fluid inlet (refer to 220 of FIG. 2 ) formed on one side of the mixer 200 . At this time, the culture medium transfer unit 300 and the mixer 200 may be connected by a flange coupling. That is, the first flange 301 formed at the rear end of the culture medium transfer unit 300 is connected to the second flange 201 formed at the front end of the mixer 200 by flange coupling, the first flange 301 and the second flange The bolt 901 is inserted into the fastening hole 903 formed on the circumference of the 201 , and the conduit can be connected by coupling the bolt 901 with the nut 902 . When the culture medium transfer unit 300 and the mixer 200 are connected, the culture medium transferred through the culture medium transfer unit 300 is introduced into the mixer 200 .

The carbon monoxide supply unit 400 may be connected to one side of the culture medium transfer unit 300 , and carbon monoxide may be introduced into the mixer 200 in the same direction as the transfer culture medium. By this same direction inflow, the transfer culture solution and carbon monoxide form a gas-liquid fluid, which is a flow composed of carbon monoxide and the transfer culture solution.

In this way, the gas-liquid fluid composed of the transfer culture solution and carbon monoxide forms a flow in the same direction.

The transfer culture medium and carbon monoxide flowing in the same direction pass through the classification unit (refer to 240 in FIG. 3) fixed inside the mixer while maintaining the flow naturally. As described above, the classifying unit 240 may include a mixing unit (refer to 241 of FIG. 3 ) formed of one or more shapes selected from protrusions or plate shapes.

The mixing unit 241 may be made of a plurality, each mixing unit is formed in a plate shape, and the other mixing unit connected to one mixing unit is connected in series, and may be coupled to each other in a twisted state, Each mixing unit also has a shape twisted with respect to the flow direction in which the transfer culture solution and carbon monoxide flow, so that the mixing of the gas-liquid fluid formed by the transfer culture solution and carbon monoxide can be performed more effectively and efficiently. Referring to FIG. 5, the mixing of gas-liquid fluid is primarily classified (or divided) as it passes through the mixing unit as each mixing unit is coupled to each other in a twisted state, as shown in FIG. can be done (see arrow). In addition, as the gas-liquid fluid moves along the surface of the mixing unit having a twisted shape, as shown in FIG. 5B , the direction of the flow may be changed (see arrow). In addition, as shown in (c) of FIG. 5, the gas-liquid fluid causes a vortex between the inner wall of the housing and the twisted inclined surface formed in the mixing unit itself, and the reverse of the flow is induced (see arrow). Therefore, the gas-liquid fluid can be mixed naturally by the classification unit.

Through such mixing, gaseous carbon monoxide is evenly dispersed in the liquid transfer culture medium to form microbubbles, and the mass transfer efficiency of carbon monoxide is increased. The microbubbles may have an average diameter of 100 to 1000 μm. Since the hydrogen-producing microorganisms exist in a state in which microbubbles are formed evenly, the environmental change is maintained, and the hydrogen-producing microorganisms seem to be less stressed by the environmental change. In addition, the gas-liquid fluid is pressurized while passing through the mixing unit, so that the gaseous carbon monoxide is more effectively dissolved in the liquid-phase transfer culture solution.

As a result, in a stable environment and in the presence of carbon monoxide suitable for use by being dissolved in the transfer culture medium, the hydrogen-producing microorganisms can produce stable hydrogen.

With this structure, more stable hydrogen production is possible without adding additional rotational force for mixing or power for generating high-pressure injection force, and since high pressure is not applied to the device, durability of the device can be secured and stable operation is also possible. .

In addition, the mixed carbon monoxide and the transfer culture solution are discharged to the fluid discharge unit (refer to 230 in FIG. 3 ), pass through the fluid discharge unit connection pipe 310 and move to the incubator.

The fluid discharge unit (refer to 230 in FIG. 3) and the fluid discharge unit connection pipe 310 are also similar to the above-described connection method between the mixer 200 and the culture medium transfer unit 300, the fluid discharge unit (refer to 230 in FIG. 3). A fastening hole formed on the circumference of the third flange (refer to 202 in FIG. 4) formed at the rear end of the fourth flange (refer to 311 in FIG. 4) formed at the front end of the fluid discharge connection pipe (refer to 310 in FIG. 4) (Refer to 903 in FIG. 4), it can be fixed by flange coupling with a bolt (refer to 901 in FIG. 4) and a nut (refer to 902 in FIG. 4).

As the gas-liquid fluid flows naturally by the classification unit (refer to 240 in FIG. 3) fixed inside the mixer 200 and mixing is made during the flow, the pressure exerted on the hydrogen-producing microorganisms inside the transfer culture solution constituting the gas-liquid fluid Rapid changes can be avoided, and bubbles generated in the gas-liquid fluid can be uniformly dispersed, so that the exposure of hydrogen-producing microorganisms to environmental resistance stress is reduced. In addition, gas-liquid mass transfer is effectively performed even in a state in which power consumption is relatively low. As described above, in the case of the present invention, since it is possible to maintain a constant width of the pressure change, the environmental stress on the hydrogen-producing microorganisms is small, and the gas-liquid mass transfer efficiency is excellent even at low power, so that hydrogen production is possible effectively. This will be described in more detail in specific examples and experimental examples to be described later.

In addition, since the transferred culture medium continuously introduced into the mixer is a part of the culture medium accommodated inside the incubator, it is possible to prevent dilution of the hydrogen-producing microorganisms contained in the culture medium, thereby enabling stable hydrogen production.

As described above, with a simple structure, hydrogen can be produced without additional power consumption, and thus hydrogen can be effectively produced according to the present invention. This will also be described in more detail through specific examples and experimental examples to be described later.

The collecting unit 500 collects gaseous hydrogen generated from the incubator 100 . The collecting unit 500 includes a known hydrogen storage unit 510 and a gas discharge pipe 570 such as a pipe having an end connected to a hydrogen demander or a gas storage tank. The collecting unit 500 may collect gas generated during the culturing process in addition to hydrogen, and the gas collected by the collecting unit 500 may undergo a purification process to increase the purity of hydrogen.

The tablet may be integrally formed in the collecting unit 500 . A filter or the like may be disposed at the front end of the hydrogen storage unit 510 to prevent unwanted substances from entering. In addition, by installing a cooling unit 550 in the gas discharge pipe 570 to lower the temperature of the discharged gas, the volume is reduced to increase the capacity of the hydrogen storage unit 510 or to prevent damage due to high temperature. effect can be shown. The cooling unit 550 may be a known cooling device, and may cool the discharged gas by circulating a refrigerant.

Hereinafter, with reference to FIG. 6, it will be described in more detail with respect to another embodiment of the hydrogen production apparatus of the present invention.

Contents overlapping with one embodiment of the hydrogen production apparatus of the present invention are omitted as much as possible to avoid overlap, and differences are mainly described.

6 is a schematic diagram showing another embodiment of the hydrogen production apparatus of the present invention, showing an example in which a plurality of mixers are applied.

As shown in FIG. 6 , the hydrogen production device 1 ′ includes an incubator 100 , and mixers 200 and 200 ′. As shown, the mixer consists of a plurality. By applying a plurality of mixers in this way, it is possible to easily increase the amount of the transfer culture solution and the carbon monoxide mixture. When the amount of the transfer culture medium and the carbon monoxide mixture is increased, the amount of microbubbles is also increased accordingly, so that mass transfer can occur more effectively.

In this case, one mixer 200 may be disposed in parallel with at least another mixer 200 ′. By disposing one mixer 200 in parallel with at least another mixer 200 ′, it is possible to more easily increase the amount of the transfer culture solution and carbon monoxide mixture supplied to the incubator. In this way, by allowing one mixer 200 to be arranged in parallel with at least another mixer 200 ′, it is possible to increase the amount of generation of the transfer culture solution and carbon monoxide mixture, as well as increase the amount of gas-liquid fluid transferred per hour. because there is In order to introduce the transfer culture solution to the mixer, a pump may be connected. Although not limited thereto, a pump may be connected upstream of the mixer.

One mixer 200 and the other mixer 200' may be connected to different pumps. For example, one pump 350 may be connected to one mixer 200 , and the other pump 350 ′ may be connected to another mixer 200 ′. In this case, it is possible to easily increase the transfer speed of the transfer culture medium only by adding a relatively low-capacity pump in a small number. That is, each mixer 200, 200' is applied in parallel, and a relatively low-capacity pump is added to each mixer, respectively, to easily increase the amount of the transfer culture medium and carbon monoxide mixture and the transfer speed of the transfer culture liquid. it can be This is also confirmed from the results of the experimental examples. In addition, although not limited thereto, different pumps may be connected to the front end of each of the one mixer 200 and the other mixer 200 ′, respectively.

Each mixer placed in parallel can be connected to the incubator in a variety of ways. Although it is shown in the drawing that each mixer 200, 200' is connected to face each other at an angle of 180 degrees, the present invention is not limited thereto. It may be connected to have various angles such as 240 degrees. As shown in FIG. 6 , if the respective mixers 200 and 200 ′ are connected to face each other, drift that may occur when a large amount of the culture solution is introduced only from one side can be effectively prevented.

In order to connect the incubator and the plurality of mixers, the hydrogen production device 1 ′ may include a plurality of fluid discharge unit connection pipes 310 and 310 ′. The fluid discharge part connecting pipe is a pipe connecting the other side of the mixer and the incubator. One mixer 200 and the other mixer 200 ′ may be connected to the incubator 100 through different fluid discharge connection pipes 310 and 310 ′. One fluid discharge unit connection pipe 310 is substantially the same as the fluid discharge unit connection pipe 310 of an embodiment, and the other fluid discharge unit connection pipe 310 ′ is one fluid discharge unit connection pipe 310 . ) is practically the same as Through each of the fluid discharge part connection pipes 310 and 310', the mixture generated in each mixer can be introduced into the incubator without being affected by other mixers.

In addition, the hydrogen production device (1 ') may include a plurality of culture medium transfer unit (300, 300'), each pump (350, 350') to be included in each culture medium transfer unit (300, 300'). can Each culture medium transfer unit may include a transfer tube and a suction tube in addition to the pump, respectively, and one mixer 200 and the other mixer 200 ′ may be connected to different culture medium transfer units 300 and 300 ′. there is. The different culture medium transfer unit comprises one culture transfer unit and the other culture medium transfer unit. At this time, one culture medium transfer unit may be connected to one mixer, and the other culture medium transfer unit may be connected to the other mixer. Each of the one culture medium transfer unit and the other culture medium transfer unit may have substantially the same range as the culture medium transfer unit described in one embodiment. That is, one culture medium transfer unit 300 is substantially the same as the culture medium transfer unit of an embodiment, and the other culture medium transfer unit 300 ′ may be substantially the same as one culture medium transfer unit 300 . therefore. The transfer tube, pump, and suction tube described in one embodiment are substantially the same as one transfer tube 330 , one pump 350 , and one suction tube 370 included in one culture medium transfer unit 300 , respectively. and the other transfer pipe 330 ′, the other pump 350 ′, and the other suction pipe 370 ′ included in the other culture medium transfer unit 300 ′ may be substantially the same. At this time, different culture medium transfer units may share at least a portion of the suction tube. For example, the other suction pipe 370 ′ is branched from one suction pipe 370 as shown in FIG. 6 , and may be of a shared form. However, the suction tube (370, 370') is not limited to the branching method in which the connection method with the incubator 100, each suction tube (370, 370') is spaced apart from each other and may be directly connected to the incubator 100 Of course.

In the drawing, one mixer 200 and the other mixer 200 ′ are connected to different pumps, and each pump is transferred from one suction pipe 370 and the other suction pipe 370 ′ branched therefrom. is transferred, and one mixer 200 and the other mixer 200 ′ are illustrated as being connected to the incubator 100 through different fluid discharge connection pipes 310 and 310 ′, respectively, but the present invention is not limited thereto. .

In addition, the hydrogen production device 1 ′ may include a plurality of carbon monoxide supply units 400 and 400 ′. Each of the carbon monoxide supply units 400, 400' may include a respective carbon monoxide supply source (410, 410'), gas supply pipes (430, 430'), and the flow rate controller (450, 450'). Each carbon monoxide supply unit including each carbon monoxide supply source, the gas supply pipe, and the flow regulator may also be substantially the same as described in the embodiment. With such a configuration, at least a portion of the culture medium inside the incubator 100 is transferred to the plurality of mixers 200 and 200 ′ as a transfer culture liquid, and carbon monoxide can be supplied to the transfer culture liquid being transferred, and carbon monoxide is supplied The transferred culture solution may be introduced into the incubator 100 .

In addition, the hydrogen production device 1 ′ may further include a collecting unit 500 . The collecting unit 500 is a device for collecting gaseous hydrogen generated from the incubator 100 , and may be substantially the same as the collecting unit 500 of an embodiment. Accordingly, the hydrogen storage unit, the cooling unit, and the gas discharge pipe described in one embodiment are the hydrogen storage unit 510, the cooling unit 550, and the gas discharge pipe 570 included in the collecting unit 500 of another embodiment, respectively. may be substantially the same as

In addition, the contents mentioned in the hydrogen production apparatus 1 according to an embodiment of the present invention can be applied to the hydrogen production apparatus 1 ′ according to another embodiment of the present invention in the same range as long as they do not contradict each other.

Hereinafter, an embodiment of the method for producing hydrogen of the present invention will be described in more detail with reference to FIG. 7 .

The contents mentioned in one embodiment and another embodiment of the hydrogen production apparatus of the present invention are applied in the same range to one embodiment of the hydrogen production method, and the contents to be mentioned in one embodiment of the hydrogen production method are also hydrogen production in the same range Applies to one embodiment and another embodiment of the device.

7 is a flowchart showing an embodiment of the hydrogen production method of the present invention.

As shown in FIG. 7 , the hydrogen production method according to an embodiment of the present invention comprises (A) an inlet step, (B) a mixing step, (C) a hydrogen generation step, and (D) a hydrogen capture step.

(A) In the inflow step, in an incubator accommodating therein a culture solution for culturing hydrogen-producing microorganisms that produce hydrogen using carbon monoxide, at least a portion of the culture solution is transferred to one side of the mixer in which a fractionation part fixed therein is formed. and introducing carbon monoxide from the front end of the classification unit toward the classification unit. The transfer culture solution is a part of the culture solution, and refers to the culture solution introduced into the mixer 200 . The mixer 200 may be applied in the same range as those mentioned in an embodiment of the hydrogen production device, which is an embodiment of the present invention.

(B) In the mixing step, the transferred culture solution introduced into the mixer and the introduced carbon monoxide flow together toward the other side of the mixer to form a gas-liquid fluid, and at least a part of the gas-liquid fluid is classified by the dividing unit so that carbon monoxide and the transferred culture solution are mixed to form a mixture. The transfer culture medium and carbon monoxide flow together, form a gas-liquid fluid, pass through the mixing unit forming the classification unit, and are classified, and the gas-liquid fluid is further mixed through a flow conversion or reverse process to form a mixture. In this process, uniformly and finely dispersed microbubbles can be naturally formed in the mixture. Through these steps, the hydrogen-producing microorganisms in the transfer culture medium can be more easily supplied with carbon monoxide by the uniformly dispersed microbubbles, and can receive less environmental stress, thereby making it easier to generate hydrogen.

(C) The hydrogen generation step is a step of generating hydrogen by culturing hydrogen-producing microorganisms by moving the mixture into the incubator through the other side of the mixer. At this time, the culture may be carried out under pressure.

In step (C), hydrogen generation can be carried out by changing the volume of CO added to medium volume per minute; CO volume/medium volume/minute; vvm) to increase with the elapsed culture time. there is. In this way, by changing the vvm according to the elapsed culture time, hydrogen can be produced more effectively and stably. By changing the volume ratio (vvm) of the amount of carbon monoxide injected to the culture solution per minute to increase with the elapsed culture time, the hydrogen-producing microorganisms adapt to carbon monoxide, and hydrogen production is possible in a state suitable for hydrogen production.

The volume ratio (vvm) of the amount of carbon monoxide injected with respect to the culture solution per minute may be variously changed and applied.

As an example, the starting vvm that is vvm at the start of the culture may be 0.10 vvm. At the starting vvm, the hydrogen-producing microorganisms adapt to the environment and grow to a state suitable for hydrogen production, and then increase the transfer amount of the culture medium while maintaining the starting vvm to determine the amount of hydrogen that the hydrogen-producing microorganisms can produce using carbon monoxide. can be increased more effectively. In addition, if vvm is increased, the supply rate of carbon monoxide that can be used by hydrogen-producing microorganisms for hydrogen production increases, so the hydrogen production rate may also increase. For example, the starting vvm may be 0.10 vvm, and the change vvm in which the starting vvm is changed and increased to vvm may be 0.20 to 0.24 vvm.

In addition, by increasing the pressure inside the incubator, the solubility of a gas (eg carbon monoxide) can be increased, and as a result, it seems that effective hydrogen production is possible. At this time, the pressure inside the incubator may be, for example, 0.5 to 1 bar pressurized. That is, the culture may be performed by pressurizing the internal pressure of the incubator by 0.5 to 1 bar.

As described above, the solubility of carbon monoxide gas in the culture medium can be increased through the mixer supplying carbon monoxide, and it seems that stable hydrogen production is possible due to high mass transfer efficiency. In addition, hydrogen can be effectively produced compared to the amount of electricity consumed. This effect can also be confirmed in an experimental example to be described later.

(D) The hydrogen capture step is a step in which the hydrogen-producing microorganisms collect the hydrogen produced by using carbon monoxide. It is possible to capture by applying a hydrogen collecting unit in the same range as that mentioned in the description of the hydrogen production device, which is an embodiment of the present invention.

The capture may be to capture the hydrogen produced by the hydrogen-producing microorganisms using carbon monoxide.

In order to avoid repetition, descriptions of overlapping parts are omitted, but the contents mentioned in the hydrogen production method according to an embodiment of the present invention are applied in the same range to the hydrogen production apparatus according to one embodiment and another embodiment of the present invention.

Hereinafter, a hydrogen production apparatus and a hydrogen production method using the same, which are an embodiment and another embodiment of the present invention, will be described in more detail through specific examples and experimental examples.

< specific example 1> Hydrogen production device including mixer

1-1. Hydrogen production unit preparation

An apparatus of the type shown in FIG. 1 was prepared. The incubator has a capacity of 70L and is made of stainless steel and includes a steam heating automatic temperature control device, a sampling port, and an observation window, and is equipped with an MFC that can automatically control the amount of carbon monoxide input. The specifications of the pump used to operate the mixer are: power consumption of 2.2 kW, head 54.0m, and flow rate of 6.9 m ³ /h. A mixer of the type shown in FIG. 2 was used. The inner diameter of the housing included in the mixer was 15 mm or 32 mm, and the number of classification units was 6, 12, 24, or 30 mixing units.

1-2. Experiment to confirm the change of the mass transfer coefficient according to the change in the number of mixing units of the mixer

Among the hydrogen production devices of Specific Example 1-1., the inner diameter of the housing of the mixer was 15 mm, and the same number of mixing units as 6, 12, 24, or 30 was prepared. Put 50 L of 3.5% (w/v) NaCl solution in the incubator, and in order to compare the mass transfer efficiency of oxygen, nitrogen was injected into the incubator at a reaction temperature of 40 to make the dissolved oxygen amount (Dissolved Oxygen, DO) 0 ppm. prepared.

With this device, the mass transfer coefficient was measured by changing the vvm and the number of mixing units using air. That is, the mass transfer coefficient was measured while increasing the volume ratio (air volume/NaCl medium volume/minute, vvm) of air to NaCl solution per minute instead of carbon monoxide to 0.1, 0.2, 0.3, 0.4, 0.5 vvm. The mass transfer coefficient (K _L a,h ^{- 1} ) refers to the efficiency of transferring a gaseous substrate to a liquid phase. K _L means the oxygen transfer rate coefficient (cm/hr) of the liquid dura mater, and a represents the gas-liquid interface area per unit volume (cm ² /cm ³ ). The mass transfer coefficient was measured by a dynamic method. A sensor of a dissolved oxygen meter is attached to the inside of the incubator filled with 3.5% NaCl solution, and nitrogen is introduced into the incubator to replace oxygen in the 3.5% NaCl solution with nitrogen. After the dissolved oxygen of the NaCl solution becomes 0 ppm, the amount of dissolved oxygen in the NaCl solution is measured by time while increasing the air to 0.1, 0.2, 0.3, 0.4, and 0.5 vvm again, and the mass transfer coefficient is calculated using Equation 1.

Equation 1

는 용액 중 포화 상태에 도달하였을 때의 산소농도이며, C_AL1(mg/L)은 시간 t₁에서의 용액 중 산소농도이고, C_AL2(mg/L)는 시간 t₂에서의 용액 중 산소농도이다. In the above formula, K _L a (h ^-1 ) is the mass transfer coefficient,

is the oxygen concentration in solution when saturation is reached, C _AL1 (mg/L) is the oxygen concentration in solution at time t ₁ , C _AL2 (mg/L) is oxygen concentration in solution at time t ₂ am.

The results are shown in FIG. 8 .

8 is a graph showing the mass transfer coefficient according to the volume ratio of the air injection amount to the NaCl solution per minute for each number of mixing units, the x-axis represents the volume ratio of the air injection amount to the NaCl solution per minute (vvm), and the y-axis is the mass transfer coefficient (K _L a ,h ^{- 1} ).

As can be seen in FIG. 8 , the mass transfer coefficient shows a tendency to increase as the volume ratio (vvm) of the amount of air injected per minute (vvm) and the number of mixing units increase. In particular, when the number of mixing units is 24, a wide range of It can be seen that the mass transfer coefficient is high in the volume ratio (vvm) of the amount of air injected to the NaCl solution per minute. That is, when the number of mixing units is increased to 30, the mass transfer coefficient is increased, but considering the amount of power consumption, it seems that the number of mixing units is 24 is more preferable. As such, when the number of mixing units is 24, a high mass transfer coefficient is shown in a wide range of the volume ratio of the NaCl solution per minute to the air injection amount. is expected to be used by hydrogen-producing microorganisms.

Therefore, in the following experiment, the number of mixing units was 24.

In addition, in the case of Specific Example 1-1., it was easy to change the number of mixing units, and it was easy to change the operating conditions accordingly. Therefore, according to the present invention, it can be seen that hydrogen can be produced while easily responding to changes in circumstances.

1-3. mixer of the housing in sight Experiment to confirm the change of the mass transfer coefficient per power consumption

Among the hydrogen production devices of Specific Example 1-1, the number of mixing units of the mixer is 24 and the housing inner diameter is 15mm (15A) or 32mm (32A) Prepare the same, and measure the amount of power used for each transfer flow rate And the mass transfer coefficient per power consumption was calculated according to the volume ratio (vvm) of the amount of air injected to the NaCl solution per minute.

The power value was measured by measuring the power consumption of the pump included in the culture medium transfer unit.

The results are shown in FIGS. 9 and 10 .

9 is a graph showing the experimental results of Example 1, showing the amount of power per NaCl solution transfer amount. The x-axis represents the NaCl solution transfer flow rate (LPM), and the y-axis represents the amount of power (kW).

In addition, FIG. 10 is a graph showing the experimental results of Example 1, and shows the mass transfer coefficient per power consumption according to the volume ratio of the air injection amount to the NaCl solution per minute. The x-axis represents the volume ratio (vvm) of the amount of air injected to the NaCl solution per minute, and the y-axis represents the mass transfer coefficient (kW ^-1 h ^-1 ) per power consumption.

As can be seen in FIG. 9 , the power consumption value is 0.55 kW for the 15A mixer when the flow rate is 40 LPM, and 0.34 kW for the 32A mixer when the flow rate is 80 LPM. It can be seen that this is lower. In addition, as shown in FIG. 10 , it can be seen that the mass transfer coefficient per power consumption increases as the volume ratio of the air injection amount to the NaCl solution per minute increases. In addition, it can be seen that as the inner diameter through which the fluid is transferred increases, the increase in the mass transfer coefficient relative to the amount of power increases.

From the above results, it can be seen that when the amount of the transfer culture solution is increased, the tube diameter can be enlarged to respond easily, and the mass transfer can be made effectively compared to the amount of electricity according to the increase in the diameter of the tube. Therefore, according to the present invention, it can be seen that hydrogen production is possible while easily responding to changes in circumstances.

Hereinafter, the hydrogen production apparatus of the present invention will be described in more detail by comparing the hydrogen production apparatus to which the mixer of the present invention is applied and the hydrogen production apparatus to which the gas bubble generator is applied, based on the above-mentioned contents.

< Reference example 1> gas bubble generator Hydrogen production device including

1-1. Preparation of hydrogen production equipment

An apparatus of the type shown in FIG. 11 was prepared.

11 is a schematic diagram of a hydrogen production apparatus to which the gas bubble generator of Reference Example 1 is applied.

The apparatus shown in FIG. 11 is the same as in Example 1-1., except that a gas bubble generator is applied instead of a mixer. Compared to the method of generating gas bubbles by the rotational force of the apparatus disclosed in Korean Patent Publication No. 10-1190842, the gas bubble generator is more efficient than the method by high-pressure injection, considering that the method by high-pressure injection is more efficient. The same method as disclosed in was used. However, for comparison with Example 1, the gas bubble generator is installed inside the housing 210 " from the outside of the incubator, and the gas supply pipe 430 and the culture medium transfer unit including the carbon monoxide supply unit in the housing 210 " 300) to be connected.

The gas bubble generator 200" forms gas bubbles by high pressure, and the gas bubbles injected to the outside of the gas bubble generator 200" may flow out of the housing through the outlet connection pipe 310". FIG. is a perspective view of the gas bubble generator of FIG. 11 . Referring to FIG. 12 , a culture fluid inlet connection pipe 331 formed on one side of the gas bubble generator 200 " to allow the culture solution to flow into the gas bubble generator 331 and gas bubbles A carbon monoxide supply connection pipe 431 is formed on the other side of the generator 200 " so that carbon monoxide flows into the gas bubble generator, and the culture medium inlet connection pipe 331 can be connected to the culture medium transfer unit 300 and , the carbon monoxide supply connection pipe 431 may be connected to the gas supply pipe 430. That is, the culture solution introduced into the culture solution transfer unit 300 and the carbon monoxide introduced into the gas supply pipe 430 have a small cross-sectional area at the outlet 230 "), the culture medium and carbon monoxide are sprayed under strong pressure to create gas bubbles. The injected gas bubbles are discharged from the inner space of the housing to the incubator 100 through the outlet connection pipe 310 ″.

1-2. specific example Contrast mass transfer coefficient and power consumption measurement

Reference Example 1-1. By operating the device of Specific Example 1-2. and the mass transfer coefficient and power consumption were measured in the same manner as in 1-3. As a result, when the volume ratio (vvm) of the air injection volume to the solution per minute was 0.5 vvm and the transfer flow rate was 30 LPM (L/min), the mass transfer coefficient was 213.7 h ^-1 and the power consumption was 0.772 kW.

On the other hand, in the device of Specific Example 1-1., for the case where the housing inner diameter of the mixer was 15 mm and the number of mixing units was 24, the operation was performed under the same conditions (volume ratio of air injection volume to solution 0.5 vvm per minute, transfer flow rate 30 LPM), The mass transfer coefficient was 229.3 h ^-1 and the power consumption was 0.268 kW.

These results indicate that the mass transfer coefficient was 15.6 (h ^{- 1} ) higher compared to the case where the gas bubble generator of Reference Example 1-1. was applied, whereas the power value was reduced by 34%.

Therefore, it can be seen that the device of Specific Example 1-1. is better than Reference Example 1-1. in that gaseous carbon monoxide is better transferred to the culture medium, and as a result, hydrogen-producing microorganisms can effectively use carbon monoxide to produce hydrogen more effectively. can In particular, it can be seen that the hydrogen productivity is more excellent compared to the power consumption because the power consumption is small while having the above effect.

< specific example 2> Hydrogen production method using mixer

2-1. Preparation of hydrogen production equipment

2-1-1. Preparation of hydrogen production equipment with incubator capacity of 20L

Except for using a 20L capacity incubator instead of 70L, the same apparatus as that of the apparatus of Specific Example 1-1. with a housing inner diameter of 15 mm and the number of mixing units of 24 was prepared.

2-1-2. Prepare a hydrogen production device with a capacity of 100L incubator

An apparatus of the type shown in FIG. 6 was prepared. The incubator has a capacity of 100L and is made of stainless steel and includes a steam heating automatic temperature control device, a sampling port, and an observation window, and is equipped with an MFC that can automatically control the amount of carbon monoxide input. For the operation of two mixers, two pumps were connected to each mixer and used. The specifications of each pump were a power consumption of 2.2 kW, a lift of 54.0 m, and a flow rate of 6.9 m ³ /h. A mixer of the type shown in FIG. 2 was used. The inner diameter of the housing included in the mixer was 32 mm, and the number of mixing units was 24 in the classification unit.

2-2. hydrogen production

2-2-1. Hydrogen production using a hydrogen production device with a capacity of 20L incubator

Hydrogen was produced using the hydrogen production apparatus of Specific Example 2-1-1.

First, distilled water in the initial medium {yeast extract (yeast extract) 10 g / L; NaCl 35 g/L; KH ₂ O ₄ 1.28 g/L; Cystein-HCl 0.45 g/L; MgSO ₄ ·7H ₂ O 1.2 g/L; Vitamin solution 3 ml/L; Trace elemental solution 3 ml/L, FeSO ₄ ·7H ₂ O 0.009 g/L, NiCl ₂ 0.003 g/L} was dissolved or suspended in 10 L of a culture medium and administered to an anaerobic incubator. The pH of the culture medium suspended by adding 4N NaOH solution was adjusted to 6.5. After raising the internal temperature of the anaerobic incubator filled with the culture medium to 85 degrees Celsius, the pump located outside the incubator is operated to allow some of the culture medium inside the incubator to flow into the mixer, and carbon monoxide is also introduced into the mixer, so that the culture medium inside the incubator It was saturated with this carbon monoxide gas bubble. In a culture medium saturated with carbon monoxide gas bubbles, Thermococcus on New Renews {obtained from the Korea Institute of Ocean Science and Technology, isolated and identified by a known method (Journal of Microbiology Biotechnology 2006 vol. 16. No. 11 1826-1831)} was cultured 2% by volume of the volume was inoculated. The Thermococcus on New Renews strain was Thermococcus on New Renews NA1.

After that, the volume ratio (vvm) of the amount of carbon monoxide injection to the culture medium (initial amount of culture in the incubator) per minute starts with 0.10 vvm (start vvm), and changes to 0.20 vvm (change vvm). By culturing Thermococcus onnews, hydrogen was produced. At this time, the transfer speed of the culture medium was 30 LPM, and the pressure of the incubator was normal pressure.

2-2-2. Hydrogen production using a hydrogen production device with an incubator capacity of 100L

Specific Example 2-2-1, except that the hydrogen production device of Specific Example 2-1-2. was used instead of the hydrogen production device of Specific Example 2-1-1, and 60 L of the culture solution was administered to an anaerobic incubator instead of 10 L Hydrogen was produced in the same way as . However, vvm, culture medium transfer speed, and incubator pressure were performed under the conditions described in FIG. 13 instead of those described in Specific Example 2-2-1.

< Reference example 2> gas bubble generator Hydrogen production method using

2-1. Preparation of hydrogen production equipment

The same device as the device prepared in Reference Example 1-1. was prepared, except that a volume 20L incubator was used instead of the volume 70L.

2-2. hydrogen production

Hydrogen was produced in the same amount of culture medium and operating conditions as in Example 2-2-1., except that the hydrogen production apparatus of Reference Example 2-1. was used instead of the hydrogen production apparatus of Specific Example 2-1-1.

< Experimental example 1> Hydrogen production and electricity consumption vs. hydrogen production test

In Specific Example 2-2-1. and Reference Example 2-2., the hydrogen produced was measured.

First, the hydrogen content in the exhaust gas was measured by gas chromatography (Youngin Instrument, Korea). In addition, a wet gas meter that can measure the total amount of exhaust gas is installed in the gas discharge pipe to measure the total gas flow per unit time, and then from the measured value of the total gas flow per unit time using the measured value of the hydrogen content in the exhaust gas. Hydrogen production per unit time was calculated.

Power consumption was measured by measuring the power consumption of the pump included in the culture medium transfer unit. When the volume ratio (vvm) of the amount of carbon monoxide injected to the culture solution per minute was 0.10 vvm (start vvm) and 0.20 vvm (change vvm), the hydrogen production was divided by the power consumption to calculate the hydrogen production compared to the power consumption. The results are shown in Table 1.

Specific Example 2-2-1.
Reference Example 2-2. Volume ratio of the amount of carbon monoxide injected to the culture solution per minute (vvm) 0.10 0.20 0.10 0.20 Hydrogen production (mmol/L/h) 170.0 332.8 182.5 296.0 Hydrogen production compared to electricity consumption ( mmol /L/h/kW) 570.6 1163.8 132.7 215.3

As can be seen in Table 1, when the mixer is applied, it can be seen that the hydrogen production amount compared to the electric power consumption is increased by about 5 times compared to the hydrogen production method using the gas bubble generator. That is, in the case of Specific Example 2-2-1., it can be confirmed that hydrogen can be produced very effectively compared to the power consumption compared to Reference Example 2-2.

< Experimental example 2> Scale- up Experiment to confirm hydrogen production in the device

In the hydrogen production method of Specific Example 2-2-2., the produced hydrogen was measured. Production of hydrogen was measured in the same manner as in Experimental Example 1, and the amount of electricity was also measured in the same manner as in Experimental Example 1.

The results are shown in Tables 2 to 4 and FIG. 13 .

Table 2 below shows the results of measuring hydrogen production by changing the transfer rate of the culture under the condition that the incubator pressure is atmospheric pressure and the volume ratio (vvm) of the amount of carbon monoxide injected per minute is 0.10 vvm.

Culture medium transfer rate (L/min) Hydrogen production (mmol/L/h) 160 120.5 240 179.5

As can be seen in Table 2 and Figure 13, the volume ratio (vvm) of the amount of carbon monoxide injected per minute after the start of culture is maintained at 0.10, which is the starting vvm, and the hydrogen-producing microorganisms adapt to the environment. When the culture medium transfer rate was increased from 160 L/min to 240 L/min, the hydrogen production increased from 120.5 mmol/L/h to 179.5 mmol/L/h.

In addition, when comparing Table 1, which is the experimental result conducted in an incubator capacity of 20 L (culture medium 10 L), and Table 2, the experimental result conducted in an incubator capacity 100 L (culture medium 60 L), the scale-up was made despite , it can be seen that the hydrogen production was efficiently maintained. Moreover, when the transfer rate of the culture medium is increased to 240 LPM, it can be seen that the hydrogen production amount is more increased compared to before the scale-up is made (Specific Example 2-2-1.). Therefore, it can be seen that scale-up is very easy in the case of the present invention to which a mixer is applied.

Table 3 below shows the results of measuring hydrogen production by changing the volume ratio (vvm) of the amount of carbon monoxide injected to the culture solution per minute under the conditions that the incubator pressure is normal pressure and the feed rate of the culture medium is 240 LPM.

Volume ratio of the amount of carbon monoxide injected to the culture solution per minute (vvm) Hydrogen production (mmol/L/h) 0.10 179.5 0.20 317.7

As can be seen in Table 3 and FIG. 13, the volume ratio (vvm) of the amount of carbon monoxide injected per minute was changed from 0.10 to 0.20 while maintaining the transfer rate of the culture medium at 240 L/min. It can be confirmed that the hydrogen production is further increased to 317.7 mmol/L/h.

In addition, through these results, it can be confirmed that the present invention can increase the feed rate per minute without unreasonableness, thereby effectively responding to scale-up. For example, in the case of the gas bubble generator of Reference Example 1-1. to which the same pump as in Specific Example 1-1. was applied, the feed rate per minute was 30 LPM, and it was difficult to increase the feed rate per minute beyond that, but in Specific Example 1- In the case of Specific Example 2-1-2. in which the same mixer and two pumps as in 1. were applied in parallel, in the hydrogen production method of Specific Example 2-2-2. hydrogen could be produced.

After all, in order to increase the feed rate per minute up to 240 LPM, it is possible to connect eight gas bubble generators and a pump in parallel, but it can be seen that the present invention is possible by connecting two mixers and a pump in parallel. Therefore, in the case of the present invention, it is possible to easily increase the feed rate per minute by adding a small number of relatively low-capacity pumps and connecting them in parallel with the mixer, so that it is possible to easily cope with scale-up.

Table 4 below shows the results of measuring hydrogen production by changing the pressure under the condition that the transfer rate of the culture medium is 240 LPM and the volume ratio (vvm) of the amount of carbon monoxide injected per minute is 0.20 vvm. At this time, the hydrogen production amount under the 0.5 bar pressurization condition of Table 4 represents the average value of the hydrogen production amount measured at the start and end of the measurement of the hydrogen production amount.

pressure (bar) Hydrogen production (mmol/L/h) atmospheric pressure 317.7 0.5 bar 408.6

As can be seen in Table 4 and FIG. 13, when the volume ratio (vvm) of the amount of carbon monoxide injected per minute is maintained at 0.20 at normal pressure, and finally, the pressure of the incubator is pressurized to 0.5 bar, the amount of carbon monoxide injected per minute is The volume ratio (vvm) was measured to be 0.22 to 0.24 vvm, and the average hydrogen production amount was 408.6 mmol/L/h. That is, the solubility of gaseous carbon monoxide increases by pressurization, so that carbon monoxide can be more effectively dissolved in the liquid transfer culture medium, resulting in effective hydrogen production.

As a result, as confirmed in Tables 2 to 4 and FIG. 13, according to the present invention, it is possible to stably scale-up so that continuous and stable hydrogen production is possible, and the hydrogen productivity is also higher.

From the above results, it can be seen that the hydrogen production apparatus and the hydrogen production method of the present invention are easy to scale-up and have excellent hydrogen productivity compared to power consumption. In addition, it can be seen that carbon monoxide is well transferred to the culture medium, so that hydrogen production is more stable and effective, and carbon monoxide can be easily supplied according to an increase in the culture medium volume, so that it can be easily scaled-up by responding to flow rate changes.

Although embodiments of the present invention have been described above with reference to the accompanying drawings, those of ordinary skill in the art to which the present invention pertains can realize that the present invention can be embodied in other specific forms without changing its technical spirit or essential features. you will be able to understand Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

1: hydrogen production device 100: incubator
200: mixer 201: second flange
202: third flange 210: housing
220: fluid inlet 221: step
230: fluid discharge unit 240: classification unit
241: mixing unit 250: fixed part
251: body part 252: fluid hole
300: culture medium transfer unit 301: first flange
310: fluid discharge part connection pipe 311: fourth flange
330: transfer pipe 350: pump
370: suction pipe 400: carbon monoxide supply unit
410: carbon monoxide source 430: gas supply pipe
450: flow regulator 500: collection unit
510: hydrogen storage unit 550: cooling unit
570: gas discharge pipe 901: bolt
902: nut 903: fastening hole

Claims (18)

an incubator in which a culture solution for culturing hydrogen-producing microorganisms that produce hydrogen using carbon monoxide is accommodated therein; and
It includes a mixer in which one side and the other side are connected to the incubator from the outside of the incubator, and a fixed fractionation part is formed therein,
A plurality of the mixers are arranged, one mixer being connected to the incubator in parallel to face at least another mixer,
The transfer culture medium, which is at least a part of the culture medium, is transferred from the incubator to the mixer and flows into one side of the mixer, and the carbon monoxide flows toward the dividing unit from the front end of the divider and flows toward the other side of the mixer together with the conveyed culture medium. to form a gas-liquid fluid,
After at least a portion of the gas-liquid fluid is classified by the fractionation unit, it rejoins and moves to the incubator through the other side of the mixer, and the carbon monoxide and the transfer culture solution are mixed by the fractionation. According to claim 1,
The classification unit is a hydrogen production device comprising a mixing unit made of one or more shapes selected from the protrusion or plate shape. 3. The method of claim 2,
The mixing unit is in plurality, each mixing unit is made of a plate shape, and the other mixing unit connected to one mixing unit is connected in series, a hydrogen production device coupled to each other in a twisted state. 4. The method of claim 3,
Each of the mixing units is a hydrogen production device having a shape twisted with respect to the flow direction as a reference axis. According to claim 1,
The mixing is a hydrogen production device that occurs while additionally undergoing a process of conversion or reverse change of the flow of the gas-liquid fluid. delete According to claim 1,
Hydrogen production apparatus further comprising a collecting unit for collecting the hydrogen produced by the hydrogen-producing microorganisms. According to claim 1,
Hydrogen production apparatus further comprising a culture medium transfer unit connecting one side of the mixer and the incubator. 9. The method of claim 8,
Hydrogen production device to which the carbon monoxide supply unit is connected to one side of the culture medium transfer unit. 9. The method of claim 8,
The culture medium transfer unit
Hydrogen production apparatus comprising a pump, a suction pipe for transferring the transfer culture solution to the pump, and a transfer pipe for transferring the transfer culture solution from the pump to the mixer. According to claim 1,
the mixer
A tubular housing, a fluid inlet part formed on one side of the housing and into which the carbon monoxide and the transfer culture solution are introduced, and a fluid discharge part formed on the other side of the housing and mixed with the carbon monoxide and the transfer culture solution Hydrogen comprising: production equipment. 12. The method of claim 11,
The division unit is fixed inside the housing by a fixing unit, and the fixing unit is formed on one side of the division unit. 13. The method of claim 12,
The fixing unit is a hydrogen production device coupled to one side of the fluid inlet. 14. The method of claim 13,
A step is formed on one side of the fluid inlet, and the fixing unit is a hydrogen production device coupled to the step by fitting. 15. The method of claim 14,
The fixing unit is a hydrogen production device that is fixed in close contact with the fluid inlet by the pressure of the transfer culture solution. According to claim 1,
The hydrogen-producing microorganism is a hydrogen production device of the genus Thermococcus. (A) In an incubator accommodating therein a culture solution for culturing hydrogen-producing microorganisms that produce hydrogen using carbon monoxide, at least a portion of the culture solution is transferred to one side of the mixer in which a fixed fractionation part is formed. and an inflow step of introducing the carbon monoxide from the front end of the dividing unit toward the dividing unit;
(B) the introduced transfer culture solution and the introduced carbon monoxide flow together toward the other side of the mixer to form a gas-liquid fluid, and at least a portion of the gas-liquid fluid is classified by the dividing unit so that the carbon monoxide and the transferred culture solution are mixed a mixing step to form a mixture;
(C) generating hydrogen by moving the mixture into the incubator through the other side of the mixer, culturing the hydrogen-producing microorganisms to generate hydrogen; and
(D) comprising a hydrogen capture step of collecting the hydrogen produced by the hydrogen-producing microorganisms using the carbon monoxide,
A hydrogen production method in which a plurality of the mixers are connected and disposed in parallel with one mixer to face at least another mixer. 18. The method of claim 17,
The culturing in step (C) is a hydrogen production method that is carried out under pressure.

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