CN1485003A - Method and apparatus of semiconductor generating electricity and producing hydrogen using temperature difference and liquid natural gas providing cooling energy - Google Patents
Method and apparatus of semiconductor generating electricity and producing hydrogen using temperature difference and liquid natural gas providing cooling energy Download PDFInfo
- Publication number
- CN1485003A CN1485003A CNA021383499A CN02138349A CN1485003A CN 1485003 A CN1485003 A CN 1485003A CN A021383499 A CNA021383499 A CN A021383499A CN 02138349 A CN02138349 A CN 02138349A CN 1485003 A CN1485003 A CN 1485003A
- Authority
- CN
- China
- Prior art keywords
- heat exchanger
- semiconductor
- seawater
- lng
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
A method of generating electricity and preparing hydrogen taking advantage of difference in temperature of semiconductors. It is characterized in, the semiconductor genertrix by thermal difference is composed of cold or heat surfaces of a thermopile closely contacting with cooling-source heat exchanger with LNG flowing, and heating-source heat exchanger with sea flowing. While heating LNG, the semiconductor genertrix by thermal difference produces direct currents; connecting the power with anode and cathode of an electrobath, water is electrolyzed into hydrogen and oxygen; some seawater first cools the alkali liquor of electrolyzed water, then is transmitted to the heating-source heat exchanger. Sea water provides cooling water when preparing hydrogen, as well as provides heating source of LNG, which improve efficiency of semiconductor; electricity produced in recycling LNG could be used to prepare hydrogen, which saves the area of heat exchanger and cooling water for preparing hydrogen.
Description
Technical field:
The invention belongs to energy technology field, particularly relate to the interleaving techniques field of recycling, semiconductor temperature differential generating and the water electrolysis hydrogen production of liquefied natural gas (LNG) cold energy.
Background technology:
Along with the continuous appearance with various high-quality semi-conducting materials of developing rapidly of semiconductor technology, semiconductor refrigerating technology has been obtained remarkable progress, and the semiconductor temperature differential generating technology has caused great concern and many practical examples are arranged.According to the Seebeck principle, its loop can produce electromotive force when there is the temperature difference in the two ends that the P type contacts with N-type semiconductor, also is thermoelectrical potential, and the open circuit two ends in loop produce electrical potential difference.Used semi-conductor thermoelectric material mainly contains lead telluride (PbTe) and bismuth telluride (Bi2Te) at present.So far, utilizing the technology of semiconductor temperature differential generating and research only to notice that utilization is higher than the waste heat aspect of environment temperature, is 89211854 low temperature difference TRT as China Patent No.; And for example the patent No. is 92223002 semiconductor thermal electric organ, and its hot-side temperature maintains on about 200 ℃; And utilize cryogenic cold energy, particularly utilize the semiconductor temperature differential generating technology of cold energy of liquefied natural gas still not to be reported.Liquefied natural gas (being called for short LNG) is a kind of liquid clean fuel that generally adopts in the world based on methane.To ℃ be heated to be the gas of normal temperature to it from temperature-161 with seawater or air when making fuel and using, consume and add the about 900kJ/kg of heat.Therefore, the cold that contains a large amount of preciousnesses among the LNG can utilize.China played every year in 2003 and wants 2,000,000 tons of LNG of import, contained the cold of 700,000,000 degree electricity nearly.Reclaiming the LNG cold energy is a valuable job.The 1997 annual inquiry reports of writing according to New Energy and Industrial Technology Development Organization (NEDO-NP-9734) " about the investigation of the cascade utilization of heat energy (heat energy of cold heat energy and temperature) ", the method of currently used recovery LNG cold energy generation is to be that thermal source, LNG are low-temperature receiver, are the power cycle electricity-generating method of working medium with the cold-producing medium with seawater, this square law device complexity, require LNG gasification use amount stable, but the LNG demand fluctuate.
The electricity that semiconductor sends is a direct current, deliver to the difficulty that electrical network not only has the electric power policy, and needs inverter that direct current become to exchange etc., and installation cost is more expensive.On the other hand, hydrogen is senior clean fuel and valuable raw material of industry gas, and demand is very big, and how high-purity hydrogen is produced with the brine electrolysis method.During the prior art water electrolysis hydrogen production, the Joule heat that electric current produces by the aqueous solution fails to utilize, and power consumption is big; In addition,, avoid the temperature of electrolytic aqueous solution to rise so high and remove the hydrogen of generation and the steam in the oxygen, need to consume a large amount of cooling waters, hydrogen manufacturing cost height in order to take away Joule heat.
Summary of the invention:
The present invention proposes a kind ofly to utilize the semiconductor thermal difference generation method and the device of cold energy of liquefied natural gas and utilize this electric energy to come the method and apparatus of water electrolysis hydrogen production.
The present invention utilizes the semiconductor thermal difference generation method of cold energy of liquefied natural gas, it is characterized in that: with liquefied natural gas (LNG) is low-temperature receiver, with the seawater is thermal source, the both ends of the surface of semiconductor temperature difference thermoelectric pile are closely contacted with seawater thermal source heat exchanger with LNG low-temperature receiver heat exchanger respectively make semiconductor thermoelectric generator, allow LNG and seawater respectively by low-temperature receiver heat exchanger and seawater thermal source heat exchanger, the heat of seawater is passed to LNG after by the semiconductor temperature difference thermoelectric pile, low-temperature liquefaction natural gas heat absorption evaporation, semiconductor temperature difference thermoelectric pile two ends produce electrical potential difference by the temperature difference and generate electricity.
The present invention utilizes the semiconductor thermo-electric generation apparatus of cold energy of liquefied natural gas, comprise the semiconductor thermoelectric generator that the semiconductor thermoelectric module sheet that is made of P type and N-type semiconductor material 1 and low-temperature receiver heat exchanger and thermal source heat exchanger constitute, it is characterized in that: described low-temperature receiver heat exchanger is to grip the LNG low-temperature receiver heat exchanger that the good filler 2 of filling heat conduction forms between LNG heat exchanger tube 5, tube sheet by two metal plates 4; Semiconductor thermoelectric module sheet 1 is close to two metal plates, 4 outsides; Metallic plate strip of paper used for sealing 3 hard-pressed bales form flat box-like semiconductor thermoelectric generator unit piece E in semiconductor thermoelectric module sheet 1 outside; Its top is provided with the seawater spraying pipe 6 that is connected with the seawater conveyance conduit, and seawater is flow through from the surface of metallic plate strip of paper used for sealing 3, forms seawater thermal source heat exchanger; Electric wire A and B that every semiconductor thermoelectric generator unit piece E has respectively the LNG inlet pipe that links to each other with LNG heat exchanger tube 5 two ends of drawing in the box and the natural gas (NG) that has gasified go out pipe and link to each other with 1 two electrodes of semiconductor thermoelectric module sheet respectively.
Described semiconductor thermoelectric generator can be semiconductor thermoelectric generator unit piece E, also can be the semiconductor generating set component C that is combined by two or more semiconductor thermoelectric generator unit pieces E; Between each generator unit spare E of semiconductor generating set component C, accompany keeping the filler strip 7 in the seawater runner gap between two unit pieces, and a plurality of generator unit spares are clamped with pressing plate and bolt; Above semiconductor thermoelectric generator, be provided with seawater spraying pipe 6.
Metallic plate strip of paper used for sealing 3 outsides of described thermal source heat exchanger can have the fin of the enhanced heat exchange that flows to downstream.
The good filler 2 of the heat conduction of filling can be selected lead, babbit or copper powder, aluminium powder for use between the tube sheet of described low-temperature receiver heat exchanger.
The described semiconductor temperature difference thermoelectric pile sheet 1 that is attached to metal plate 4 outsides pastes one deck at least, also can paste two layers or multilayer.
The present invention utilizes the method for cold energy of liquefied natural gas semiconductor temperature differential generating hydrogen manufacturing, it is characterized in that: the power supply that semiconductor temperature differential generating partly provides water electrolysis hydrogen production to use is by being thermal source with the seawater, being the direct current that the semiconductor thermoelectric generator of low-temperature receiver provides with liquefied natural gas (LNG); Seawater is pumped up the thermal source heat exchanger that back branch two tunnel: a tunnel is delivered to one group of semiconductor thermoelectric generator, after containing liquid hydrogen gas and containing liquid oxygen gas and backflow electrolyte of cooling water electrolysis hydrogen production device sent on another road earlier, deliver to the thermal source heat exchanger of another group semiconductor thermoelectric generator again; Fall warm seawater through the thermal source heat exchanger and discharged go back to the sea; LNG by force feed to the low-temperature receiver heat exchanger of semiconductor thermoelectric generator; When seawater was passed to LNG in the low-temperature receiver heat exchanger to heat from the thermal source heat exchanger by the semiconductor thermoelectric module sheet, semiconductor thermoelectric generator sent direct current; This direct current is connected to the both positive and negative polarity of hydrogen manufacturing electrolytic cell, the raw water that enters electrolytic cell is by electrolysis, the alkaline aqueous solution electrolysis produces and contains liquid hydrogen gas and contain liquid oxygen gas, collect respectively after separate generation hydrogen, oxygen, again through having a surplus cold natural gas (NG) cooling, further remove and send to the compression bottling behind the steam or liquefaction stores; Isolated raffinate by cooled with seawater after the blowback electrolytic cell; Natural gas after the gasification compiles output.
The present invention utilizes the device of cold energy of liquefied natural gas semiconductor temperature differential generating hydrogen manufacturing, it is characterized in that comprising semiconductor thermoelectric generator and water electrolysis hydrogen production device H; Described semiconductor thermoelectric generator is to combine with parallel vertical panel form by being flat box-like semiconductor thermoelectric generator unit piece E; Wherein LNG low-temperature receiver heat exchanger adopts and is being gripped by two metal plates 4 that the good filler 2 of filling heat conduction constitutes between the band-tube type heat exchanger structure, tube sheet of LNG heat exchanger tube 5; Semiconductor thermoelectric module sheet 1 is close to two metal plates, 4 outsides of gripping LNG low-temperature receiver heat exchanger; Metallic plate strip of paper used for sealing 3 hard-pressed bale again constitutes and to be flat box-like semiconductor thermoelectric generator unit piece E outside, and its top is provided with the seawater spraying pipe 6 that is connected with the seawater conveyance conduit, and seawater is flow through from the surface of metallic plate strip of paper used for sealing 3, forms seawater thermal source heat exchanger; Electric wire A and B that every semiconductor thermoelectric generator unit piece E has respectively the LNG inlet pipe that links to each other with LNG heat exchanger tube 5 two ends of drawing in the box and the natural gas (NG) that has gasified go out pipe and link to each other with 1 two electrodes of semiconductor thermoelectric module sheet respectively; Seawater divides two the tunnel, the one tunnel to be connected to the seawater spraying pipe LB1 of one group of semiconductor generator sub-assembly BD1 top through control valve V1 after pipe is sent into seawater carrier pipe L2 by pump WP; Another road with after the cooling tube of hydrogen alkali lye-seawater heat exchanger Q1 and oxygen depletion-seawater heat exchanger Q2 links to each other, is connected to the seawater spraying pipe LB2 of another group semiconductor thermoelectric generator sub-assembly BD2 top through control valve V2 again; The total inlet pipe N1 of LNG receives the LNG heat exchanger tube import of the low-temperature receiver heat exchanger of semiconductor thermoelectric generator sub-assembly BD1 and BD2 behind valve V3, the outlet of LNG heat exchanger tube is connected with the tube connector N2 of natural gas (NG), and joins through control valve V4 and the total efferent duct N4 of natural gas; After dividing the heat exchanger tube of a branch road N3 and oxygen cooling water devaporation device Y2 and hydrogen cooling water devaporation device Y1 to join from N2 pipe, join through valve V5 and the total efferent duct N4 of natural gas again; The electrode of semiconductor thermoelectric generator is drawn through electric wire A and B respectively, by behind the required series/parallel of electrolysis, is connected with the positive and negative electrode plate of the electrolytic cell D of water electrolysis hydrogen production device H respectively; Among the described water electrolysis hydrogen production device H, the hydrogen gas side of electrolytic cell D is connected with hydrogen-gas-liquid separator F1, hydrogen cooling water devaporation device Y1 successively; The oxygen side of electrolytic cell D is connected with oxygen-gas-liquid separator F2, oxygen cooling water devaporation device Y2 successively; After Y1 and Y2 leave hydrogen outlet and oxygen outlet and pressure balance adjuster respectively and join, be sent to user or compression bottling more respectively; Hydrogeneous alkali lye loop is connected to hydrogen-gas-liquid separator F1 bottom by hydrogen cooling water devaporation device Y1 bottom, is joined by F1 outlet at bottom and hydrogeneous alkali lye loopback pump P1 again, then meets hydrogen alkali lye-seawater heat exchanger Q1, is transmitted back to electrolytic cell D again; Contain oxonium base liquid loop and be connected to oxygen-gas-liquid separator F2 bottom by oxygen cooling water devaporation device Y2 bottom, again by the F2 outlet at bottom with contain oxonium base liquid loopback pump P2 and join, then meet oxonium base liquid-seawater heat exchanger Q2, be transmitted back to electrolytic cell D again;
The present invention is a low-temperature receiver owing to having taked with the liquefied natural gas, with the seawater is thermal source, the cold and hot both ends of the surface of semiconductor temperature difference thermoelectric pile sheet are closely contacted with seawater thermal source heat exchanger with LNG low-temperature receiver heat exchanger respectively make semiconductor thermoelectric generator, allow LNG and seawater respectively by the semiconductor thermal difference generation method of low-temperature receiver heat exchanger and seawater thermal source heat exchanger, in seawater heating LNG, reclaimed electric energy.
It is low-temperature receiver that the present invention also takes with the liquefied natural gas, is thermal source with seawater with the used heat that reclaims water electrolysis hydrogen production, allows LNG and seawater respectively by the semiconductor thermal difference generation method of low-temperature receiver heat exchanger and seawater thermal source heat exchanger, cold and hot complementation is arranged, the advantage of two-way benefit.Semiconductor generator had both improved the semiconductor generating efficiency because increased the Cooling and Heat Source temperature difference, had saved two heat exchanger areas again.The direct current that sends when utilizing seawater heating LNG is as the power supply of water electrolysis hydrogen production, can save is incorporated into the power networks when only reclaiming the LNG cold energy generation send the required change of electricity to send device, need transfer 220 volts alternating current to about 20 volts of galvanic AC-DC converters when also having saved, water electrolysis hydrogen production power consumption cost and equipment cost are greatly reduced with the AC power water electrolysis hydrogen production.
Apparatus of the present invention are taked gripping LNG heat exchanger tube 5 by two metal plates 4, and the LNG low-temperature receiver heat exchanger of filling heat conduction good material can improve low-temperature receiver heat exchange effect between tube sheet; Adopt metallic plate that the semiconductor thermoelectric generator unit piece E that thermoelectric pile sheet 1 and LNG low-temperature receiver heat exchanger all tightly wrap in its inner structure is combined into semiconductor thermoelectric generator, have compact conformation, combination is easy to advantage; By the shower 6 that is located at the semiconductor thermoelectric generator top seawater spraying on the metallic plate strip of paper used for sealing 3 of semiconductor thermoelectric generator to hard-pressed bale, can be strengthened the heat-transfer effect of seawater thermal source heat exchanger; Apparatus of the present invention movement-less part, reliable.
China's plan Liquefied Natural Gas Import (LNG) 2,000,000 tons in 2003, containing cold when LNG is converted into 20 ℃ of natural gases of 20 atmospheric pressure (the 97%th, methane) is 935kJ/kg, theoretical calculating contains can be function 642kJ/kg; If adopt the inventive method and device, to do 30% of function by recovery and generate electricity, then recyclable electric energy 100,000,000 degree can be produced 2,200 ten thousand m
3Hydrogen, if by reached 5,000,000 tons of calculating by 2010, can make 5,400 ten thousand m
3Hydrogen.Its economic worth is very considerable.
Accompanying drawing and explanation thereof:
Fig. 1 is the system flow schematic diagram of the method for the present invention's semiconductor temperature differential generating of utilizing the LNG cold energy.
Fig. 2 is the structural representation of semiconductor generator unit spare E of the device of the present invention's semiconductor temperature differential generating of utilizing the LNG cold energy.
Fig. 3 is the structural representation of semiconductor generating set component C.
Fig. 4 is the principle schematic that the present invention utilizes LNG cold energy semiconductor temperature differential generating device for producing hydrogen.
The specific embodiment:
Embodiment 1: the semiconductor thermal difference generation method and the device that utilize the LNG cold energy
The present invention who provides as accompanying drawing 1 utilizes a kind of apparatus system schematic flow sheet of method of the semiconductor temperature differential generating of LNG cold energy, comprised semiconductor generator assembly C in the present embodiment apparatus system, sea water pump P1, seawater suction line L1, seawater carrier pipe L2, seawater return pipe or canal L3, seawater spraying pipe 6, total inlet pipe N1 of LNG and gasification natural gas always go out to manage N2, and the electric current total input-wire A and the total outlet B that have protection tube; Semiconductor generator assembly C is combined by several semiconductor electric organ unit piece E.The structure of described semiconductor generator unit spare E as shown in Figure 2, low-temperature receiver heat exchanger wherein adopts the band-tube type structure, metal plate 4 is selected good aluminium sheet of heat conduction or copper coin for use, 4 of two metal plates accompany the copper tube that is connected with low-temperature receiver catalyst carrier delivery pump and pipeline as LNG heat exchanger tube 5, and LNG flows through in copper tube; The good filler 2 of filling heat conduction is generally selected fusible metal for use between copper tube and flat board, for example selects lead, babbit or copper powder, aluminium powder for use.For requiring the not high occasion of pressure after the LNG gasification, copper tube also can select flat pipe; One deck semiconductor thermoelectric module sheet 1 at least all is close in the outside of two metal plates 4 of LNG low-temperature receiver heat exchanger, also can paste two layers or three layers; The thermal source heat exchanger is a seawater thermal source heat exchanger, to be close to the aluminium metal sheet strip of paper used for sealing 3 in thermoelectric pile sheet 1 outside, thermoelectric pile sheet 1 and LNG low-temperature receiver heat exchanger are all tightly wrapped within it, form flat box-like semiconductor thermoelectric generator unit piece E, its top is provided with the seawater spraying pipe 6 that is connected with thermal source catalyst carrier delivery pump and pipeline, make seawater from metallic plate strip of paper used for sealing surface current mistake, form seawater thermal source heat exchanger; Two electrodes of every semiconductor thermoelectric generator unit piece E are drawn through electric wire A and B respectively.
Accompanying drawing 3 has provided the structural representation of a kind of semiconductor generating set component C, it is made of side by side 3 semiconductor generator unit spare E, accompany the filler strip 7 that keeps the seawater ebb interval between the two adjacent generator unit spare E, and from two generator unit spares of outermost a plurality of generator unit spares are clamped with pressing plate and bolt.For keeping the critical piece diagrammatic sketch clear, do not draw in the structure chart that conventional pressing plate and bolt compress mode.Common every chip semiconductor temperature difference heat pile all indicates specified operating voltage and electric current, for example 12 volts * 5 pacify, according to the requirement of the electrolytic cell that will use the electric lead-out wire of each semiconductor thermoelectric module sheet is connected and/or parallel connection after (for example, make bringing onto load output that 16～20 volts of voltages be arranged), draw by electric wire A and B.
The power generation process that the present invention utilizes the semiconductor generating to reclaim the device of LNG cold energy is: start sea water pump P1, seawater from seawater suction line L1 suction, deliver to the seawater spraying pipe 6 that is located at semiconductor generating set component C top through seawater carrier pipe L2, the seawater that sprays out flows down along the thermal source heat exchanger metallic plate strip of paper used for sealing outside of each semiconductor generator unit spare E, is discharged go back to the sea by seawater return pipe or canal L3 collection back; The LNG that is risen to about 2～4MPa pressure by LNG liquid pump is diverted to from the total inlet pipe N1 of LNG in the LNG heat exchanger tube 5 of the LNG low-temperature receiver heat exchanger in each semiconductor generator unit spare E, and the natural gas after the gasification flows out from always going out to manage N2; The heat of seawater thermal source is passed to the LNG of LNG low-temperature receiver heat exchanger after by semiconductor thermoelectric module sheet 1, ocean temperature will be reduced to 5 ℃ from about 25 ℃,-161 ℃ LNG will be-110 ℃ of heat absorption evaporation and intensifications down, and the semiconductor thermoelectric generator two ends produce the temperature difference and generate electricity, and send through electric wire A and B; Semiconductor generator unit spare at the very low firm entrance of LNG temperature can post multi-lager semiconductor thermoelectric pile sheet, and purpose is the seawater icing that prevents heat exchanger 2.
Embodiment 2: utilize the hydrogen manufacturing of cold energy of liquefied natural gas semiconductor temperature differential generating
Fig. 4 is a kind of specific embodiment principle schematic of utilizing LNG cold energy semiconductor temperature differential generating device for producing hydrogen.It comprises semiconductor thermoelectric generator sub-assembly and water electrolysis hydrogen production device.Semiconductor thermoelectric generator sub-assembly in the present embodiment is divided into two groups according to the temperature difference of Cooling and Heat Source: one group of BD1 is drenched normal seawater, and another group BD2 is drenched has reclaimed hydrogen manufacturing used heat and the higher seawater of temperature.Among the described water electrolysis hydrogen production device H, the hydrogen gas side of electrolytic cell D is connected with hydrogen-gas-liquid separator F1, hydrogen cooling water devaporation device Y1 successively; The oxygen side of electrolytic cell D is connected with oxygen-gas-liquid separator F2, oxygen cooling water devaporation device Y2 successively; Hydrogeneous alkali lye loop is connected to hydrogen-gas-liquid separator F1 bottom by hydrogen cooling-steam condenser Y1 bottom, is joined by F1 outlet at bottom and hydrogeneous alkali lye loopback pump P1, and after hydrogen alkali lye filter meets hydrogen alkali lye-seawater heat exchanger Q1, is transmitted back to electrolytic cell D again; Contain oxonium base liquid loop and be connected to oxygen-gas-liquid separator F2 bottom by oxygen cooling-steam condenser Y2 bottom, again by the F2 outlet at bottom with contain oxonium base liquid loopback pump P2 and join, and, be transmitted back to electrolytic cell D again after the oxonium base liquid filter meets oxonium base liquid-seawater heat exchanger Q2; The power supply of this water electrolysis hydrogen production device H is by being low-temperature receiver with LNG and being that semiconductor thermoelectric generator sub-assembly BD1, the BD2 of thermal source provides with the seawater; The seawater suction line L1 of salt water system meets sea water pump WP, meets seawater carrier pipe L2 again: the one tunnel is connected to the seawater spraying pipe LB1 of one group of semiconductor thermoelectric generator BD1 top through valve V1, two tunnel cooling tubes that are connected to hydrogen alkali lye-seawater heat exchanger Q1 and oxygen depletion-seawater heat exchanger Q2 are respectively divided on another road again behind valve V2, be connected to the seawater spraying pipe LB2 of another group semiconductor thermoelectric generator BD2 top again; After seawater drenched semiconductor thermoelectric generator BD1, BD2, fall into backwater collecting-tank W, flow back to the sea from seawater return pipe or canal L3 again; The total inlet pipe N1 of LNG receives the LNG heat exchanger tube of the low-temperature receiver heat exchanger of semiconductor thermoelectric generator BD1, BD2 respectively behind valve V3, and after the total efferent duct N4 of natural gas pipe N2 and valve V4 and natural gas join; Can be from the lower natural gas of the temperature of LNG heat exchanger tube outlet through another road natural gas tube N3, after joining with the heat exchanger tube of oxygen cooling water devaporation device Y2 and hydrogen cooling water devaporation device Y1, join through valve V5 and the total efferent duct N4 of natural gas again; The electrode of semiconductor thermoelectric generator is connected with the positive and negative electrode plate of water electrolysis hydrogen production device H electrolytic cell D with B through electric wire A respectively; When seawater is flowed through the thermal source heat exchanger of semiconductor thermoelectric generator BD1, BD2, by the semiconductor thermoelectric module sheet heat is passed to LNG, semiconductor thermoelectric generator sends direct current simultaneously, and the both positive and negative polarity by the hydrogen manufacturing electrolytic cell, make the raw water that enters electrolytic cell by electrolysis, after the natural gas cooling through having a surplus cold of hydrogen that electrolysis produces and oxygen is further removed steam, after joining with the pressure balance adjuster respectively, be sent to user or compression bottling more respectively; Sending to compression bottling or liquefaction stores; The seawater of cooling drains into the sea; Output is compiled near the natural gas (NG) of environment temperature in the gasification back.
Waste thermal energy when this method can reclaim water electrolysis hydrogen production simultaneously.Every heating 50～80kgLNG, but about hydrogen manufacturing 1m
3, the about 250～350kg of consumption seawater, pure water 1kg.
Claims (8)
1, a kind of semiconductor thermal difference generation method that utilizes the LNG cold energy, it is characterized in that: with liquefied natural gas (LNG) is low-temperature receiver, with the seawater is thermal source, the both ends of the surface of semiconductor temperature difference thermoelectric pile are closely contacted with seawater thermal source heat exchanger with LNG low-temperature receiver heat exchanger respectively make semiconductor thermoelectric generator, allow LNG and seawater respectively by low-temperature receiver heat exchanger and seawater thermal source heat exchanger, the heat of seawater is passed to LNG after by the semiconductor temperature difference thermoelectric pile, low-temperature liquefaction natural gas heat absorption evaporation, semiconductor temperature difference thermoelectric pile two ends produce electrical potential difference by the temperature difference and generate electricity.
2, a kind of device that utilizes the semiconductor temperature differential generating of LNG cold energy, comprise the semiconductor thermoelectric generator that the semiconductor thermoelectric module sheet that is made of P type and N-type semiconductor material and low-temperature receiver heat exchanger and thermal source heat exchanger constitute, it is characterized in that: described low-temperature receiver heat exchanger is to grip the LNG low-temperature receiver heat exchanger that the good filler of filling heat conduction forms between LNG heat exchanger tube, tube sheet by two metal plates; The semiconductor thermoelectric module sheet is close to the two metal plates outside; Metallic plate strip of paper used for sealing hard-pressed bale forms flat box-like semiconductor thermoelectric generator unit piece in the semiconductor thermoelectric module sheet outside; Its top is provided with the seawater spraying pipe that is connected with the seawater conveyance conduit, and seawater is flow through from the surface of metallic plate strip of paper used for sealing, forms seawater thermal source heat exchanger; The electric wire that every semiconductor thermoelectric generator unit piece all has respectively the LNG inlet pipe that links to each other with LNG heat exchanger tube two ends of drawing in the box and the natural gas (NG) that has gasified go out pipe and link to each other with two electrodes of semiconductor thermoelectric module sheet respectively.
3,, be characterised in that the good filler of heat conduction of filling between the tube sheet of described low-temperature receiver heat exchanger can be selected lead, babbit or copper powder, aluminium powder for use as utilizing as described in the claim 2 semiconductor temperature differential generating to reclaim the device of cold energy of liquefied natural gas.
4, as described in claim 2, utilize semiconductor temperature differential generating to reclaim the device of cold energy of liquefied natural gas, be characterised in that the described semiconductor temperature difference thermoelectric pile sheet that is attached to the metal plate outside, paste one deck at least, also can paste two layers or multilayer.
5, as described in claim 2, utilize semiconductor temperature differential generating to reclaim the device of cold energy of liquefied natural gas, be characterised in that described semiconductor thermoelectric generator, can be the semiconductor thermoelectric generator unit piece, also can be the semiconductor generating set component that is combined by two or more semiconductor thermoelectric generator unit pieces; Accompanying between each generator unit spare of semiconductor generating set component keeping the filler strip in the seawater runner gap between two unit pieces, and a plurality of generator unit spares are being clamped with pressing plate and bolt; Above semiconductor thermoelectric generator, be provided with the seawater spraying pipe.
6, as described in claim 2, utilize semiconductor temperature differential generating to reclaim the device of cold energy of liquefied natural gas, be characterised in that the metallic plate strip of paper used for sealing outside of described thermal source heat exchanger has the fin of the enhanced heat exchange that flows to downstream.
7, a kind of method of utilizing the hydrogen manufacturing of cold energy of liquefied natural gas semiconductor temperature differential generating, the power supply that partly provides water electrolysis hydrogen production to use by semiconductor temperature differential generating is provided, is by being thermal source with the seawater, being the direct current that the semiconductor thermoelectric generator of low-temperature receiver provides with liquefied natural gas (LNG); Seawater is pumped up the thermal source heat exchanger that back branch two tunnel: a tunnel is delivered to one group of semiconductor thermoelectric generator, after containing liquid hydrogen gas and containing liquid oxygen gas and backflow electrolyte of cooling water electrolysis hydrogen production device sent on another road earlier, deliver to the thermal source heat exchanger of another group semiconductor thermoelectric generator again; Fall warm seawater through the thermal source heat exchanger and discharged go back to the sea; LNG by force feed to the low-temperature receiver heat exchanger of semiconductor thermoelectric generator; When seawater was passed to LNG in the low-temperature receiver heat exchanger to heat from the thermal source heat exchanger by the semiconductor thermoelectric module sheet, semiconductor thermoelectric generator sent direct current; This direct current is connected to the both positive and negative polarity of hydrogen manufacturing electrolytic cell, the raw water that enters electrolytic cell is by electrolysis, the alkaline aqueous solution electrolysis produces and contains liquid hydrogen gas and contain liquid oxygen gas, collect respectively after separate generation hydrogen, oxygen, again through having a surplus cold natural gas (NG) cooling, further remove and send to the compression bottling behind the steam or liquefaction stores; Isolated raffinate by cooled with seawater after the blowback electrolytic cell; Natural gas after the gasification compiles output.
8, a kind of device that utilizes the hydrogen manufacturing of cold energy of liquefied natural gas semiconductor temperature differential generating is characterized in that: comprise semiconductor thermoelectric generator and water electrolysis hydrogen production device; Described semiconductor thermoelectric generator is to combine with parallel vertical panel form by being flat box-like semiconductor thermoelectric generator unit piece; Wherein LNG low-temperature receiver heat exchanger adopts and is being gripped by two metal plates that the good filler of filling heat conduction constitutes between the band-tube type heat exchanger structure, tube sheet of LNG heat exchanger tube; The semiconductor thermoelectric module sheet is close to the two metal plates outside of gripping LNG low-temperature receiver heat exchanger; Metallic plate strip of paper used for sealing hard-pressed bale is outside the semiconductor thermoelectric module sheet, constitute and be flat box-like semiconductor thermoelectric generator unit piece, its top is provided with the seawater spraying pipe that is connected with the seawater conveyance conduit, and seawater is flow through from the surface of metallic plate strip of paper used for sealing, forms seawater thermal source heat exchanger; The electric wire that every semiconductor thermoelectric generator unit piece all has respectively the LNG inlet pipe that links to each other with LNG heat exchanger tube two ends of drawing in the box and the natural gas (NG) that has gasified go out pipe and link to each other with semiconductor thermoelectric module sheet two electrodes respectively; Seawater is connected to the seawater spraying pipe of one group of semiconductor generator sub-assembly top through control valve by branch two tunnel, a tunnel after being pumped into the seawater carrier pipe through pipe; Another road with after the cooling tube of hydrogen alkali lye-seawater heat exchanger and oxygen depletion-seawater heat exchanger links to each other, is connected to the seawater spraying pipe of another group semiconductor thermoelectric generator sub-assembly top through control valve again; The total inlet pipe of LNG is received the LNG heat exchanger tube import of the low-temperature receiver heat exchanger of semiconductor thermoelectric generator sub-assembly behind valve, the outlet of LNG heat exchanger tube is connected with the tube connector of natural gas (NG), and joins through control valve and the total efferent duct of natural gas; After dividing the heat exchanger tube of a branch road and oxygen cooling water devaporation device and hydrogen cooling water devaporation device to join from tube connector, join through valve and the total efferent duct of natural gas again; Two electrodes of semiconductor thermoelectric generator are drawn through electric wire respectively, by behind the required series/parallel of electrolysis, are connected with the positive and negative electrode plate of the electrolytic cell of water electrolysis hydrogen production device respectively; In the described water electrolysis hydrogen production device, the hydrogen gas side of electrolytic cell is connected with hydrogen-gas-liquid separator, hydrogen cooling water devaporation device successively; The oxygen side of electrolytic cell is connected with oxygen-gas-liquid separator, oxygen cooling water devaporation device successively; After the cooling water devaporation device of hydrogen and oxygen leaves hydrogen outlet and oxygen outlet and pressure balance adjuster respectively and joins, be sent to user or compression bottling more respectively; Hydrogeneous alkali lye loop is connected to hydrogen-gas-liquid separator bottom by hydrogen cooling water devaporation device bottom, is joined by outlet at bottom and hydrogeneous alkali lye loopback pump again, then connects hydrogen alkali lye-seawater heat exchanger, is transmitted back to electrolytic cell again; Contain oxonium base liquid loop and be connected to oxygen-gas-liquid separator bottom by oxygen cooling water devaporation device bottom, again by outlet at bottom with contain oxonium base liquid loopback pump and join, then connect oxonium base liquid-seawater heat exchanger, be transmitted back to electrolytic cell again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021383499A CN1485003A (en) | 2002-09-24 | 2002-09-24 | Method and apparatus of semiconductor generating electricity and producing hydrogen using temperature difference and liquid natural gas providing cooling energy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA021383499A CN1485003A (en) | 2002-09-24 | 2002-09-24 | Method and apparatus of semiconductor generating electricity and producing hydrogen using temperature difference and liquid natural gas providing cooling energy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1485003A true CN1485003A (en) | 2004-03-31 |
Family
ID=34147221
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA021383499A Pending CN1485003A (en) | 2002-09-24 | 2002-09-24 | Method and apparatus of semiconductor generating electricity and producing hydrogen using temperature difference and liquid natural gas providing cooling energy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1485003A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006089459A1 (en) * | 2005-02-28 | 2006-08-31 | Dongru Wang | Single heating-source generator |
| CN101499746A (en) * | 2008-10-28 | 2009-08-05 | 无锡明惠通科技有限公司 | Plate type semiconductor thermo-electric generation apparatus |
| CN102575361A (en) * | 2009-11-10 | 2012-07-11 | 松下电器产业株式会社 | Photoelectrochemical cell and energy system using same |
| CN102677084A (en) * | 2012-05-22 | 2012-09-19 | 浙江师范大学 | Method and device for manufacturing hydrogen by electrolyzing water |
| CN103151967A (en) * | 2013-01-27 | 2013-06-12 | 南京瑞柯徕姆环保科技有限公司 | Cold energy thermoelectric power generating device |
| CN103174549A (en) * | 2013-04-03 | 2013-06-26 | 河南农业大学 | Liquefied natural gas (LNG) engine energy recovery device and energy recovery method based on thermoelectric power generation technology |
| CN103997256A (en) * | 2014-05-08 | 2014-08-20 | 南通天工深冷新材料强化有限公司 | Emergency power supply for cryogenic treatment process |
| CN104923073A (en) * | 2015-05-26 | 2015-09-23 | 上海大学 | Treatment device for optically degrading waste gas by utilizing waste gas waste heat |
| WO2017185403A1 (en) * | 2016-04-26 | 2017-11-02 | 彭斯干 | Method and device for washing and purifying ocean engineering engine tail gas by means of seawater with zero energy consumption |
| CN108917291A (en) * | 2018-07-06 | 2018-11-30 | 辽宁石油化工大学 | A kind of system and method for gas station exhaust gas waste cold cascade utilization |
| CN110486627A (en) * | 2019-07-24 | 2019-11-22 | 西安交通大学 | A kind of polygenerations systeme based on LNG cold energy use |
| CN110805831A (en) * | 2019-11-12 | 2020-02-18 | 西南石油大学 | Recovery process and device for liquid-phase ethane pipeline emptying liquid |
| CN111793813A (en) * | 2020-07-06 | 2020-10-20 | 中国原子能科学研究院 | Thermopile manufacturing process |
| CN113060264A (en) * | 2021-03-15 | 2021-07-02 | 集美大学 | Thermoelectric life support propulsion system of underwater vehicle |
| CN113604827A (en) * | 2021-07-23 | 2021-11-05 | 哈尔滨工业大学 | System for generating electricity and producing hydrogen by utilizing cold energy of liquefied natural gas |
| CN113931711A (en) * | 2021-09-06 | 2022-01-14 | 北京市燃气集团有限责任公司 | Independent power supply system for natural valve station |
| CN114717576A (en) * | 2022-05-07 | 2022-07-08 | 阳光氢能科技有限公司 | Hydrogen production system and alkali liquor circulation method |
-
2002
- 2002-09-24 CN CNA021383499A patent/CN1485003A/en active Pending
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006089459A1 (en) * | 2005-02-28 | 2006-08-31 | Dongru Wang | Single heating-source generator |
| CN101499746A (en) * | 2008-10-28 | 2009-08-05 | 无锡明惠通科技有限公司 | Plate type semiconductor thermo-electric generation apparatus |
| CN102575361A (en) * | 2009-11-10 | 2012-07-11 | 松下电器产业株式会社 | Photoelectrochemical cell and energy system using same |
| CN102575361B (en) * | 2009-11-10 | 2014-08-20 | 松下电器产业株式会社 | Photoelectrochemical cell and energy system using same |
| US8821700B2 (en) | 2009-11-10 | 2014-09-02 | Panasonic Corporation | Photoelectrochemical cell and energy system using same |
| CN102677084A (en) * | 2012-05-22 | 2012-09-19 | 浙江师范大学 | Method and device for manufacturing hydrogen by electrolyzing water |
| CN103151967A (en) * | 2013-01-27 | 2013-06-12 | 南京瑞柯徕姆环保科技有限公司 | Cold energy thermoelectric power generating device |
| CN103151967B (en) * | 2013-01-27 | 2015-06-10 | 南京瑞柯徕姆环保科技有限公司 | Cold energy thermoelectric power generating device |
| CN103174549A (en) * | 2013-04-03 | 2013-06-26 | 河南农业大学 | Liquefied natural gas (LNG) engine energy recovery device and energy recovery method based on thermoelectric power generation technology |
| CN103174549B (en) * | 2013-04-03 | 2015-09-23 | 河南农业大学 | Based on thermoelectric generation LNG engine power recovering device and method |
| CN103997256A (en) * | 2014-05-08 | 2014-08-20 | 南通天工深冷新材料强化有限公司 | Emergency power supply for cryogenic treatment process |
| CN104923073A (en) * | 2015-05-26 | 2015-09-23 | 上海大学 | Treatment device for optically degrading waste gas by utilizing waste gas waste heat |
| WO2017185403A1 (en) * | 2016-04-26 | 2017-11-02 | 彭斯干 | Method and device for washing and purifying ocean engineering engine tail gas by means of seawater with zero energy consumption |
| CN108917291A (en) * | 2018-07-06 | 2018-11-30 | 辽宁石油化工大学 | A kind of system and method for gas station exhaust gas waste cold cascade utilization |
| CN110486627A (en) * | 2019-07-24 | 2019-11-22 | 西安交通大学 | A kind of polygenerations systeme based on LNG cold energy use |
| CN110486627B (en) * | 2019-07-24 | 2020-06-19 | 西安交通大学 | Poly-generation system based on LNG cold energy utilization |
| CN110805831A (en) * | 2019-11-12 | 2020-02-18 | 西南石油大学 | Recovery process and device for liquid-phase ethane pipeline emptying liquid |
| CN110805831B (en) * | 2019-11-12 | 2021-02-26 | 西南石油大学 | Recovery process and device for liquid-phase ethane pipeline emptying liquid |
| CN111793813B (en) * | 2020-07-06 | 2021-07-20 | 中国原子能科学研究院 | Thermopile manufacturing process |
| CN111793813A (en) * | 2020-07-06 | 2020-10-20 | 中国原子能科学研究院 | Thermopile manufacturing process |
| CN113060264A (en) * | 2021-03-15 | 2021-07-02 | 集美大学 | Thermoelectric life support propulsion system of underwater vehicle |
| CN113604827A (en) * | 2021-07-23 | 2021-11-05 | 哈尔滨工业大学 | System for generating electricity and producing hydrogen by utilizing cold energy of liquefied natural gas |
| CN113931711A (en) * | 2021-09-06 | 2022-01-14 | 北京市燃气集团有限责任公司 | Independent power supply system for natural valve station |
| CN113931711B (en) * | 2021-09-06 | 2024-01-30 | 北京市燃气集团有限责任公司 | Independent power supply system for natural valve station |
| CN114717576A (en) * | 2022-05-07 | 2022-07-08 | 阳光氢能科技有限公司 | Hydrogen production system and alkali liquor circulation method |
| CN114717576B (en) * | 2022-05-07 | 2024-03-29 | 阳光氢能科技有限公司 | Hydrogen production system and alkali liquor circulation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1485003A (en) | Method and apparatus of semiconductor generating electricity and producing hydrogen using temperature difference and liquid natural gas providing cooling energy | |
| CN107893237B (en) | Hydrogenation stations based on high-temperature electrolysis vapor hydrogen producing technology | |
| Kuchonthara et al. | Energy recuperation in solid oxide fuel cell (SOFC) and gas turbine (GT) combined system | |
| CN107059042A (en) | A kind of thermal power plant's electric power passes through electrolytic cell hydrogen generating system | |
| CN113889648B (en) | MW-level combined heat and power supply fuel cell power station | |
| CN2602186Y (en) | Semiconductive temperature difference power generating and hydrogen production apparatus using cold energy of liquefied natural gas | |
| CN112886040A (en) | Utilize organic liquid to store up hydrogen energy power generation system | |
| JP2022105292A (en) | System and method of recovering waste heat from electrolyte for generating power, by using organic rankine cycle | |
| CN220099216U (en) | AEM electrolytic water hydrogen production integrated equipment | |
| WO2023238015A1 (en) | Hydrogen energy uninterruptible power system | |
| CN210560792U (en) | Amino solar thermochemical solid oxide water electrolysis hydrogen production system | |
| CN218561628U (en) | Hydrogen production and hydrogenation process system based on photovoltaic power generation along highway | |
| CN107628589B (en) | High-purity hydrogen production system and method by high-temperature bubbling methane direct cracking driven by concentrating solar energy | |
| CN216639661U (en) | Electrolytic hydrogen production waste heat utilization system | |
| CN113756885A (en) | Natural gas cold energy combined power generation system | |
| CN114672834A (en) | Thermoelectric coupling system and method based on photovoltaic hydrogen production coupling fuel cell | |
| CN114412599A (en) | Electrolysis hydrogen production coupling gas turbine power generation system | |
| CN115036549A (en) | High power solid oxide fuel cell/electrolyser system | |
| CN211284557U (en) | Production system for producing hydrogen and oxygen by using distilled water through electrolysis | |
| CN114032563A (en) | Wave energy power supply-based maritime solid oxide electrolytic cell co-electrolysis system | |
| CN113193217A (en) | Hydrogen-oxygen fuel cell system | |
| CN214499174U (en) | Natural gas cold energy combined power generation system | |
| CN105552406B (en) | The heat energy utilization method and its device to be generated electricity using fume afterheat by molten salt battery | |
| CN214327902U (en) | Solar hydrogen production system | |
| CN215366000U (en) | Hydrogen production system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |