KR102417097B1 - blue hydrogen production device using natural gas, liquefied device for waste gas generated during combustion of raw materials, and steam turbine power generation device using high-temperature steam - Google Patents

Abstract

The present invention provides a process flow diagram and a process configuration, in which fresh water is supplied to a hydrogen production process, and after steam turbine power generation using high-temperature steam, is transferred to a demineralized water reservoir for recycling or the remaining hot water and the fresh water can be supplied to regions in need. A blue hydrogen production device using natural gas comprises: a steam generating part (110); and a gas reforming reactor (120). According to the present invention, hydrogen can be obtained at a low cost, and energy waste can be reduced to a minimum while minimizing environmental pollution.

Description

Blue hydrogen production device using natural gas, liquefaction device of waste gas generated during raw material combustion, and steam turbine power generation device using high-temperature steam turbine power generation device using high-temperature steam}

The present invention relates to blue hydrogen production and steam power generation and hot water supply technology, and more particularly, high-temperature steam and natural gas reformer generated from a complex process system and a steam generator using natural gas of the blue hydrogen production system. And hydrogen production is increased by oxidation-reduction in the vapor-gas reduction reactor, and hydrogen sulfide and carbonyl sulfide generated during combustion of the fuel of a water heater at a high temperature of 1,500 to 2,000 ℃ are converted into sulfur dioxide, and carbon dioxide It is a method that extracts and liquefies this waste gas to effectively use it and recycles it. At this time, a desalination plant is used to produce the necessary steam to supply cooling water to the system, and to operate the blue hydrogen production process. A blue hydrogen production device using natural gas that can use the generated high-temperature steam to generate steam turbine power generation and hot water, and to recycle the rest or supply hot water and fresh water to each required area through a pipe, and liquefaction of waste gas generated during raw material combustion It relates to a device, a steam turbine generator using high-temperature steam.

Hydrogen is an important chemical used in energy, oil refining, fine chemical and petrochemical processes. Typically, it is used in many refinery processes. Recently, as the fossil fuel-based economy is shifting to a hydrogen economy society, the process development of a reformer for a small fuel cell, a hydrogen station for a fuel cell vehicle, and a chemical plant for producing large-capacity hydrogen is attracting attention.

However, in the related art, unnecessary by-products such as carbon dioxide are generated in the process of producing hydrogen, and there are problems such as requiring excessive energy consumption.

Patent Publication No. 10-2021-0086015 (published on Jul. 08, 2021)

The present invention is to solve the problems of the prior art as described above, blue hydrogen using natural gas to produce blue hydrogen from natural gas, liquefy the generated waste gas, and produce electricity using high-temperature steam An object of the present invention is to provide a hydrogen production device, a liquefaction device for waste gas generated during raw material combustion, and a steam turbine generator using high-temperature steam.

The above object is provided with a combustion device and a blower using a burner or plasma, a steam generator that produces high-temperature steam of 370 ℃, 48.04 bar from fresh water flowing in at a high temperature of 1,750 ~ 2,000 ℃, from the steam generator A first natural gas heater that converts natural gas into high-temperature gas of 370° C. and 48.04 bar by introducing high-temperature steam of 370° C. and 48.04 bar, 370° C., high-temperature steam of 48.04 bar generated from the steam generator Steam having second and third natural gas heaters that are respectively introduced and converted in the first natural gas heater into ultra-high temperature natural gas of 370 to 500 ℃ and 48.04 to 46.08 bar and supplied to the gas reforming reactor generator; And high-temperature steam is introduced from the steam generator and ultra-high-temperature natural gas is introduced from the third natural gas heater, so that hydrocarbons and steam present in the natural gas react with an alumina or nickel-based catalyst to generate hydrogen and carbon monoxide. It is achieved by a blue hydrogen production apparatus using natural gas, which consists of a reforming reactor.

According to one aspect of the present invention, further comprising a natural gas pretreatment unit having a dehydration device for removing moisture from natural gas, and first and second desulfurization devices for removing hydrogen sulfide from the natural gas from which the moisture has been removed characterized in that

According to another aspect of the present invention, a screen filter for filtering seawater, a coagulant and sodium hypochlorite are added together with the seawater that has passed through the screen filter, and a sedimentation tank for washing and sterilizing the seawater, the washing that is put together with a biodegradable polymer And the initial filter storage tank for primary filtering of the sterilized seawater, the suspension filter storage tank for removing suspended matter from the primary filtered seawater, the fresh water from which the suspended matter is removed, which is added together with an acid-resistant agent and a reverse osmosis membrane expansion inhibition pretreatment agent, is filtered primarily A cartridge primary filter that uses a high-pressure pump for reverse osmosis from the cartridge primary filter together with sodium hydrogen sulfite, a seawater reverse osmosis system that sterilizes browning and microorganisms of fresh water, and adsorption of fresh water flowing in the seawater salt osmosis system A storage tank, a service water storage tank in which the fresh water from the adsorption tank is introduced by reducing the reverse pressure through the reverse osmosis permeation pump, and the floating materials are removed from the service water storage tank by the reverse osmosis pump Secondary cartridge for secondary filtering of fresh water A filter, a permeate storage tank for floating matter reverse osmosis that removes additional suspended matter from the fresh water of the cartridge secondary filter from which suspended matter is removed by flowing into the suspended matter reverse osmosis device by a high-pressure pump for float reverse osmosis, and the permeate through the ion exchange device inlet pump It characterized in that it further comprises a desalination plant equipped with an ion exchange device for producing excellent quality fresh water from the fresh water of the reverse osmosis permeation storage tank and storing it in the demineralized water storage tank.

According to another aspect of the present invention, it is characterized in that it further comprises a filtering blower for injecting filtered air into the initial filter storage tank and the float filter storage tank.

According to another aspect of the present invention, it further comprises a backwash reservoir for re-filtering the seawater from which suspended matter has not been removed from the float filter reservoir in the initial filter reservoir and the float filter reservoir through a backwash filtration pump. do it with

According to another aspect of the present invention, High-temperature steam that converts carbon monoxide contained in the gas reformed in the gas reforming reactor and the remaining steam with steam at a temperature range of 310 to 370 ℃ in the presence of iron oxide and chromium catalyst to convert it to carbon dioxide at 350 to 400 ℃ -Gas reduction reactor, and the high-temperature steam-process gas of the gas reduction reactor is cooled to 200 ℃, carbon monoxide in the process gas is converted to carbon dioxide by a catalyst composed of metal copper, zinc oxide, and one or more consumable oxides of alumina and chromia a low-temperature steam-reducing reactor having a low-temperature steam-reduction reactor for converting and transferring the fresh water to a cooler into which fresh water is introduced; An amine carbon dioxide absorber that adsorbs and removes carbon dioxide by introducing gas from the low-temperature steam-reduction reactor, fresh water at 25-30 ℃, and monoethanolamine at 25-30 ℃ from the regenerator ethanol amine storage tank, 220 ℃ A monoethanolamine regenerator for regenerating monoethanolamine from the gas in which steam is introduced and the carbon dioxide is removed by adsorption and storing it in a regenerated monoethanolamine storage tank, and filtering the gas discharged from the monoethanolamine regenerator to convert carbon monoxide and carbon dioxide into carbon dioxide a carbon dioxide removal device having an amine filter supplied to the liquefaction system, a settling tank for transferring nitrogen containing hydrogen in gas discharged from the amine carbon dioxide absorber and the monoethanolamine regeneration device to a pressure circulation type adsorption device; and a compressor for increasing the pressure of nitrogen containing hydrogen at 29 to 30 ℃ and 23 bar from the settling tank to 30 bar, a cooler for cooling nitrogen containing the pressurized hydrogen with fresh water, hydrogen discharged from the cooler It characterized in that it further comprises a pressure circulation type adsorption device having a hydrogen separator for storing a small amount of carbon monoxide, carbon dioxide, methane, and a large amount of nitrogen contained in the buffer tank to adsorb and remove.

In addition, another object of the present invention, blue hydrogen production apparatus using natural gas; desulfurization facility reaction unit; carbon dioxide removal device; and a carbon dioxide liquefaction device, wherein the desulfurization facility reaction unit receives the waste gas of 677∼721 ℃, 19 bar generated from the steam generator to generate hydrogen sulfide (H ₂ S) and carbonyl sulfide (COS) from zinc oxide Desulfurization reactor in which zinc sulfide (ZnS) to iron sulfide (FeS), water vapor (H ₂ O) and carbon dioxide (CO ₂ ) are generated while reacting with (ZnO) to iron Ⅲ oxide (Fe ₂ 2O ₃ ), sulfation of the desulfurization reactor A separator for separating sulfur dioxide from zinc (ZnS) to iron sulfide (FeS), water vapor (H ₂ O) and carbon dioxide (CO ₂ ), zinc sulfide (ZnS) to iron sulfide (FeS), water vapor (H) from which sulfur dioxide is separated in the separator ₂ O) and carbon dioxide (CO ₂ ) react with zinc oxide (ZnO) to iron Ⅲ (Fe ₂ O ₃ ) to separate zinc sulfide (ZnS) to iron sulfide (FeS) and oxygen (O ₂ ) into a direct desulfurization reactor; Zinc sulfide (ZnS) to iron sulfide (FeS) generated in the separator and the direct desulfurization reactor is combined with oxygen in the external air of the air heater that has passed through the cooler to regenerate zinc oxide (ZnO) to iron oxide III (Fe ₂ O ₃ ) A regeneration device, a regeneration separator in which sulfide gas is separated from zinc sulfide (ZnS) to iron sulfide (FeS) and sulfide gas not regenerated in the regeneration device and flows into the separator through a desulfurization reactor, and oxidation-reduction is completed in the direct desulfurization reactor It consists of a sulfur condenser that condenses the generated sulfur dioxide, and the carbon dioxide removal device converts the waste gas of 677-721 ℃, 19 bar generated from the steam generator into high-temperature steam of 600-650 ℃, 30 bar by water. A waste heat recovery device that is stored in a vapor buffer tank, and an aqueous solution of 25-30 ℃ water (H ₂ O) and 25-30 ℃ monoethanolamine from the waste gas flowing from the waste heat recovery device is 0.7% of carbon monoxide A carbon dioxide absorber that absorbs 9% of a large amount of carbon dioxide, and a small amount of 0.7% of carbon monoxide to 9% of a large amount of the carbon dioxide absorber from the carbon dioxide absorber. It consists of a monoethanolamine regenerator that regenerates monoethanolamine from the waste gas to which carbon dioxide has been adsorbed and stores it in a regenerated monoethanolamine storage tank, wherein the carbon dioxide liquefaction device cools the carbon dioxide gas absorbed in the amine carbon dioxide absorber with fresh water. a cooler, a separator that separates a condensed component such as water from the gas cooled by the cooler, a compressor that compresses carbon dioxide from which a condensed component such as water is separated in the separator to a high pressure, and the compressor compresses it at a high pressure A cooler that cools the carbon dioxide, an exchanger that lowers the temperature of the carbon dioxide cooled in the cooler and liquefies it while passing through a Joule-Thomson valve, separating non-liquefied carbon dioxide from the liquefied carbon dioxide and re-supplying it to the heat exchanger and re-supplying the liquefied carbon dioxide to the heat exchanger It is achieved by a liquefaction device for waste gas generated during raw material combustion, characterized in that it consists of a separator to be stored in an external storage tank.

According to one aspect of the present invention, a cooler for cooling the sulfur dioxide gas not condensed in the sulfur condenser by receiving fresh water, a separator for separating condensed components such as water from the sulfur dioxide gas cooled in the cooler, in the separator A compressor that compresses sulfur dioxide from which condensed components such as water are separated to high pressure, a cooler that cools the compressed sulfur dioxide at high pressure in the compressor, lowers the temperature of the cooled sulfur dioxide in the cooler and passes it through a Joule-Thomson valve to liquefy it It is characterized in that it further comprises a sulfur dioxide liquefaction treatment unit having a separator for separating non-liquefied sulfur dioxide from among the liquefied sulfur dioxide and re-supplying it to the heat exchanger and storing the liquefied sulfur dioxide in a storage tank.

And another object of the present invention, a hydrogen production device using natural gas; and a vapor buffer tank into which high-temperature steam is introduced from the steam generator; A turbine, an intermediate steam turbine generating power by steam of 280 ℃, 60 bar discharged from the high-pressure steam turbine, a low-pressure steam turbine generating power by steam of 210 ℃, 30 bar discharged from the intermediate steam turbine, the high-pressure steam turbine, This is achieved by a steam turbine generator using high-temperature steam, which is composed of a steam turbine generator having a generator that generates electricity from the electric energy generated by the intermediate steam turbine and the low-pressure steam turbine and sends it to a substation.

According to the present invention, hydrogen can be obtained at low cost by producing hydrogen using natural gas, generating electricity using steam generated in the process of producing hydrogen, and liquefying and utilizing waste gas, the main culprit of environmental pollution. Not only that, but it also has the effect of reducing energy waste to a minimum while minimizing environmental pollution.

1A to 1D are diagrams showing a blue hydrogen production apparatus using natural gas, a liquefaction apparatus of waste gas generated during raw material combustion, a steam turbine generator using high-temperature steam, and a hot water desalination apparatus according to an embodiment of the present invention. .

Looking at blue hydrogen produced by the present invention before describing specific embodiments of the present invention, blue hydrogen is a hydrogen-based economy that is used as a hydrogen fueled vehicle, hydrogen power generation, hydrogen fuel cell, chemical feedstock, etc. It is a product that can be used very usefully in paraffin: 2CO ₂ + 7H _{2 → CH 3 -CH 3 + 4H 2 O} ), Olefin: 2CO ₂ + 6H ₂ → CH ₂ -CH2 + 4H ₂ O), DME: 2CO ₂ + 6H ₂ → CH ₃ OCH ₃ + 3H ₂ O), Ethanol: 2CO ₂ + 6H ₂ → CH ₃ CH ₂ OH + 3H ₂ O), methanol: 2CO ₂ + 6H ₂ → 2CH ₃ OH + 2H ₂ O After removal, some water vapor is discharged to the outside through a vent, goes through a compressor, and goes through paraffin, olefin, DME, ethanol, and methanol reactors in a buffer tank to produce separately necessary products. There are attractive reasons for this, as well as the burning of hydrogen and oxygen to produce electricity and other power sources, which results in only unpolluted water. Hydrogen is advantageous for storage of hydrogen at room temperature because the metal-hydrogen bond is much weaker than the metal-oxygen or metal-chlorine bond, which is mainly present in light metal ores, which is a source of fuel without fertilizer production or storage of liquid or hydrogen. It can be usefully used in other processes such as metal) production.

Hydrogen obtained from natural gas can be obtained from gas production processes such as steam methane reformers, in which the hydrocarbon content of natural gas is converted into the main components of hydrogen and carbon monoxide according to the supply of steam. In addition, by producing hydrogen by reforming natural gas and capturing or storing carbon or combining it with other molecules, overall carbon dioxide emission is greatly reduced, and fresh water at room temperature is supplied using a desalination plant to supply steam generators and coolers. It is very economical by completely recycling energy because the high-temperature steam generated from the steam power generation and supply of hot water and remaining fresh water.

In addition, the present invention is a hydrogen production complex process system that develops an industrial hydrogen plant capable of capturing carbon using natural gas as the main raw material, and also uses heat generated during the hydrogen production process to generate steam turbine power generation, hot water and fresh water around This process is very simple as it can be supplied locally. In particular, for methane-steam reforming, a separate fuel must be used to produce steam at a high temperature of 370 ℃ and 48 to 50 bar in the steam generator. In this case, sulfur dioxide (SO ₂ ) and carbon dioxide (CO ₂ ) generated from combustion at a high temperature ), carbon dioxide (CO ₂ ) generated during the reforming process is captured and liquefied to combine with other molecules as well as environmental benefits. They are converted into products, which are usefully used in the production of plastic bags or in the pharmaceutical industry.

In addition, it is judged that it will contribute to economic profit creation if sold separately, such as for the manufacture of carbonated beverages. In particular, sulfur dioxide (SO ₂ ) is a reactant of four oxidation-reduction reactions [SO ₂ + 2H ₂ O+Cl ₂ → H ₂ SO ₄ (sulfuric acid). ) + 2HCl, SO ₂ + 2H ₂ S → 2H ₂ O + 3S, SO ₂ + H ₂ O → H ₂ SO ₃ (sulfite), SO ₂ + NaOH → NaHSO ₃ (sodium hydrogen sulfite)] SO ₂ ) is used in a wide variety of fields such as fertilizer manufacturing, ore treatment, wastewater treatment, and petroleum refining. In addition to wine, it is widely used as a preservative for general foods, beverages, and medicines, so it can contribute to economic profit creation if sold to necessary areas. Hereinafter, in an embodiment of the present invention, a detailed description of products using such carbon dioxide (CO ₂ ) and sulfur dioxide (SO ₂ ) will be omitted.

Looking at these characteristics of the present invention, natural gas contains up to 22-25% of hydrogen (H2) in %mol (moles of hydrogen/moles of raw materials), and %weight (weight of hydrogen/weight of input fuel) is 2.2- It becomes 2.5%, and this natural gas passes through a gas reformer, a high-temperature steam-gas reduction reactor (HTWGS) and a low-temperature steam-gas reduction reactor (LTWGS), but the general hydrogen fuel cell hydrogen production process is As the molar ratio of carbon = 3 to 3.5, the % weight of hydrogen (H ₂ ) is about 40%, but the present invention provides alumina/nickel catalyst and 870-920 ℃ ultra-high temperature steam for a faster reaction compared to the general hydrogen fuel cell hydrogen production process. The molar ratio of water vapor/carbon = ₃ to 5 is possible using A three-stage low-temperature steam-gas reduction reactor is used to increase production by about 3-4%.

Although the % weight (weight of hydrogen produced / weight of input fuel) of the present invention (H ₂ ) varies slightly depending on the natural gas production region, it is about 1.2 to 1.45 times more hydrogen in general hydrogen fuel cells, from 48 to 58 %. Compared to the production process (a natural gas reformer → high-temperature steam-gas reduction reactor (HTWGS) two-step process), it is produced at the maximum value, and, in particular, cooling water for hydrogen production is Fresh water is supplied to the system, and for this purpose, it is a three-step process: natural gas reformer → high temperature steam-gas reduction reactor (HTWGS) → low temperature steam-gas reduction reactor (LTWGS).

However, only when 8.3 tons (10mmscfd) of natural gas are input per hour, the steam turbine power generation is at least 42MW, and the high-temperature steam using the waste gas of the steam generator is 1,002 tons per hour, and the high-temperature steam injected into the monoethanolamine regeneration boiler is The steam can produce _2,607-3,400 tons _of hot water generated through this process per hour, and the rest of the fresh water is supplied to the necessary areas. It is a process that can be produced, in this case carbon dioxide (CO ₂ ) is carbon monoxide generated during reforming and generated during combustion in a steam generator, and sulfur dioxide (SO ₂ ) is generated during combustion in a steam generator, carbon dioxide (CO ₂ ), sulfur dioxide (SO ₂ ) ) may be slightly different depending on the type of fuel for combustion of the steam generator, and if plasma is used for the combustion of the steam generator, it can be reduced by about 20 to 40 %. The combustion method of the heater) is not specifically mentioned in the embodiment of the present invention, and the large amount of carbon dioxide (CO2) and sulfur dioxide (SO2) generated is due to the combustion method or fuel of the steam generator (Water Heater).

Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1A to 1D are diagrams showing a blue hydrogen production apparatus using natural gas, a liquefaction apparatus of waste gas generated during raw material combustion, a steam turbine generator using high-temperature steam, and a hot water desalination apparatus according to an embodiment of the present invention. .

As shown in FIG. 1A , in the embodiment of the present invention, the cooling water flowing in from the natural gas pretreatment unit 100 and the desalination plant 400 through the underground pipe 434 to the steam generator 112 . Hydrogen sulfide and carbonyl sulfide generated by burning fuel in a combustion device are reformed into sulfur dioxide in the desulfurization facility reaction unit 200, which is a desulfurization recovery process, and transferred to a liquefaction process, a first natural gas heater (NG Heater) ( 111), the second natural gas heater 113, and the gas reforming process (Gas Reformer) in the gas reforming reactor 120 of natural gas that has passed through the additional two-stage heater of the third natural gas heater 114 (Gas Reformer), desalination plant (Desalination) Plant) 400, the cooling process in the cooler 170 of the coolant introduced through the pipe 434, the vapor-gas reduction reactor process (WGS) in the vapor-gas reduction reaction unit 130, and the cooler process again After moving to the condensate storage tank 135 through the condensate, the condensate is sent to the underground pipe 320 for recycling, and the remaining hot water is transported through the pipe of the pump 437 to each required area.

In addition, the cooling water passing through the steam generator (Water Heater) or the heater and cooler using fresh water supplied from the desalination plant (400) facility to the underground pipe (434) is converted into high-temperature steam, such high-temperature steam is transferred to the steam turbine, and the cooling water introduced through the pipe 434 from the steam-gas reduction reaction process (WGS) in the steam-gas reduction reaction unit 130 and the desalination plant 400 Since the gas that has passed through this cooler contains carbon dioxide, it is transferred to the device for collecting carbon dioxide through the amine carbon dioxide removal device 140, which is a carbon dioxide removal device, and the gas containing nitrogen and hydrogen is adsorbed by pressure circulation. It represents a process in which hydrogen with a purity of 99.99% is sent to a buffer tank through a pressure circulation type adsorption process for hydrogen capture by the device 150 and transferred to a required place, and is supplied from the desalination plant 400 facility to the underground pipe 434 The high-temperature steam from the fresh water passed through the cooler passes through the vapor buffer tank 161, through the compressor 162, through the high-pressure steam turbine 163, the intermediate steam turbine 164, the low-pressure steam turbine 165, and the generator 166. In the process of producing electricity, the substation 168 is a transformer that boosts and transmits electricity produced in the power plant 166 . The steam passing through the steam turbine system is connected to the underground pipe 320 to recycle the condensed water through the condenser 167 or to supply hot water.

As shown in FIG. 1B, in the embodiment of the present invention, fresh water supplied to the underground pipe 434 from the desalination plant 400 of FIG. 1A is produced by the steam generator 112 to produce high-temperature steam. For this purpose, carbon dioxide (CO ₂ ) and sulfur dioxide (SO ₂ ) of 780-800 ℃, 19 bar, generated at the time of combustion, _first undergo a recovery process, and then in the reaction unit 200 of the desulfurization facility. (SO ₂ ) Through the recovery process, the fresh water supplied to the underground pipe 434 from the desalination plant 400 recovers the high-temperature steam of 600 to 650 ℃ in the waste heat recovery device 226, FIG. 1a It is sent to the steam buffer tank 161 of the steam turbine power generation unit 160 of or stored in the demineralized water storage tank 432 . Since the gas that has passed through the waste heat recovery device 226 contains carbon dioxide, it is transferred to the device for collecting carbon dioxide through the amine carbon dioxide removal device 220 which is a carbon dioxide removal device.

As shown in Figure 1c, in the embodiment of the present invention, sulfur dioxide and synthesis gas that have undergone the desulfurization recovery process in the desulfurization facility reaction unit 200 of Figure 1b are the carbon dioxide removal device 140 and amine carbon dioxide removal of Figure 1a After going through the device 220, since the maximum cooling is required for the carbon dioxide liquefaction process in the carbon dioxide liquefaction device 300 and the sulfur dioxide liquefaction process in the sulfur dioxide liquefaction processing unit 310, this gas is discharged from the desalination plant (400) through the pipe ( 434), the gas is compressed by the respective compressors 303 and 313 through the coolers 301, 311, and then liquefied through the Joule-Thompson valves 306 and 316.

As shown in FIG. 1D, in the desalination plant 400 of the embodiment of the present invention, seawater that has passed through the screen filter 401 passes through a Seawater Reverse Osmosis Systems 418 to demineralize water. It is stored in Demineralized Water Storage tanks 432 and is supplied to a natural gas heater (NG Heater) through a pump 433 and a pipe 434 through the steam generator 110 of FIG. 1A. The cooling water required for the cooler of the natural gas reforming reactor (Reformer) 120, the vapor-gas reduction reaction unit 130, and the cooler of the carbon dioxide removal device 140 is supplied, and the amine carbon dioxide removal device 140 and It is supplied to the pressure circulation type adsorption device 150 for capturing hydrogen, is supplied to the amine carbon dioxide removal device 140 of FIG. As for the production of supplied cooling water, the fresh water required for each process, that is, the cooling water, is re-supplied to the hydrogen production process through the pipe 434, and the remaining fresh water is transferred to the supply pump 436 through the underground pipe through the pump 435. The hot water generated in the hydrogen production process is supplied to the required area, and is transferred to the hot water supply pump 438 through the underground pipe through the pump 437 and supplied to the required area.

The operation of the blue hydrogen production apparatus using natural gas according to the embodiment of the present invention configured as above, the liquefaction apparatus of waste gas generated during raw material combustion, and the steam turbine generator using high-temperature steam will be described. Hereinafter, in order to help the understanding of the invention, an embodiment of the present invention configured as shown in FIGS. 1A to 1D will be described separately for each drawing.

First, FIG. 1a is a configuration for a blue hydrogen production process from natural gas, a natural gas pretreatment unit 100 , a steam generator (Water Heater) 112 , a first natural gas heater 111 , and a gas reforming reactor 120 . ), a vapor-gas reduction reaction unit 130 , an amine carbon dioxide absorption device 140 which is a carbon dioxide removal device, a pressure swing adsorption device for hydrogen separation (Pressure Swing Adsorption, PSA) 150 and a steam turbine power generation unit 160 ) as the main component.

A natural gas pretreatment unit 100 for pretreating natural gas to remove halogen compounds such as sulfides and chlorides such as hydrogen sulfide (H ₂ S) and carbon dioxide (CO ₂ ) contained in natural gas from a gas well is provided. In general, natural gas is supplied to the liquefied gas facility through the natural gas pre-processing unit 100, but in the embodiment of the present invention, when the hydrogenation process is performed directly in a gas well, a pre-treatment process for natural gas must be performed, and mainly included The impurity gas is hydrogen sulfide (H ₂ S) and water (H ₂ O), even if it contains a small amount, since corrosion of the device is serious and must be removed. Then, since hydrogen sulfide (H ₂ S) must be removed, a desulfurization facility consisting of a primary desulfurization device 102 and a secondary desulfurization device 103 is installed to remove hydrogen sulfide.

Natural gas, which has been pre-processed in the natural gas pre-processing unit 100, flows into a first natural gas heater (NG Heater) 111, and an underground pipe 434 from the desalination plant 400 of FIG. 1D. ), fresh water (H2O) is introduced by the warper pump 116 and enters the steam generator 112 to produce steam at a high temperature of 370 ℃ and 48.04 bar, at this time the combustion device 115 burner or plasma In order to supply fuel with the used fuel and burn it at a high temperature of 1,750 to 2,000 ℃, air is injected into the air injector with the blower 117 to produce high-temperature steam.

And, some of the high-temperature steam of 370 ℃, 48.04 bar produced by the steam generator 112 enters the first natural gas heater 111 through the pipe, and converts natural gas into a high-temperature gas of 370 ℃, 48.04 bar The gas from the first natural gas heater (NG Heater) 111 enters the second stage heater of each of the second natural gas heater 113 and the third natural gas heater 114 again. In this case, the steam generator (Water The high-temperature steam of 370 ℃ and 48.04 bar produced by the heater) 112 enters the second and third natural gas heaters 113 and 114 through the pipe, and the natural gas is heated at 370 ℃ and 48.04 bar at 500 ℃, respectively. By increasing the temperature of natural gas to an ultra-high temperature of 46.08 bar, and 870 ° C., 44.12 bar, the high-temperature natural gas of the third natural gas heater 114 is introduced into the gas reforming reactor 120, and the corresponding steam generator 112 Some of the high-temperature steam produced in the is introduced into the gas reaction reformer (Gas Reformer) 120 to reform the steam and methane.

Since the high-temperature steam generated from the steam generator 112 as above flows into the gas reaction reformer 120, hydrogen in the gas reaction reformer 120 is methane and other light hydrocarbons in the reformed gas at 870 to 900 ° C. It is produced by a chemical reaction with ultra-high temperature steam and a pressure of 20 to 25 bar. The reaction is further reacted by an alumina or nickel-based catalyst to increase the reaction rate, and the water vapor/carbon molar ratio (%mol _H2O /%mol _C ) is between 3 and 5. The gas reforming reactor 120 must contain sufficient steam to prevent thermal cracking from hydrocarbon and coke formation, and a higher steam to carbon ratio also partially reduces the risk of carbon deposition on the catalyst surface. And, inside the natural gas reforming reactor 120, hydrocarbons present in natural gas react with steam to generate hydrogen and carbon monoxide. In this process, most of the hydrogen is produced, and the reaction produces carbon monoxide as a by-product, and ultimately requires an additional process to produce more hydrogen.

After that, the reformed gas and the remaining steam in the gas reforming reactor (Reformer System) 120 are cooled to a temperature of 350 ˚C and 40 bar by the cooler 170 (400) Desalination Plant (400) The cooling water is introduced through the pipe 434 from the Gas and steam are introduced into the vapor-gas reduction reaction unit 130 .

The above-described steam enters the high-temperature steam-gas reduction reactor (HT-WGS) 131 of the steam-gas reduction reaction unit 130 , and also a cooler 170 to further cool the gas of the gas reforming reactor 120 . In this case, the cooling water introduced through the pipe 434 from the desalination plant 400 produces high-temperature steam of 800 ° C. and 60 bar. At this time, the The main composition of the gas is carbon monoxide (CO). Additional hydrogen gas can be obtained by the catalytic reaction of carbon monoxide (CO) and steam, and becomes CH ₄ +H ₂ O→CO+3H ₂ , CO+H ₂ O→CO ₂ +H ₂ , and finally CO ₂ It becomes +4H ₂ . This reaction is exothermic and is commonly referred to as a vapor-gas reduction reaction or a shift reaction. Because the reaction is exothermic and regulated by equilibrium, the equilibrium constant means that the reaction is favorable at low temperatures as a function of temperature. Therefore, the heat generated during the reaction must be thoroughly removed. Nevertheless, the reaction rate decreases at lower temperatures.

Therefore, in the vapor-gas reduction reaction unit 130 of the embodiment of the present invention, a high-temperature vapor-gas reduction reactor 131 and a low-temperature vapor-gas reduction reactor 133 are introduced.

Inside the high-temperature steam-gas reduction reactor (HTWGS) 131, carbon monoxide reacts with steam at a temperature range of 310 to 370 ℃ in the presence of an iron oxide/chromium-based catalyst, and the outlet temperature range is 350 to 400 ℃. Most of the carbon monoxide (CO) in the process gas is converted to carbon dioxide (CO2). The remaining carbon monoxide (CO) in the exhaust gas is between 2 and 3 %. After that, the process gas leaves the high-temperature steam-gas reduction reactor (HTWGS) 131 and the reformed gas is cooled to a temperature of 200° C. by the cooler 132, and then enters the low-temperature steam-gas reduction reactor (LTWGS) 133. . In this case, the cooling water introduced through the pipe 434 from the desalination plant 400 to the cooler 132 cools the gas, and then is converted into high-temperature steam of about 500 ° C. to the steam turbine power generation unit ( It is guided to the vapor buffer tank 161 of 160, and is used for steam power generation.

In the case of a low-temperature steam-gas reduction reactor (LTWGS) (133), an inlet in the range of 190 to 230 °C and an outlet in the range of 220 to 250 °C are typical. Cold transfer reactions typically use catalysts composed of metallic copper, zinc oxide and one or more consumable oxides such as alumina, chromia, and the like. Most of carbon monoxide (CO) is converted to carbon dioxide (CO ₂ ), so that the content of carbon monoxide (CO) drops to less than 0.2 vol%. Then, the gas from the low-temperature vapor-gas reduction reactor (LTWGS) 133 is transferred to the cooler 134 . In this case, the temperature of the gas passing through the cooler 134 is reduced to 55 ℃. The cooling water introduced through the pipe 434 from the desalination plant 400 to the cooler 134 is converted into high-temperature steam of 500° C., and this high-temperature steam is the steam buffer of the steam turbine power generation unit 160. It is guided to the tank 161, and is used for steam turbine power generation.

The gas from the cooler 134 goes into the condenser 135, and the condensed water vapor is introduced into a separate pipe 320 of FIG. The amine carbon dioxide absorption device 147 is introduced into the device 140 .

It is composed of an amine carbon dioxide absorber that is a carbon dioxide removal device 140 , a pressure swing adsorption (PSA) 150 for hydrogen separation, and a steam turbine power generation unit 160 , and the Since the gas contains a small amount of carbon monoxide of 0.7% and a large amount of carbon dioxide of 50%, the gas passing through the condenser 135 of the amine carbon dioxide absorption device 147, which is the carbon dioxide removal device 140, passes through the inlet 141 The cooling water introduced into the amine carbon dioxide absorber 147 through the desalination plant 400 and through the pipe 434 from the desalination plant 400 is water (H 2 O) and amine at 25 to 30 ° C in the fresh water injection pump 142 In the injection pump 146, monoethanolamine (MEA) at 25-30 ° C., in the carbon dioxide absorber 147, water and an aqueous solution of monoethanolamine adsorb 0.7% of carbon monoxide to 50% of a large amount of carbon dioxide. After that, it is introduced into a monoethanolamine (MEA) regeneration device (steam boiler) 143 .

At this time, in order to maintain the interior of the monoethanolamine regenerating device 143 at 118 ° C. and 13.5 bar, the cooling water introduced through the pipe 434 from the desalination plant 400 is a pipe with a high temperature steam of 220 ° C. Through the steam pump 149, the steam introduced into the monoethanolamine regeneration device (boiler) 143 and reduced to 118 ° C. is sent to the underground pipe 320 of FIG. 1C to recycle or supply hot water. 1d flows into the demineralized water storage tank 432, and at the same time, the gas of the amine carbon dioxide absorber 141 absorbs carbon monoxide and carbon dioxide in the carbon dioxide absorber 147, and the remaining gas is some sediment (condensate) in the settling tank 145. ) and the like are introduced into the carbon dioxide absorber 147, and nitrogen including hydrogen is introduced into the pressure swing adsorption (PSA) 150 for hydrogen separation.

The cooling water introduced through the pipe 434 from the desalination plant 400 to the monoethanolamine (MEA) regeneration device 143 converts high-temperature 220° C., 23.2 bar steam to the steam pump 149 for monoethanol When it is put into the amine (MEA) regeneration device (boiler) 143 and the internal temperature is maintained at 228 ° C. and 13.5 bar, a small amount of carbon monoxide and carbon dioxide is gasified, and water is converted into water vapor, monoethanolamine (MEA) ) becomes a liquid, and monoethanolamine (MEA) is cooled in the recycled monoethanolamine (MEA) storage tank 148 and recycled again as monoethanolamine 146, and the vapor generated here is cooled again and then used again. It is transferred to the underground pipe 320 so that a minute amount of carbon monoxide and carbon dioxide gas is introduced into the cooler 301 of the carbon dioxide liquefaction device 300 of FIG. 1c through the amine filter 144.

The gas from the settling tank 145 is introduced into a pressure swing adsorption (PSA) 150 for hydrogen separation, and the gas at 29-30 ℃ and 23 bar is passed through the compressor 151 for 30- In order to maintain the temperature of the gas at a low temperature of 20 °C after increasing the pressure to 35 bar, the cooling water introduced through the pipe 434 from the desalination plant 400 is sent to the cooler 152 and used desalination plant Cooling water introduced through the pipe 434 from the (desalination plant) 400 is low temperature and therefore cannot be used for steam turbine power generation, so it is regenerated and sent to the pipe 320 of FIG.

The gas from the cooler 152 is 20 ℃, 25 bar, mainly hydrogen (H2) and very trace amounts of carbon monoxide (CO) as impurities, very trace amounts of carbon dioxide (CO ₂ ), very trace amounts of methane (CH ₄ ), a large amount of It flows into the adsorber 153 as nitrogen (N ₂ ), through which impurities (CO, CO ₂ , CH ₄ , N2) are removed and 99.99% of hydrogen is finally released. ) and finally delivered to the area where hydrogen is required through onshore piping.

The hydrogen separator 153 performs a cycle process of adsorbing impurities (CO, CO ₂ , CH ₄ , N ₂ ) from a hydrogen-rich gas stream at high pressure on a solid adsorbent such as molecular sieve. The process is carried out at room temperature and at an improved gas pressure of 20 to 25 bar. For the adsorption process, two adsorption vessels (adsorbers) are used. The feed gas is switched from one adsorption vessel to another, and while adsorption takes place in one filter, the adsorbent is regenerated in the other, a process carried out in a fresh adsorber (hydrogen separator) 153 which always produces a high purity gas. , the impurities are adsorbed on the inner surface of the adsorption filter. When this adsorber 153 has reached its adsorption capacity and can no longer remove impurities, it is switched off-line and the feed is switched to another new adsorber. In order to recover the hydrogen trapped in the adsorption space in the adsorber 153, the adsorber 153 is decompressed from the product side in the same direction as the feed flow direction (cocurrent) to discharge high-purity hydrogen. At this time, the desorbed impurities are excluded as off-gas in the adsorber 153 .

The cooling water introduced through the pipe 434 from the desalination plant 400 is the remainder used in the gas reforming reactor 120 among the high-temperature steam of the steam generator 112, high-temperature steam from the cooler 121, The high-temperature steam from the coolers 132 and 134 flows into the steam turbine power generation unit 160 , and all of the high-temperature steam flows into the steam buffer tank 161 . The high-temperature steam of 520-563 ℃ is difficult to operate the steam turbine despite the pressure of 29-35 bar, so it is converted into high-pressure steam of 400 ℃, 100 bar or more using the steam compressor 162, and the high-pressure steam turbine (163) is used for power generation, and then the steam is lowered to 280 ° C., 60 bar and introduced into the intermediate steam turbine 164 to be used for steam power generation, and then the steam is lowered to 210 ° C., 30 bar again to the low pressure steam turbine (165). ) and used for steam power generation, the energy generated in the high-pressure steam turbine 163, the intermediate steam turbine 164, and the low-pressure steam turbine 165 is used to generate electricity in the generator 166 to generate electricity in the internal wire (Spur line). is connected to the substation 168 with an underground box, and the voltage is boosted at the substation and transmitted to the required area through a transmission line. In addition, finally, the steam from the low pressure steam turbine 165 becomes 130 ° C., 6 bar, and the recondenser 167 converts the steam to 25 ° C., 5 bar condensate water to be used again. it becomes

Next, the steam generator (Water Heater) 112 of FIG. 1b uses fuel necessary to produce high-temperature steam of 370 °C and 48.04 bar. In this case, during combustion, waste gas (acid gas) such as carbon dioxide (CO ₂ ) and sulfur dioxide (SO ₂ ) is generated. Therefore, capture use and storage techniques are being utilized to mitigate the emission of man-made and environmentally harmful gases.

As described above, waste gas is generated due to the fuel used in the steam generator 112, and this waste gas passes through the sulfur dioxide condenser 207, which is the desulfurization facility reaction unit 200, sulfur dioxide (SO ₂ ) and carbon dioxide (CO ₂ ) Removal device Carbon dioxide (CO ₂ ) from the amine filter 224, which is an amine carbon dioxide absorption device of 220, is delivered to FIG. 1c, respectively, and sulfur dioxide (SO ₂ ) is introduced into the sulfur dioxide liquefaction processing unit 310, and carbon dioxide (CO ₂ ) is introduced into the carbon dioxide liquefaction apparatus 300 .

In addition, the waste gas burned at a high temperature of 677 ~ 721 ℃, 19 bar in the steam generator 112 is first transferred to the desulfurization reactor 201 of the desulfurization facility reaction unit 200 and the desulfurization reactor 201 which is a part of the desulfurization facility apparatus. In the reaction of hydrogen sulfide (H ₂ S) and carbonyl sulfide (COS) with zinc oxide (ZnO) to iron Ⅲ oxide (Fe ₂ O ₃ ), zinc sulfide (ZnS) to iron sulfide (FeS), water vapor (H ₂ O) and Carbon dioxide (CO ₂ ) is generated and separated in the separator 204 , in which case sulfur dioxide (SO ₂ ) is directly reacted with zinc oxide (ZnO) to iron oxide III (Fe ₂ O ₃ ) in a desulfurization reactor (DSRP) 205 . Thus, zinc sulfide (ZnS) to iron sulfide (FeS) and oxygen (O ₂ ) are separated.

In addition, zinc sulfide (ZnS) to iron sulfide (FeS) generated in the separator 204 and the direct desulfurization reactor (DSRP) 205 is compressed from the air heater 202 to the compressor 208 through the cooler 209 . Thus, the temperature of the air is raised to about 10° C. or more, and the zinc oxide (ZnO) to iron Ⅲ (Fe ₂ O ₃ ) are regenerated and used again by combining with oxygen (O ₂ ) in the air through the regeneration device 203 . Among them, those containing non-regenerated zinc sulfide (ZnS) to iron sulfide (FeS) and sulfide gas enter the separator 204 through the regeneration separator 211, the sulfide gas passes through the desulfurization reactor 201, and zinc sulfide ( ZnS) to iron sulfide (FeS) enter the air heater 202 again and enter the zinc oxide (ZnO) to iron III oxide (Fe ₂ O ₃ ) regenerating device 203 , to enter the zinc oxide (ZnO) to iron III oxide (Fe ₂ O). ₃ ) is regenerated and recycled. Direct desulfurization reactor (DSRP) (205) oxidation-reduction is completed and the generated sulfur dioxide (SO ₂ ) enters the cooler 210 and is sent to the sulfur condenser 207 at a temperature of 700 ° C. or less to the sulfur dioxide liquefaction processing unit of FIG. 1c (310). In addition, the sulfur dioxide (SO ₂ ) gas not condensed in the sulfur condenser 207 enters the desulfurization reactor 201 through the compressor 206 again and is separated again.

In this way, hydrogen sulfide (H ₂ S), carbonyl sulfide (COS), and sulfur dioxide (SO ₂ ) contained in the waste gas of the combustion gas are removed from the desulfurization facility reaction unit 200 and separated into sulfur dioxide (SO ₂ ) gas. It flows into the cooler 311 of the sulfur dioxide liquefaction processing unit 310 of 1c.

Carbon dioxide (CO ₂ ) contained in the high-temperature burned waste gas of 677-721 ℃, 19 bar in the steam generator 112 is 677-721 ℃, 19 bar before being introduced into the amine carbon dioxide absorber, which is the carbon dioxide removal device 220 The high-temperature waste gas is introduced into the boiler, which is the waste heat recovery device 226, and the cooling water introduced through the pipe 434 from the desalination plant 400 is converted into high-temperature steam at 600 to 650 ℃, 30 bar. It is introduced into the vapor buffer tank 161 of FIG. 1A and used for steam turbine power generation, and some of it is transferred to the pipe 320 of FIG. 1C so that hot water is supplied to an area requiring hot water.

And the waste gas, which has been reduced from 677 to 721 ℃ to 600 ℃, is introduced into the amine carbon dioxide absorber, which is the carbon dioxide removal device 220, and the waste gas contains 0.7% of carbon monoxide (CO) and 9% of a large amount of carbon dioxide ( CO2) is partially included, so this waste gas is introduced into the carbon dioxide (CO2) absorber 228 through the gas inlet 221 through the boiler 226, which is a waste heat recovery device, and is fed into the fresh water injection pump 222 from 25 to In the carbon dioxide (CO2) absorber 228, in which 30 °C water (H ₂ O) and 25-30 °C monoethanolamine (MEA) are introduced into the amine injection pump 227, an aqueous solution of water and monoethanolamine is 0.7 % of carbon monoxide (CO) to 9% of a large amount of carbon dioxide (CO2) is adsorbed and then introduced into the monoethanolamine (MEA) regeneration device (boiler) 223 .

At the same time, the gas introduced from the waste heat recovery device 226 through the inlet 221 is carbon monoxide and carbon dioxide absorbed by the carbon dioxide absorber 228, and the remaining gas is precipitated in the sedimentation tank 225, so that some condensed water is is again introduced into the carbon dioxide absorber 228 . At this time, the aqueous solution of water and monoethanolamine (MEA) is introduced into the monoethanolamine (MEA) regeneration device 223 in order to be regenerated, and the fresh water introduced through the pipe 434 from the desalination plant 400 . Produces high-temperature 220 ℃, 23.2 bar steam, produces high-temperature steam at 220 ℃ through the steam pump 229, and puts it into the boiler to maintain the internal temperature at 118 ℃, 13.5 bar, 0.7% of the fine amount Carbon monoxide, 9% carbon dioxide is gasified, water is changed to water vapor, monoethanolamine (MEA) becomes liquid, and regenerated monoethanolamine (MEA) is cooled in regenerated monoethanolamine (MEA) storage tank (230) The amine injection pump 227 is injected again, and the carbon dioxide absorber 228 is recycled again.

Here, the generated vapor is cooled again and then introduced into the pipe 320 of FIG. 1C to use it again, and a small amount of carbon monoxide and carbon dioxide is passed through the amine filter 224 to the cooler of the carbon dioxide liquefaction device 300 of FIG. 1C ( 301) is introduced.

In addition, one of the inevitable consequences of fuel consumption and production processes is the generation of waste gases such as carbon dioxide (CO ₂ ) and sulfur dioxide (SO ₂ ), so the use of capture to mitigate artificial and environmentally harmful gas emissions. and storage techniques.

Carbon dioxide (CO2) from the amine filter 144, which is an amine carbon dioxide absorber, which is the carbon dioxide removal device 140 of FIG. (CO ₂ ) and sulfur dioxide (SO ₂ ) gas that is not condensed in the sulfur condenser 207 of the desulfurization facility reaction unit 200 of FIG. is brought in

1C is a configuration for the liquefaction of carbon dioxide and sulfur dioxide as described above, based on gas direct compression and internal cooling by expansion and recirculation of liquefied gas.

Carbon dioxide (CO 2 ) extracted from the carbon dioxide (CO ₂ ) gas generated in the natural gas reforming reactor 120 and 130 of FIG. 1a through the amine filter 144 from the steam-gas reduction reaction unit 130 (CO ₂ ), Sulfur dioxide (SO ₂ ) gas that is not condensed in the sulfur condenser 207 of the desulfurization facility reaction unit 200 from the waste gas is sent to the cooler 311, the sulfur dioxide is removed from the waste gas, and the waste heat recovery device ( 226), the carbon dioxide (CO ₂ ) gas from _the amine filter 224 of the amine carbon dioxide absorption device, which is the carbon dioxide removal device 220, enters the carbon dioxide liquefaction device 300 and enters the desalination plant. ) 400 , the cooling water introduced through the pipe 434 is cooled by the cooling water sent through the cooler 301 . Then, the supply of carbon dioxide (CO2) at 26 °C and 35 bar is transferred to the first separator 302 to separate condensed components such as water before compression, and the condensed water generated at this time is received in the condensed water storage tank 308 and received externally discharged with

In addition, carbon dioxide (CO ₂ ) is compressed to a high pressure of 60 bar by the compressor 303 and then cooled and expanded by the second cooler 304 (if necessary) to decrease the temperature, which passes through the heat exchanger 305 while passing Lowering the temperature, it is liquefied while passing through the Joule-Thompson valve 306 and enters the separator 307. At this time, if a part is not liquefied, this carbon dioxide (CO ₂ ) gas passes through the heat exchanger 305 again to pass through the separator 307 It goes to (302) and goes through a circulation process again to liquefy. Thereafter, this liquefied carbon dioxide (CO ₂ ) is sold as fuel in a necessary area or a production plant using carbon dioxide (CO ₂ ), a gas welding machine, and the like.

677 ~ 721 ℃, 19 bar high temperature sulfur dioxide (SO ₂ ) gas in FIG. 1c enters the sulfur dioxide liquefaction processing unit 310 and the desalination plant 400 from the desalination plant 400 through the pipe 434 flows into the cooler ( 311) is cooled through the pump and is cooled by the cooling water sent. Then, the carbon dioxide supply at 26 ° C. and 46 bar is transferred to the first separator 312 to separate condensed components such as water before compression, and when condensed water is generated, it is received in the condensed water storage tank 318 and discharged to the outside.

Sulfur dioxide (SO ₂ ) is compressed to 50 bar high pressure by the compressor 313 and then cooled and expanded in the second cooler 314 (if necessary) to lower the temperature, which passes through the heat exchanger 315 to lower the temperature. It is lowered and liquefied as it passes through the Joule-Thompson valve 316 and enters the separator 317 . If a part is not liquefied, this sulfur dioxide gas enters the separator 312 through the heat exchanger 315 again to be liquefied through a circulation process again. After that, liquefied sulfur dioxide (SO ₂ ) is sold to factories using products such as sulfur dioxide (SO ₂ ). The condensed water from the re-condenser 167 of the steam turbine power generation unit 160 of FIG. 1A , a portion generated from the monoethanolamine (MEA) regeneration device 143 of the amine carbon dioxide absorption device, which is the carbon dioxide removal device 140 of FIG. 1A . Pressure swing adsorption (PSA) 150 for steam and hydrogen separation, some hot water from the boiler, which is the waste heat recovery device 226 of FIG. 1B2, and the amine carbon dioxide absorption device as the carbon dioxide removal device 220 The hot water generated by the monoethanolamine (MEA) regeneration device 223 and the hot water used as cooling water in the carbon dioxide liquefaction device 300 and the sulfur dioxide liquefaction processing unit 310 of FIG. 1c are all collected by the underground pipe 320 of FIG. 1c. After that, it is transferred to the demineralized water storage tanks 432 of FIG. 1d , and such hot water is sent through the pump 437 of FIG. 1d to an area requiring hot water.

4D is a desalination plant 400 according to an embodiment of the present invention, which supplies cooling water to the first natural gas heater 111 through the steam generator 110 of FIG. 1A. On the other hand, cooling water required for the cooler of the natural gas reforming reactor (Reformer) 120, the vapor-gas conversion reactor 133 of the vapor-gas reduction reaction unit 130, and the cooler of the carbon dioxide removal device 140 is supplied, and the amine Cooling water is also supplied to the carbon dioxide absorber 140 and the pressure circulation type adsorption device (PSA) 150 for capturing hydrogen.

In addition, the desalination plant 400 produces fresh water, that is, cooling water, supplied to the cooler of the amine carbon dioxide absorption device 220, the carbon dioxide liquefaction device 300 and the sulfur dioxide liquefaction treatment unit 310 of Fig. 1C. ) can supply cooling water to each component of the present invention, and at the same time, the remaining fresh water other than cooling water can be arbitrarily supplied to a required area.

In order to produce hydrogen (H ₂ ) from natural gas, which is a hydrogen production fuel, the desalination plant 400 requires a large amount of high temperature steam. In order to supply cooling water for cooling the high temperature steam, it must be It is a required component.

This desalination plant 400 is preferably located in the coastal zone (Basin) because seawater is used. The seawater is taken in by the seawater suction pump 403 through the injection pipe 402 through the screen filter 401 and is injected into the Flocculation Tank 406. Before being injected, the coagulant injection pump A coagulant is put into the 404, and sodium hypochlorite is directly introduced into the sodium hypochlorite injection pump 405, which is for cleaning and sterilizing seawater.

After removing the sediment injected into the sedimentation tank 406 together with seawater, the seawater from which the sediment has been removed is transferred to the filter storage tank after the polymer is injected into the biodegradable polymer injection pump 407 , is put into the primary filter storage tank (Primary Filters) 409 by the filter pump (408) to perform primary filtration, and is put into the floating filter storage tank (Polishing Filters) (410), while the suspended matter filter is filtered Removes up to 90% of suspended matter (more than 20 microns) through Air can be injected to remove floating matter more effectively.

Floating matter not removed even through the above-mentioned floatation process is put into the backwash tank 412, at this time, using a filter backwash pump 413, again the primary filters (Primary Filters) ( 409) and the suspension filter storage tank (Polishing Filters) 410 is filtered again.

In this way, the fresh water from which the suspended matter has been completely removed from the floating filter storage tank (Polishing Filters) 410 is sent to the cartridge primary filter (Cartridge Filter) 415, and an anti-acid agent is injected with an anti-acid injection pump (414). , a reverse osmosis (RO, Reverse Osmosis) membrane expansion inhibition pre-treatment agent is injected, and is first filtered in a cartridge primary filter (Cartridge Filter) 415 .

Thereafter, sodium bisulfite is added to the fresh water for browning of the fresh water and sterilization of microorganisms with a sodium bisulfite injection pump 416, and the high-pressure pump for reverse osmosis (SWRO Booster Pumps) 417 is used to supply the fresh water. It is fed to a Seawater Reverse Osmosis Systems (418), which uses a high pressure pump to filter the brine forcing it through a semi-porous membrane that prevents the flow of salt and other organic matter. Thereafter, the waste salt water (Rejected Brine) is returned to the sea with the waste salt water discharge pump (419), and the clean fresh water is stored in an adsorption tank (Suckback Tank) (420).

Here, the reverse osmosis permeate pump (SWRO Permeate Pump) 421 of the adsorption storage tank 420 is used to greatly reduce the reverse pressure of the storage tank of the reverse osmosis (RO) device, at this time the service water storage tank (Service Water) Removal of suspended matter from fresh water flowing into the Storage Tank) 422 Reverse osmosis pumps (Polishing Ro Feed Pumps) 423 are used to remove suspended matter.

The fresh water from which the suspended matter has been removed is put into a cartridge secondary filter 424, the secondary filtration is performed, and the suspended matter reverse osmosis device (Polishing RO Booster Pumps) 425 It flows into the Polishing RO Unit (426) to further remove suspended matter. Thereafter, the waste brine is returned to the sea to remove the waste fresh water containing salt with the waste brine discharge pump 427, and the clean fresh water is collected in a Polishing RO Permeate Tank 428. In addition, the float is removed.

In addition, fresh water introduced by the ion exchange unit inflow pump (Mixed Bed FEED Pump) 429 is produced as fresh water of excellent quality in the ion exchange unit (Mixed Bed Units) 430 . This process is generally the last treatment step of the water treatment process, and the treated fresh water is finally stored in demineralized water storage tanks 432 using the demineralized water pump 431 .

In addition, the condenser 167 of the steam turbine power generation unit 160 of FIG. 1A and the hot water recycled in FIG. 1C are stored in Demineralized Water Storage tanks 432 through the underground pipe 320 or supplied to the hot water area. Through the pump 437, the hot water is transferred to the required supply pump 438 according to each region through the underground pipe 320, whereby each hot water is transferred from the pump 438 to the required region through the underground pipe. And the fresh water in the demineralized water storage tanks (432) is re-transferred to the hydrogen (H2) production plant through the underground fresh water supply pipe (434) by the desalination water supply pump (433), or the local cooling water supply pump (435) In this case, the pump 435 sends the remaining fresh water through an underground pipe to the supply pump 436 for a required amount of cooling water according to each region, or is transferred to an area where each fresh water is required.

The fresh water coming out through the Seawater Reverse Osmosis Systems (418) of the desalination plant according to an embodiment of the present invention is calcium (Calcium) 4.5 ppm (0.00045%), magnesium (Magnesium) 24.8 ppm (0.00248%), Sodium 236.3 ppm (0.02363%), Potassium 7.5 ppm (0.00076%), Bicarbonate 1.5 ppm (0.00015%), Chloride 260.3 ppm (0.02603%), Sulphate 11.3 ppm (0.00113%) or less, and conductivity >>800mS/cm of fresh water, but nothing else.

In addition, fresh water passed through the Polishing RO Unit 426 and passed through the Polishing RO Permeate Tank 428 is Magnesium 0.5 ppm (0.00005%), Sodium ) 6.5 ppm (0.00065%), Potassium 0.3 ppm (0.00003%), Bicarbonate 0.8 ppm (0.00008%), Chloride 6.1 ppm (0.00061%), Sulphate 0.4 ppm (0.00004%) ) or less, and conductivity >> 25mS/cm, fresh water that has finally passed through the ion exchange unit (Mixed Bed Units) (430) is sodium 0.01 ppm (0.000001%), silicate 0.01 ppm (0.000001%) or less, conductivity < 0.2 mS/cm, which satisfies the standards for drinking water.

Therefore, the present invention is a desalination plant, hydrogen production, extraction and liquefaction of sulfur dioxide and carbon dioxide, a steam turbine, hot water supply, and a process for supplying the remaining fresh water to the necessary areas, so clean energy and renewable energy and carbon dioxide (CO ₂ ) and It is an innovative technology for the production of blue hydrogen that has undergone a comprehensive complex process of sulfur dioxide (SO ₂ ) capture technology.

Since the description of the present invention described above is merely an embodiment for structural or functional description, the scope of the present invention should not be construed as being limited by the embodiment described herein. That is, the present invention is not limited by the above-described embodiment and the accompanying drawings, but is limited by the following claims, and the configuration of the present invention is variously changed within the scope without departing from the technical spirit of the present invention. And since it can be modified, the embodiment of the present invention can be variously changed and can have various forms. Accordingly, it should be understood that the scope of the present invention includes equivalents capable of realizing the technical idea.

100: natural gas pre-processing unit 101: dewatering device
102, 103: desulfurization device 110: steam generator
111: first natural gas heater 112: steam generator
113, 114: second, third natural gas heater 115: combustion device
116: fresh water injection pump 117: air injection blower
120: gas reforming reactor 130 steam-gas reduction reaction unit
131: high-temperature steam-gas reduction reactor 133: low-temperature steam-gas reduction reactor
132, 134, 152, 209, 210, 301, 304, 311, 314: cooler
135: condensate storage tank 140: carbon dioxide removal device
141. 221: gas inlet 142, 222: fresh water injection pump
146, 227: regeneration monoamine injection pump 149, 229: steam (steam) injection pump
143, 223: monoethanolamine regeneration device 144, 224: amine filter
145, 225: sedimentation tank 147: amine carbon dioxide absorber
148: regenerated monoethanolamine storage tank 150: pressure circulation type adsorption device
151, 208, 313, 303 compressor 153 hydrogen separator
154: buffer tank 160: steam turbine power generation unit
161 vapor buffer tank 162 vapor compressor
163: high pressure steam turbine 164: intermediate steam turbine
165: low pressure steam turbine 166: generator
167: vapor recondensation tank 168: substation
200: desulfurization facility reaction unit 201: desulfurization reactor
202: air heater 203: regeneration device
204, 302, 307, 312, 317 Separator 205 Direct Desulfurization Reactor
206: residual gas recompressor 207: sulfur condenser
211: regeneration separator 220: carbon dioxide removal device
226: waste heat recovery device 228: carbon dioxide absorption device
230: regenerated mono-ethanolamine storage tank 223: mono-ethanolamine regenerating device
300: carbon dioxide liquefaction device 305, 315: exchanger
306, 316: Joule-Thompson valve 310: sulfur dioxide liquefaction processing unit
320: underground pipe 400: desalination plant 401: screen filter 402: seawater injection pipe 403: seawater pump 404: coagulant injection pump 405: sodium hypochlorite injection pump 406: settling tank
407: biodegradable polymer injection pump 408: filter pump 409: initial filter storage tank 410: floating filter storage tank 411: filtering blower 412: backwash storage tank 413: backwash filtration pump 414: acid-resistant agent injection pump
415: Cartridge primary filter 416: Sodium hydrogen sulfite input pump 417: Reverse osmosis high pressure pump 418: Seawater reverse osmosis system 419, 427: Waste brine discharge pump 420: Adsorption storage tank 421: Reverse osmosis permeation pump 422: Service water storage tank 423: Floating matter removal reverse osmosis pump 424: Cartridge secondary filter 425: Floating matter reverse osmosis high pressure pump 426: Floating matter reverse osmosis device 428: Floating matter reverse osmosis permeation storage tank 429: Ion exchange device inlet pump 430: Ion exchange device 431: Demineralized water pump 432: Demineralized water Storage tank (fresh water storage tank) 433: Demineralized water (fresh water) supply pump 434: Fresh water supply pipe 435: Cooling water area transfer pump 436: Cooling water transfer pump required for each area
437: hot water area transfer pump 438: hot water transfer pump required for each area

Claims (9)

A steam generator 112 that produces steam at a high temperature of 370 ℃ and 48.04 bar from fresh water flowing in at a high temperature of 1,750 to 2,000 ℃ by having a combustion device 115 and a blower 117 using a burner or plasma, the steam A first natural gas heater 111 that converts natural gas to a high-temperature gas of 370° C. and 48.04 bar by introducing high-temperature steam of 370° C. and 48.04 bar from the generator 112, generated from the steam generator 112 The high-temperature steam of 370 ℃ and 48.04 bar is introduced, and the natural gas converted in the first natural gas heater 111 is converted into ultra-high temperature natural gas of 370-500 ℃, 48.04-46.08 bar to the gas reforming reactor ( Steam generator 110 having a second, third natural gas heater 113, 114 for supplying to 120; and
High-temperature steam is introduced from the steam generator 112 and ultra-high-temperature natural gas is introduced from the third natural gas heater 114, and hydrocarbons and steam present in the natural gas react with hydrogen and hydrogen by an alumina or nickel-based catalyst. In the blue hydrogen production apparatus using natural gas, consisting of a gas reforming reactor 120 for generating carbon monoxide,
A natural gas pretreatment unit 100 having a dehydration device 101 for removing moisture from natural gas, and first and second desulfurization devices 102 and 103 for removing hydrogen sulfide from the natural gas from which the moisture has been removed. further comprising,
The gas reformed in the gas reforming reactor 120 and carbon monoxide contained in the remaining steam are reacted with steam at a temperature range of 310 to 370 ° C in the presence of iron oxide and a chromium catalyst to convert to carbon dioxide of 350 to 400 ° C. The high-temperature steam-gas reduction reactor 131, and the process gas of the high-temperature steam-gas reduction reactor 131 is cooled to 200° C., and a catalyst composed of metal copper, zinc oxide, alumina, and chromia, at least one consumable oxide. a low-temperature steam-reducing reactor 133 for converting carbon monoxide in the process gas into carbon dioxide and transferring it to a cooler 134 into which fresh water is introduced - a vapor-gas reduction reaction unit 130;
Gas is introduced from the low-temperature steam-reduction reactor 133, fresh water of 25-30 ℃ is introduced, and monoethanolamine of 25-30 ℃ is introduced from the regeneration motor ethanol amine storage tank 148 to adsorb and remove carbon dioxide. Absorber 147, a monoethanolamine regeneration device 143 for regenerating monoethanolamine from the gas from which steam of 220° C. is introduced and the carbon dioxide is removed by adsorption and storing it in the regenerated monoethanolamine storage tank 148, the monoethanol An amine filter 144 that filters the gas discharged from the amine regeneration device 143 and supplies carbon monoxide and carbon dioxide to the carbon dioxide liquefaction system 301, the amine carbon dioxide absorber 147, and the monoethanolamine regeneration device 143 a carbon dioxide removal device 140 having a settling tank 145 for transferring nitrogen containing hydrogen in the gas discharged from the pressure circulation type adsorption device; and
A compressor 151 for increasing the pressure of nitrogen containing hydrogen at 29-30 ℃ and 23 bar from the settling tank 145 to 30 bar, and a cooler 152 for cooling the nitrogen containing the pressurized hydrogen with fresh water. ), a pressure circulation type adsorption equipped with a hydrogen separator 153 that stores a small amount of carbon monoxide, carbon dioxide, methane, and a large amount of nitrogen contained in the hydrogen discharged from the cooler 152 in a buffer tank 154 that adsorbs and removes it. Blue hydrogen production apparatus using natural gas, characterized in that it further comprises an apparatus 150.
delete According to claim 1,
A screen filter 401 that filters seawater,
A settling tank 406 for washing and sterilizing the seawater by adding a coagulant and sodium hypochlorite together with the seawater that has passed through the screen filter 401;
An initial filter storage tank 409 for primary filtering of the washed and sterilized seawater input together with the biodegradable polymer;
Floating filter storage tank 410 for removing suspended matter from the first filtered seawater,
Cartridge primary filter (415) for first filtering the fresh water from which the suspended matter is removed, which is added together with the anti-acid agent and the reverse osmosis membrane expansion inhibition pretreatment drug;
A seawater reverse osmosis system (418) for sterilizing the browning and microorganisms of fresh water fed from the cartridge primary filter (415) together with sodium hydrogen sulfite using the high-pressure pump (417) for reverse osmosis (418);
Adsorption storage tank 421 into which fresh water of the seawater reverse osmosis system 418 is introduced,
a service water storage tank 422 into which the fresh water of the adsorption storage tank 421 is introduced by reducing the back pressure through the reverse osmosis permeation pump 421;
A cartridge secondary filter 424 for secondary filtering of fresh water by removing suspended matter from the service water storage tank 422 and removing the suspended matter by the reverse osmosis pump 423,
A permeation storage tank 428 for floating matter reverse osmosis, which is introduced into the apparatus 426 for reverse osmosis of suspended matter by a high-pressure pump 425 for reverse osmosis and removes additional suspended matter from the fresh water of the cartridge secondary filter 424 from which suspended matter has been removed, and
A desalination plant equipped with an ion exchange device 430 for producing excellent quality fresh water from the fresh water of the reverse osmosis permeation storage tank 428 through the ion exchange device inlet pump 429 and storing it in the demineralized water storage tank 432 ( 400) is composed of,
Further comprising a filtering blower 411 for injecting filtered air into the initial filter storage tank 409 and the floating filter storage tank 410,
Backwash storage tank 412 for re-filtering seawater from which suspended matter has not been removed from the suspension filter storage tank 410 in the initial filter storage tank 409 and the floating material filter storage tank 410 through the backwash filtration pump 413 Blue hydrogen production apparatus using natural gas, characterized in that it further comprises.
delete delete delete Blue hydrogen production apparatus using the natural gas of claim 1;
Desulfurization facility reaction unit 200;
carbon dioxide removal device 220; and
Carbon dioxide liquefaction device (300)
Consists of further including
The desulfurization facility reaction unit 200,
Waste gas of 677∼721 ℃, 19 bar generated from the steam generator 112 is introduced, and hydrogen sulfide (H ₂ S) and carbonyl sulfide (COS) react with zinc oxide (ZnO) to iron oxide Ⅲ (Fe ₂ O ₃ ) Desulfurization reactor 201 that generates zinc sulfide (ZnS) to iron sulfide (FeS), water vapor (H ₂ O) and carbon dioxide (CO ₂ ) while
A separator 204 for separating sulfur dioxide from zinc sulfide (ZnS) to iron sulfide (FeS), water vapor (H ₂ O) and carbon dioxide (CO ₂ ) of the desulfurization reactor 201;
In the separator 204, zinc sulfide (ZnS) to iron sulfide (FeS), water vapor (H ₂ O) and carbon dioxide (CO ₂ ) from which sulfur dioxide is separated in the separator 204 are reacted with zinc oxide (ZnO) to iron Ⅲ oxide (Fe ₂ O ₃ ) a direct desulfurization reactor 205 to separate zinc sulfide (ZnS) to iron sulfide (FeS) and oxygen (O ₂ );
Zinc sulfide (ZnS) to iron sulfide (FeS) generated in the separator 204 and the direct desulfurization reactor 205) is combined with oxygen in the external air of the air heater 202 that has passed through the cooler 208 to combine with zinc oxide (ZnO). ) to iron oxide III (Fe ₂ O ₃ ) regeneration device 203 to regenerate,
A regeneration separator 211 in which sulfide gas is separated from zinc sulfide (ZnS) to iron sulfide (FeS) and sulfide gas not regenerated in the regeneration device 203 and flows into the separator 204 through the desulfurization reactor 201; and
It is composed of a sulfur condenser 207 for condensing the sulfur dioxide produced by oxidation-reduction completed in the direct desulfurization reactor 205,
The carbon dioxide removal device 220,
Waste heat recovery device 226 for converting the 677 to 721 ℃, 19 bar waste gas generated in the steam generator 112 into high temperature steam of 600 to 650 ℃ 30 bar by fresh water and storing it in the vapor buffer tank 161 ,
From the waste gas flowing from the waste heat recovery device 226, an aqueous solution of water (H ₂ O) at 25-30 ° C and monoethanolamine at 25-30 ° C. a carbon dioxide absorber 228 to adsorb, and
A monoethanolamine regeneration device for regenerating monoethanolamine from the waste gas adsorbed from the carbon dioxide absorber 228 to a large amount of carbon monoxide of 0.7% to 9% of carbon dioxide and storing it in the regeneration monoethanolamine storage tank 230 ( 223), and
The carbon dioxide liquefaction device 300,
A cooler 301 for cooling the carbon dioxide gas absorbed in the amine carbon dioxide absorber 147, 228 with fresh water;
a separator (302) for separating condensed components, such as water, from the gas cooled by the cooler (301);
Compressor 303 for compressing carbon dioxide from which condensed components such as water are separated in the separator 302 to high pressure;
A cooler 304 for cooling the carbon dioxide compressed at high pressure in the compressor 303,
An exchanger 305 that lowers the temperature of the carbon dioxide cooled in the cooler 304 and liquefies it while passing through the Joule-Thompson valve 306, and
Separator 307 for separating non-liquefied carbon dioxide from among the liquefied carbon dioxide, re-supplying it to the exchanger 305, and storing the liquefied carbon dioxide in an external storage tank
A liquefaction device for waste gas generated during raw material combustion, characterized in that it consists of. 8. The method of claim 7,
A cooler 311 cooling the sulfur dioxide gas not condensed in the sulfur condenser 207 by receiving fresh water;
a separator (312) for separating condensed components such as water from the sulfur dioxide gas cooled in the cooler (311);
A compressor 313 that compresses the sulfur dioxide from which condensed components such as water are separated in the separator 312 to a high pressure;
A cooler 314 for cooling the sulfur dioxide compressed at high pressure in the compressor 313,
an exchanger 315 that lowers the temperature of the sulfur dioxide cooled in the cooler 314 and liquefies it by passing it through a Joule-Thompson valve 316, and
Sulfur dioxide liquefaction treatment unit 310 having a separator 317 for separating non-liquefied sulfur dioxide from among the liquefied sulfur dioxide, re-supplying it to the exchanger 315, and storing the liquefied sulfur dioxide in a storage tank
The liquefaction apparatus of waste gas generated during raw material combustion, characterized in that it further comprises. delete

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