WO2014101864A1

WO2014101864A1 - Low-temperature liquid fuel reforming hydrogen generator and preparation method for high-purity hydrogen

Info

Publication number: WO2014101864A1
Application number: PCT/CN2013/090853
Authority: WO
Inventors: 刘军; 陈勇
Original assignee: Liu Jun; Chen Yong
Priority date: 2012-12-31
Filing date: 2013-12-30
Publication date: 2014-07-03
Also published as: CN103730674A; CN103738917B; CN103022537A; WO2014101858A1; CN103738917A; CN103730674B

Abstract

The present invention relates to low-temperature liquid fuel reforming hydrogen generator. The catalyst solution and the fuel solution are mixed; then, the mixed solution is delivered to a fuel reaction chamber of a reformer, and undergoes chemical reaction at the temperature of 20~200℃ and under the pressure of 0.1~20 MPa to produce a low-valence-state fuel solution with reducibility; and thus, fuel conversion is completed, and the fuel is oxidized into carbon dioxide and water; next, the low-valence-state fuel solution with reducibility undergoes heat exchange by a heat exchanger, is reduced in the temperature, and then enters an electrolysis chamber; the solution is oxidized at the anode of the electrolysis chamber to obtain a high-valence-state solution, and the high-valence-state solution reenters the heat exchanger for temperature rise and then reenters the reaction chamber for reacting with the fuel, thereby completing a complete circulation system. In addition, high-purity hydrogen is produced at the cathode of the electrolysis chamber.

Description

The invention relates to a low-temperature liquid phase fuel heavy hydrogen generator and a method for preparing high-purity hydrogen. The application is submitted to the Chinese Patent Office on December 31, 2012, and the application number is 201210589197.8, and the invention name is "a low-temperature liquid phase having two output forms. The priority of the Chinese Patent Application for the Fuel Reformer is hereby incorporated by reference in its entirety. Technical field

The invention belongs to the fuel cell technology in the field of new energy, and particularly relates to a low temperature liquid phase fuel reforming hydrogen generator applied to a proton exchange membrane fuel cell. Background technique

The fuel cell can directly convert the chemical energy of the fuel into electric energy by discharging the fuel and the oxidant on the electrodes on both sides of the battery, so that the energy conversion rate is high, which is not limited by the energy conversion efficiency of the Carnot cycle. The efficiency of traditional heat engines is more than twice. Energy conversion through hydrogen fuel cells is an efficient and clean way to use energy. However, since hydrogen fuel used in hydrogen fuel cells is a flammable and explosive gas, there are many problems in storage and transportation. At present, the main hydrogen storage methods include high-pressure hydrogen tank storage, hydrogen storage alloy storage, and high-temperature catalyst reforming. Among them, the hydrogen storage in the high-pressure hydrogen tank has the disadvantages of large energy consumption, low hydrogen storage density and large volume in the process of hydrogen storage; while the hydrogen storage alloy has hydrogen storage alloy in the hydrogen storage process, the alloy is continuously pulverized and refined, resulting in alloy storage. A series of problems such as hydrogen failure, and hydrogen storage alloy hydrogen storage also has the defects of large weight of the alloy itself; while high-temperature catalyst reforming, there is a certain concentration of carbon monoxide gas produced by the reformer, which can poison the catalyst of the fuel cell. Causes the fuel cell to not work properly. Therefore, the current development of the fuel cell field has been greatly hindered by the fuel. Summary of the invention

In order to overcome the above disadvantages of the prior art, the present invention provides a high-purity hydrogen which can be used to obtain a hydrogen fuel cell by converting a small molecule liquid fuel in a medium-low temperature liquid phase by using a low temperature liquid phase fuel reformer under low temperature liquid state. In order to solve the storage problem of fuel hydrogen battery fuel.

The invention provides a low temperature liquid phase fuel reforming hydrogen generator, comprising a fuel reaction chamber, a heat exchanger and an electrolysis chamber, wherein the fuel reaction chamber contains a solution of a catalyst; mixing the catalyst solution and the fuel solution, and then conveying the obtained mixed solution to a reaction chamber of the reformer at a temperature of 20 to 200 ° C, pressure a chemical reaction occurs under conditions of 0.1 to 20 MPa to generate a low-cost fuel solution having a reducing property, and the fuel is converted into carbon dioxide and water; the reducing low-cost fuel solution is exchanged After the heat exchanger heats up, it enters the electrolysis chamber, and after oxidation at the positive electrode of the electrolysis chamber, the high valence state is obtained, and then the heat exchanger is re-entered and then re-entered into the reaction chamber and the fuel reaction to form a complete circulation system; at the same time, a high temperature is generated at the negative electrode of the electrolysis chamber. Purity of hydrogen; the entire reformer works under the control of the system controller.

Preferably, the catalyst solution is a solution formed of a polyacid dissolved in an acidic solution, and the polyacid is one or more of the same polyacid, heteropolyacid, and doped polyacid; The polyacid is tungstic acid or molybdic acid; the anion in the heteropoly acid has the chemical formula represented by the general formula (I):

[X _a M _b O ₄₀ ] ⁿ " ( 1 );

X=P, Si, Ge or As; M=W or Mo; a: b=l:6, 1:9 or 1:12; n is 2~10; the doping element in the doped polyacid is A composition of one or more of Fe, Co, Ni, Cr, Cu, Al, Ti, Sn, Ta, Nb, and Zr elements.

Preferably, the polyacid is a supramolecular compound formed by combining a polyacid molecule having an formula of the formula (II) or (III):

[(C ₁₉ H ₁₈ N ₃ ) ₂ H][PMo ₁₂ O ₄₀ ] ( II ); (ppy) ₄ H ₆ [SiW ₁₂ O ₄₀ ] ( III ).

Preferably, the acidic solution in the reformer is one or more of a non-oxidizing organic acid and a non-oxidizing inorganic acid;

The acidic solution of hydrogen ion molar concentration ^{10_ 4 ~ K ^ mol / L} .

Preferably, the fuel in the reformer is one or a mixture of decyl alcohol, furfural and citric acid.

Preferably, the low voltage power source is a power source that is supplied from the fuel cell output power to the electrolysis chamber of the reformer through a power converter, and the voltage of the electrolysis is 0.2 to 0.4V.

Preferably: the system controller is a pressure sensor, a temperature sensor, a safety valve, a catalyst solution concentration test sensor, a S-situ test sensor, a fuel reaction chamber auxiliary heating system, a micro electric control valve, a micro pump, and a reaction container. Organic complete system.

Preferably: the auxiliary heating system is provided with fuel; the fuel and air are in the auxiliary The internal combustion of the heating system generates heat.

Preferably: the heat exchanger comprises a plurality of sets of heat exchange tubes;

The heat exchanger cools the low-temperature fuel solution having a reducing property outputted by the fuel reaction chamber to the electrolysis chamber, and preheats the catalyst solution of the low-temperature and high-valence state outputted from the electrolysis chamber. To the fuel reaction chamber, the purpose of improving the energy efficiency of the entire reformer system; the heat exchanger also absorbs the heat released by the fuel cell during operation of the fuel cell to the reformer system to maintain the constant temperature during the operation of the fuel cell Sexuality makes the fuel cell system work at its best.

Preferably, the electrolysis chamber comprises a cathode plate, an anode plate, a diaphragm, a gas storage chamber, a low-cost fuel solution inlet valve having a reducing property, a catalyst solution outlet valve having a high valence state, and a positive electrode disposed on the positive electrode. Gas outlet valve, pressure sensor and temperature sensor at the plate.

The invention provides a preparation method of high-purity hydrogen, comprising the following steps:

Mixing the catalyst solution and the fuel solution to obtain a mixed solution;

The mixed solution is subjected to a chemical reaction at a temperature of 20 to 200 ° C and a pressure of 0.1 to 20 MPa to obtain a low-cost fuel solution having reduced properties, carbon dioxide and water; and the low reduction property The valence fuel solution is subjected to electrolysis to obtain a hydrogen and a high valence state catalyst solution.

The positive effect of the present invention is that the hydrogen fuel produced by the reformer is completely free of CO, which can effectively prevent the poisoning of the hydrogen fuel cell platinum catalyst and improve the output power of the hydrogen fueled fuel cell. Completely solve the problem of storage of hydrogen fuel cell fuel; high energy conversion efficiency is much higher than that of other high temperature fuel reformers; the reformer has a low starting temperature and can start fueling at around 30 °C at low temperature. The reforming reaction has a faster reforming rate per unit time as the reaction temperature is increased. Compared with other reformers, the working temperature of up to 500 ~ 800 °C has obvious advantages; the reformer can effectively utilize the heat generated during the operation of the fuel cell, and improve the efficiency of the entire fuel cell.

DRAWINGS

1 is a schematic structural view of a low-temperature liquid phase fuel reforming hydrogen generator provided by an embodiment of the present invention; Figure 2 is an enlarged view of a portion B of Figure 1 of the present invention. detailed description

The technical solutions provided by the present invention are further described below in conjunction with the embodiments and the accompanying drawings. The invention provides a low-temperature liquid phase fuel reforming hydrogen generator, characterized in that: a heat exchanger, a feed port and a water supply reaction chamber, a first feed port and a discharge port of the fuel reaction chamber are connected An electrolysis chamber connected to a first discharge port of the heat exchanger, a system controller and a catalyst solution contained in the fuel reaction chamber, and a second feed port of the heat exchanger is connected to a discharge port of the electrolysis chamber a second discharge port of the heat exchanger is connected to a second feed port of the fuel reaction chamber, a first feed port of the fuel reaction chamber is used for inputting fuel; and the system controller controls reforming Working with the system controller, the catalyst solution and the fuel solution are mixed to obtain a mixed solution; the mixed solution is sent to the fuel reaction chamber at a temperature of 20 to 200 ° C, and the pressure is liquid Converting the fuel, the fuel is oxidized to carbon dioxide and water; the reducing low-cost fuel solution is heated by the heat exchanger and then cooled to enter the electrolysis chamber, and then electrolyzed by the low-voltage power source in the electrolysis chamber. drop a low-temperature fuel solution having a reducing property after the temperature, a hydrogen gas is obtained at a negative electrode of the electrolysis chamber, and in the positive electrode region of the electrolysis chamber, the cooled low-temperature fuel solution having a reducing property is reoxidized into a high valence state catalyst solution, the hydrogen gas obtained at the negative electrode is output to the fuel cell as a product of the reformer, and the high valence state catalyst solution enters through the discharge port of the electrolyte and the second feed port of the heat exchanger After the heat exchanger warms up, it re-enters the fuel reaction chamber to react with the fuel to form a complete circulation system; the entire reformer works under the control of the system controller.

The invention provides a low-temperature liquid phase fuel reforming hydrogen generator, which belongs to a fuel cell system in a new energy technology, and relates to a reformer applied to a proton exchange membrane fuel cell, which can produce high output. The pure CO-free hydrogen is supplied to the proton exchange membrane fuel cell, which can satisfy the small-molecule liquid fuel which is easy to transport and store similar to sterol, furfural and citric acid by using a low-temperature liquid fuel reformer under low temperature liquid state. High-purity hydrogen is converted into a medium-low temperature liquid phase to be supplied to a hydrogen fuel cell, thereby solving the storage problem of the hydrogen fuel cell fuel.

Referring to FIG. 1 , FIG. 1 is a schematic structural diagram of a low-temperature liquid phase fuel reforming hydrogen generator according to an embodiment of the present invention, wherein 1 is a fuel storage tank, 2 is a first liquid flow pump, 3 is a temperature gauge, 4 is Pressure gauge, 5 is the chart, 6 is the second liquid flow pump, 7 is a low-temperature fuel solution with reduced properties at high temperature, 8 is a heat exchanger, 9 is a low-cost fuel solution with reduced properties at low temperature, and 10 is a negative electrode. 12 is the positive electrode and 13 is the hydrogen outlet.

The cryogenic liquid phase fuel reforming hydrogen generator provided by the present invention comprises a fuel reaction chamber. The fuel reaction chamber is provided with a first feed port for fuel input and a second feed port for input of a fuel solution having a reducing property after the output of the electrolysis chamber is preheated by the heat exchanger. The fuel reaction chamber is used to mix a fuel solution and a catalyst solution to obtain a fuel solution having reduced properties, carbon dioxide, and water. In the present invention, the fuel reaction chamber is reacted to obtain a high temperature fuel solution having a reducing property. The size and material of the fuel reaction chamber of the present invention are not particularly limited, and the size, material and shape of the fuel reaction chamber well known to those skilled in the art may be used. For example, a small pressure vessel of C lOO x 150 mm can be prepared by using stainless steel. As a fuel reaction chamber.

In an embodiment of the present invention, the fuel reaction chamber may include a fuel storage tank 1, a first liquid flow pump 2, and a chemical reaction chamber, and the fuel storage tank 1 is used to store a fuel solution, that is, a small molecular organic solution; The fuel solution is transported from the fuel storage tank to the chemical reaction chamber through the first liquid flow pump 2; specifically, the side wall of the chemical reaction chamber is provided with a first feed port, a second feed port and a discharge port The first feed port and the second feed port are disposed on the same side, and the discharge port is opposite to the first feed port and the second feed port; a feed to the fuel solution; the second feed port is for feeding a fuel solution having a reducing property from the heat exchanger; the discharge port is connected to the feed port of the heat exchanger, The fuel solution having the reducing property obtained by the reaction is sent to a heat exchanger for cooling. In an embodiment of the present invention, a thermometer 3, a pressure gauge 4, and a chart 5 are further disposed in the chemical reaction chamber, and the thermometer and the chart are immersed in the chemical reaction chamber below the liquid level of the mixed solution, and used for The temperature and pressure of the chemical reaction in the chemical reaction chamber are determined to provide a suitable temperature and pressure for the chemical reaction of the catalyst solution and the fuel solution. In the present invention, the catalyst solution and the fuel solution are mixed in the chemical reaction chamber, and the resulting mixed solution undergoes a chemical reaction at a temperature of 20 to 200 ° C and a pressure of 0.1 to 20 MPa to form a low-valent state having a reducing property. Fuel solution, carbon dioxide and water. The temperature at which the catalyst solution and the fuel solution are reacted is preferably 50 to 180 ° C, more preferably 80 to 150 ° C, and most preferably 90 to 130 ° C. The pressure of the reaction between the catalyst solution and the fuel solution is preferably 0.5 to 15 °. 18 MPa, more preferably 0.5 to 5 MPa, most preferably 1 to 1.5 MPa; the reaction time of the catalyst solution and the fuel solution is preferably 5 min to 60 min, more preferably 10 min to 30 min, and most preferably 10 Min~15 min„

In the present invention, the chemical reaction chamber is preliminarily provided with a catalyst solution. In the embodiment of the present invention, the catalyst solution may be added in an amount of one-half to two-thirds of the volume of the chemical reaction chamber. The present invention is not particularly limited thereto.

In the present invention, the catalyst solution is a solution formed of a polyacid dissolved in an acidic solution, the polyacid being one or more of the same polyacid, heteropolyacid, and doped polyacid; The isopoly acid is tungstic acid or molybdic acid; the anion in the heteropoly acid has the chemical formula of the formula (I):

[X _a M _b O ₄₀ ] ⁿ " ( 1 );

X=P, Si, Ge or As; M=W or Mo; a: b=l:6, 1:9 or 1:12; n is 2~10, specifically, n is preferably 2, 3, 4, 5, 6, 8 or 10;

The doping element in the doped polyacid is a combination of one or more of Fe, Co, Ni, Cr, Cu, Al, Ti, Sn, Ta, Nb and Zr elements.

In the present invention, the poly-S history is also preferably a super-molecular compound in which a polyacid molecule and an organic molecule are combined, and the supramolecular compound preferably has a chemical composition represented by the formula (II) or (III):

The source of the polyacid described in the above technical solution is not particularly limited, and a polyacid which is well known to those skilled in the art may be used. For example, a commercially available product of the polyacid described in the above technical solution may be used, and the field may also be used. The preparation method well known to the skilled person prepares the polyacid described in the above technical solution by itself. In the present invention, the method for preparing the catalyst solution preferably comprises the steps of: mixing a polyacid and an acidic solution, and heating and maintaining the catalyst solution.

In the present invention, the polyacid is preferably dissolved in an acidic solution, and the resulting mixed solution is heated and kept warm to obtain a catalyst solution. In the present invention, when the catalyst solution is a catalyst solution containing a doped polyacid, it is preferred to dissolve the raw material containing the doping element and the polyacid in an acidic solution, and heat and heat to obtain a catalyst solution containing the doped polyacid. In the present invention, the doping element-containing raw material is preferably a salt compound containing the doping element described in the above technical solution, such as when the doping element is Fe, the doping element-containing salt The compound can be ferrous sulfate. In the present invention, the heating temperature is preferably from 70 ° C to 90 ° C, more preferably from 75 ° C to 85 ° C, most preferably 80 ° C; and the heat retention time is preferably from 20 min to 50 min. More preferably, it is 25 min to 40 min, and most preferably 30 min.

In the present invention, it is preferred to filter the mixed solution after the heat preservation to obtain a catalyst containing a polyacid. Liquid.

In the present invention, the acidic solution may be a mixed solution of one or more of a non-oxidizing organic acid and a non-oxidizing inorganic acid, which is not particularly limited in the present invention, and hydrogen ions in the acidic solution The molar concentration is preferably 10 - ⁴ ~ lOimol / In the embodiment of the present invention, the acidic solution may be prepared by mixing one or a mixture of sulphuric acid, phosphoric acid, citric acid and hydrochloric acid. The molar concentration of hydrogen ions in the solution is preferably from 10 - ⁴ to K ^ mol / L, more preferably from 1 (Τ ³ to 0 mol / L, most preferably 1 (Τ ² to 10 mol / L. In the present invention, The mass concentration of the polyacid in the acidic solution is preferably from 0.1 g/mL to lg/mL, more preferably from 0.15 g/mL to 0.8 g/mL, and most preferably from 0.2 g/mL to 0.5 g/mL.

In the present invention, the fuel is a small molecule organic substance, preferably a mixture of one or more of decyl alcohol, furfural and citric acid. In the present invention, the mass concentration of the fuel solution is preferably from 1% to 100%. Preferably, it is 20% to 80%; and the mass ratio of the fuel to the catalyst is preferably 1:100 to 100:1, more preferably 1:10 to 10:1.

The cryogenic liquid high-purity hydrogen reformer provided by the present invention comprises a fuel reforming reaction chamber and a heat exchanger, and a first feed port of the heat exchanger is connected to a discharge port of the fuel reaction chamber, the heat exchanger The first discharge port is connected to the feed port of the electrolysis chamber, and is used for conveying the high-temperature reductive low-cost fuel solution obtained in the fuel reaction chamber to the heat exchanger for heat exchange, thereby obtaining a low temperature a reducing low-cost fuel solution is sent to the electrolysis chamber for electrolysis; a second feed port of the heat exchanger is connected to a discharge port of the electrolysis chamber, and a second discharge port of the heat exchanger Connected to a second feed port of the fuel reaction chamber for transporting a high valence state catalyst solution obtained by electrolysis of the electrolysis chamber to a heat exchanger for preheating and transporting to the fuel reaction chamber and fuel The solution is subjected to a chemical reaction. In an embodiment of the present invention, a second liquid flow pump 6 is disposed between the heat exchanger and the fuel reaction chamber for controlling a low-cost state having a reducing property flowing out of the fuel reaction chamber The flow rate of the fuel solution into the heat exchanger. In an embodiment of the invention, the heat exchanger comprises a plurality of sets of heat exchange tubes. In the present invention, the heat exchanger cools the low-temperature fuel solution having a reducing property output from the fuel reaction chamber and then supplies it to the electrolysis chamber, and outputs the low-temperature high-valence catalyst solution of the electrolysis chamber. After preheating, it is injected into the fuel reaction chamber to improve the energy efficiency of the entire reformer system. The heat exchanger also absorbs the heat released during the operation of the fuel cell to the reformer system to keep the fuel cell working. The constant temperature in the process makes the fuel cell system work at its best.

The invention has no special limitation on the size, shape and material of the heat exchanger, and adopts the skill. The size, shape and material of the heat exchanger are well known to those skilled in the art. In the embodiment of the present invention, the heat exchanger housing can be prepared by using stainless steel, and those skilled in the art can design heat exchangers of different sizes and shapes according to actual needs. The present invention has no particular limitation on this.

The cryogenic liquid phase fuel reforming hydrogen generator provided by the invention comprises an electrolysis chamber, and the feed port of the electrolysis chamber is connected with the first discharge port of the heat exchanger for reducing the low temperature obtained by the cooling The low-cost fuel solution is sent to the electrolysis chamber for electrolysis to prepare hydrogen gas, and the low-cost fuel solution is oxidized to obtain a low-temperature, high-valence catalyst solution. In the present invention, the electrolysis chamber preferably includes a cathode plate, an anode plate, a diaphragm, a gas storage chamber, a low-cost fuel solution inlet valve having a reducing property, and a catalyst solution outlet valve having a high valence state. The gas outlet valve at the positive electrode plate, the pressure sensor and the temperature sensor.

Referring to Figure 2, Figure 2 is an enlarged view of B in Figure 2 of the present invention, wherein 10 is a diaphragm, 11 is a negative electrode, and 12 is a positive electrode.

In an embodiment of the invention, array electrodes can be employed to increase electrolysis efficiency. The material of the positive electrode, the separator and the negative electrode is not particularly limited, and the positive electrode material, the separator and the negative electrode material used in the preparation of the flow battery system well known to those skilled in the art may be employed. In the present invention, the negative electrode of the electrolysis chamber is preferably a composite electrode composed of a heat-treated and surface-modified polypropylene fiber carbon felt and a current collecting plate. In the present invention, the heat-treated and surface-modified polypropylene fiber carbon felt is preferably prepared by the following method:

The polypropylene fiber carbon felt is immersed in a solution containing a modifying element, and impregnated to obtain a polypropylene fiber carbon felt to which a modifying element is attached;

The polypropylene fiber carbon felt to which the modifying element is attached is subjected to heat treatment to obtain a negative electrode material for preparing a liquid flow battery.

In the present invention, the polypropylene fiber carbon felt is preferably immersed in a solution containing a modifying element, and impregnated to obtain a polypropylene fiber carbon felt to which a modifying element is attached. The source of the polypropylene fiber carbon felt of the present invention is not particularly limited, and a polypropylene fiber carbon felt well known to those skilled in the art may be used. For the size of the negative electrode material required for the present invention, a polypropylene fiber carbon felt of a suitable size is selected. In the present invention, the metal element used in the chemical treatment of the surface modification of the negative electrode is preferably one or a combination of elements of Co, Ni, Ir, Ru, Au, Ag, Pt, W and Mo. The solution containing the modifying element is preferably a solution comprising ions of the above metal element, in the solution containing the modifying element The mass concentration of the metal ions is preferably 5% to 60%, more preferably 10% to 30%. In the present invention, the mass ratio of the polypropylene fiber carbon felt to the metal element is preferably 1: (0.0000001% to 0.001%), more preferably 1: (0.0001 to 0.001%). In the present invention, a polypropylene fiber carbon felt is immersed in the solution containing the modifying element, and the solution containing the modifying element is preferably used to immerse the polypropylene fiber carbon felt in the containing The immersion time in the solution of the modifying element is preferably from 0.5 to 24 hours, more preferably from 2 to 4 hours.

After obtaining a polypropylene fiber carbon felt to which a modifying element is attached, the present invention heat-treats the polypropylene fiber carbon felt to obtain a negative electrode material for preparing a liquid flow battery. In the present invention, the polypropylene fiber carbon felt is preferably taken out from the solution containing the modifying element, the water therein is drained, and the obtained polypropylene fiber carbon felt with the modified element is heat-treated to obtain a liquid flow battery. Anode material. In the present invention, the temperature of the heat treatment is preferably from 300 to 600, more preferably from 350 to 550, most preferably from 400 to 500 ° C; the heat treatment time is preferably from 0.5 to 48 hours, more preferably from 2 ~24 hours.

In the present invention, the method for preparing the chemically modified polypropylene fiber carbon felt is preferably also prepared by the following method:

The polypropylene fiber carbon felt was immersed in a solution containing a modifying element and electrolyzed to obtain a chemically modified polypropylene fiber carbon felt.

In the present invention, the mass concentration of the modifying element, the solution containing the modifying element, the source and size of the polypropylene fiber carbon felt, and the mass ratio of the polypropylene fiber carbon felt to the modifying element are the same as those described in the above technical solution. This will not be repeated here.

In the present invention, the electrode used for the electrolysis is preferably a graphite-based electrode material, preferably a polyacrylonitrile carbon fiber felt electrode; the potential of the electrolysis is preferably 0.2 to 10 V, more preferably 0.5 to 5 V; It is 10 to 600 minutes, more preferably 3 to 60 minutes.

The size, shape and material of the electrolysis chamber are not particularly limited in the present invention. The size, shape and material of the electrolysis chamber well known to those skilled in the art may be used. In the embodiment of the present invention, the PP material may be used for electrolysis. The outdoor casing, those skilled in the art can design electrolytic chambers of different sizes and shapes as needed, and the present invention is not particularly limited thereto.

In the present invention, the low-temperature fuel solution 7 having a reducing property at a high temperature outputted from the fuel reaction chamber is cooled by a heat exchanger, and a low-temperature fuel solution 9 having a reducing property at a low temperature is obtained. The low-temperature fuel solution having a reducing property at a low temperature is sent from the feed port of the electrolysis chamber to the electrolysis chamber for electrolysis; in the electrolysis chamber, the low-temperature fuel solution 9 having a reducing property at a low temperature is at a low voltage power source Performing electrolysis to produce hydrogen and a low-temperature and high-valence catalyst solution having an oxidation state, the hydrogen entering the hydrogen storage chamber, and the low-temperature and high-valency catalyst solution having an oxidation state is discharged from the electrolysis chamber The second feed port of the heat exchanger is sent back to the heat exchanger for preheating, and the obtained high temperature and high valence catalyst solution having an oxidation state is output from the second discharge port of the heat exchanger to a fuel reaction chamber enters a fuel reaction chamber from a second feed port of the fuel reaction chamber, and reacts with a fuel solution delivered from the first feed port in the fuel reaction chamber to generate a high temperature reduced state Low-cost catalyst solution. In the present invention, the low-voltage power source used in the electrolysis is preferably a part of the electric energy of the fuel cell output power obtained by the power conversion gas, which is raised to the electrolysis chamber of the reformer.

The cryogenic liquid phase fuel reforming hydrogen generator provided by the present invention comprises a system controller, and the system controller controls the operation of the fuel reaction chamber, the heat exchanger and the electrolysis chamber. In the present invention, the system controller is preferably It includes an organic system of pressure sensor, temperature sensor, safety valve, catalyst solution concentration test sensor, S-situ test sensor, fuel reaction chamber auxiliary heating system, micro electric control valve, micro pump and reaction vessel. In the present invention, the fuel reaction chamber auxiliary heating system includes a fuel in which the fuel and air are combusted inside an auxiliary heating system to generate heat to provide energy for operation of the auxiliary heating system; The auxiliary heating system works by utilizing the heat generated by the combustion of fuel and air inside the auxiliary heating system. In an embodiment of the invention, the pressure sensor may be a pressure gauge 4, and the temperature sensor may be a thermometer 3.

The hydrogen fuel produced by the reformer provided by the invention has no CO at all, can effectively prevent the poisoning of the hydrogen fuel cell platinum catalyst, and improve the output power of the hydrogen fueled fuel cell. Completely solve the problem of storage of hydrogen fuel cell fuel; high energy conversion efficiency is much higher than other high temperature fuel reformers;

The reformer provided by the present invention has a low starting temperature, and can start a reforming reaction with a fuel at a low temperature of about 30 ° C, and the reforming rate per unit time becomes faster as the reaction temperature is increased. Compared with other reformers, the working temperature of up to 500 ~ 800 °C has obvious advantages; the reformer can effectively utilize the heat generated during the operation of the fuel cell, and improve the efficiency of the entire fuel cell; the reformer It can provide fuel conversion for large fuel reactors, and can also be designed as a micro-reactor to convert converted fuel for low-power fuel cells. The former is suitable for large and medium-sized fuel cells as a moving The power supply is used, and the latter is suitable for use as a power source for electronic fuels. In order to further illustrate the present invention, the low-temperature liquid phase fuel reforming hydrogen generator and the method for preparing high-purity hydrogen provided by the present invention are described in detail below with reference to the examples, but they are not to be construed as limiting the scope of the present invention.

In the following examples, a low-temperature liquid-phase high-purity hydrogen high-purity reformer was constructed using the structures shown in Figs. 1 and 2.

Example 1

It is made of stainless steel and processed into a small pressure vessel of C 100 X 150mm. The design pressure is 2MPa. The temperature sensor, pressure sensor, pH sensor, heating tube inlet of the auxiliary heating system are installed on the tank as shown. a feed port and a corresponding valve to obtain a desired fuel reaction chamber;

A C 100 130mm container is machined from stainless steel, and two sets of capillary copper tubes are arranged as heat exchange tubes for the heat exchanger, and corresponding valves are installed to obtain the required heat exchangers;

PP plastic is used to process the plastic tank of 300 200 150mm sealing structure. The cathode plate, diaphragm, anode plate, cathode power bus, anode power bus, inlet valve, outlet valve, gas outlet are arranged as shown inside. The valve gets the electrolysis chamber as described. Install the fuel reaction chamber, heat exchanger, electrolysis chamber, controller, and check the air tightness to obtain the required reformer.

To prepare a polyacid acid conversion solution, take 1 L of pure water, add 100 g of ammonium molybdate thereto, stir to dissolve, add 20 mL of analytically pure Η ₃ Ρ 0 ₄ thereto, and then heat the obtained solution to 80 ° C for 30 minutes. Reduce the temperature to cool, filter the solution to obtain the desired polyacid acid conversion solution, add the solution to two-thirds of the volume of the reformer fuel reaction chamber; use a peristaltic pump to add sterol to the reforming through the fuel inlet In the device, the amount of addition is controlled by the sensor; the heating of the reformer is provided by the fuel cell stack radiator; the heating of the reformer is provided by the fuel cell stack radiator; the temperature of the reforming reaction is controlled at 150° C, the reaction time is 30 minutes, and the reactor pressure is controlled at 3 MPa. The fuel reaction chamber generates a deep blue solution with strong reducing properties, which flows out from the fuel outlet to the heat exchanger, enters the electrolysis chamber after being cooled by the heat exchanger, and uses part of the current output from the fuel cell in the electrolysis chamber to pass through the converter. It is supplied to the electrolysis chamber at 0.2 ~ 0.4V. The intermediate product fuel in the electrolysis chamber is consumed by the anodization of the electrolysis chamber, and the solution re-enters the fuel reaction chamber to regenerate and continuously circulate. The hydrogen produced on the cathode plate of the electrolysis chamber is delivered to the fuel cell. The reformer is suitable for use in high power hydrogen fuel cells. The hydrogen obtained by the reformer provided by the invention does not contain co at all and has high purity.

Example 2:

According to the scheme described in the drawing, stainless steel is processed into a small pressure vessel of C lOO x 150mm with a design pressure of 2 MPa. The temperature sensor, pressure sensor, pH sensor and auxiliary heating system are separately installed on the tank as shown. The tube feed port, the discharge port and the corresponding valve provide the desired fuel reaction chamber.

According to the illustration, a C 100 130mm container is machined in stainless steel, and two sets of capillary copper tubes are arranged as heat exchange tubes for the heat exchanger, and corresponding valves are installed to obtain the required heat exchanger.

According to the illustration, PP plastic is used to process the plastic tank of 300 200 150mm sealing structure. The cathode plate, diaphragm, anode plate, cathode power bus, anode power bus, inlet valve, outlet valve, gas outlet are arranged inside. The valve gets the electrolysis chamber as described. Install the fuel reaction chamber, heat exchanger, electrolysis chamber, controller, and check the air tightness to obtain the required reformer.

To prepare a multi-acid conversion solution, take 1 L of high-purity water, add 80 g of ammonium molybdate, 20 g of ammonium tungstate and 10 g of ferrous sulfate to dissolve and dissolve. Then, add 50 g of citric acid to stir and dissolve it, then add 1 : 3 diluted analytical H ₂ S0 ₄ 45mL, then the mixed solution was heated to 80 ° C for 30 minutes, then cooled to cool, filtered to obtain the desired polyacid acid conversion solution, the solution was added to Two-thirds of the volume of the reformer fuel reaction chamber. The sterol was added to the reformer through a fuel inlet using a peristaltic pump, and the amount added was controlled by a sensor. The heating of the reformer during operation is provided by the fuel cell stack heat sink. The temperature of the reforming reaction was controlled at 200 ° C, the reaction time was 20 minutes, and the reactor pressure was controlled at 5 MPa. The fuel reaction chamber generates a deep blue solution with strong reducing properties, which flows out from the fuel outlet and enters the electrolysis chamber after being cooled by the heat exchanger. The partial current output by the fuel cell in the electrolysis chamber is reduced to 0.2 to 0.4 through the converter. V is supplied to the electrolysis chamber, and the intermediate product fuel in the electrolysis chamber is consumed by the anodization of the electrolysis chamber, and the solution is re-entered into the fuel reaction chamber to be regenerated and continuously circulated. Hydrogen gas generated on the cathode plate of the electrolysis chamber is delivered to the fuel cell as a hydrogen source for the fuel cell. The reformer is suitable for use in high power hydrogen fuel cells.

The hydrogen obtained by the reformer provided by the invention does not contain CO at all and has high purity.

Example 3

Made of stainless steel into a small pressure vessel of C 100 X 150mm, the design pressure is

2MPa, respectively, on the tank, processing temperature sensor, pressure sensor, pH transmission The sensor, the heating tube feed port of the auxiliary heating system, the discharge port and the corresponding valve, get the required fuel reaction chamber.

According to the illustration, a C 100 130mm container is machined in stainless steel, and two sets of capillary copper tubes are arranged as heat exchange tubes for the heat exchanger, and corresponding valves are installed to obtain the required heat exchangers.

According to the illustration, PP plastic is used to process the plastic tank of 300 200 X 150mm sealing structure. The cathode plate, diaphragm, anode plate, cathode power bus, anode power bus, inlet valve, outlet valve, gas output are arranged inside. The port valve is obtained as described in the electrolysis chamber. Install the fuel reaction chamber, heat exchanger, electrolysis chamber, controller, and check the air tightness to obtain the required reformer.

For the configuration of the acidic conversion solution, take 1L of high-purity water, add 100g of ammonium molybdate to it and stir it evenly, then add 1:3 analytical pure H ₂ SO _{4 to} 60mL, then heat the solution to 80 ° C, reduce the temperature and cool, filter The solution yields the desired acid conversion solution which is added to two-thirds of the volume of the reformer fuel reaction chamber. The sterol is added to the reformer through a fuel inlet using a peristaltic pump, the amount of which is controlled by the sensor. The heating of the reformer during operation is provided by the fuel cell stack heat sink. The temperature of the reforming reaction was controlled at 150 ° C, the reaction time was 30 minutes, and the reactor pressure was controlled to be 3 MPa or less. The fuel reaction chamber generates a deep blue solution with strong reducing properties, which flows out from the discharge port of the fuel reaction chamber, and then enters the electrolysis chamber after being cooled by the heat exchanger. In the electrolysis chamber, a part of the current outputted by the fuel cell is converted into a gas drop. It is supplied to the electrolysis chamber to 0.2~0.4V. The intermediate product fuel in the electrolysis chamber is consumed by the anodization of the electrolysis chamber, and the solution re-enters the fuel reaction chamber to regenerate and continuously circulate. Hydrogen gas generated on the cathode plate of the electrolysis chamber is supplied to the fuel cell as a hydrogen source for the fuel cell. The reformer is suitable for use in high power hydrogen fuel cells.

It can be seen from the above embodiments that the cryogenic liquid phase fuel reforming hydrogen generator provided by the present invention comprises a fuel reaction chamber, a heat exchanger connected to the discharge port of the fuel inlet chamber of the first feed inlet, and a feed port and a change An electrolysis chamber connected to a first discharge port of the heat exchanger, a discharge port of the electrolysis chamber being connected to a second feed port of the heat exchanger, a second discharge port of the heat exchanger and the fuel A second feed port of the reaction chamber is connected to the fuel storage tank connected to the first feed port of the fuel reaction chamber, and the fuel reaction chamber contains a catalyst solution. In the present invention, the catalyst solution and the fuel solution delivered from the fuel storage tank, in the fuel reaction chamber, the catalyst solution and the fuel solution chemically react to generate a low-temperature fuel having a reducing property at a high temperature. Solution, said The low-cost fuel solution is transported from the discharge port of the fuel reaction chamber to the heat exchanger, and the first feed port of the heat exchanger enters the heat exchanger for heat exchange, and the obtained low temperature has a reducing property. The low-cost fuel solution is sent to the electrolysis chamber from the first discharge port of the heat exchanger, enters into the electrolysis chamber through the feed port of the electrolysis chamber for electrolysis, and hydrogen is obtained in the cathode region of the electrolysis chamber, a low-cost fuel solution having a reducing property in an anode region of the electrolysis chamber is reoxidized into a high-valence catalyst solution; the high-valence catalyst solution is transported from a discharge port of the electrolysis chamber to a heat exchanger through The second feed port of the heat exchanger is input to the heat exchanger for heat exchange to obtain a low-temperature high-validation catalyst solution; the low-temperature high-validation catalyst solution is transported to the fuel reaction by the second discharge port of the heat exchanger The chamber is introduced into the fuel reaction chamber through the second feed port of the fuel reaction chamber to react with the fuel solution to form a completed circulation system. The hydrogen prepared by the reformer provided by the invention does not contain CO at all, can effectively prevent the poisoning of the fuel cell platinum catalyst, improve the output power of the hydrogen fueled fuel cell, and completely solve the storage problem of the hydrogen fuel cell fuel; The real energy conversion rate is higher than that of other high temperature fuel reformers.

The above description of the embodiments is merely to assist in understanding the method of the present invention and its core idea. It is to be understood that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention. Various modifications to these embodiments are obvious to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not intended to be limited to the embodiments shown herein, but the scope of the invention.

Claims

Rights request

1. A low-temperature liquid-phase fuel reforming hydrogen generator, characterized by: including a fuel reaction chamber, a heat exchanger and an electrolysis chamber. The fuel reaction chamber contains a catalyst solution; the catalyst solution and the fuel solution are mixed, and then The obtained mixed solution is transported to the reaction chamber of the reformer where a chemical reaction occurs at a temperature of 20 ~ 200°C and a pressure of 0.1 ~ 20MPa to generate a low-valent fuel solution with reducing properties to complete the fuel conversion. The fuel is oxidized into carbon dioxide and water; the reducing low-valence fuel solution is cooled down after being exchanged in a heat exchanger and enters the electrolysis chamber. It is oxidized at the positive electrode of the electrolysis chamber to obtain a high valence state and then re-enters the heat exchanger to heat up. Then it re-enters the reaction chamber and reacts with the fuel to form a complete circulation system; at the same time, high-purity hydrogen is produced at the negative electrode of the electrolysis chamber; the entire reformer works under the control of the system controller.

2. The low-temperature liquid phase high-purity hydrogen reformer according to claim 1, characterized in that: the catalyst solution is a solution formed of polyacid dissolved in an acidic solution, and the polyacid is a homopolyacid, One or more types of heteropoly acid and doped polyacid; the homopoly acid is tungstic acid or molybdenum acid; the anion in the heteropoly acid has a chemical formula represented by general formula (I):

[X _a M _b O ₄₀ ] ⁿ " ( 1 );

X=P, Si, Ge or As; M=W or Mo; a:b=1:6, 1:9 or 1:12; n is 2~10; the doping element in the doped polyacid is One or a combination of several elements among Fe, Co, Ni, Cr, Cu, Al, Ti, Sn, Ta, Nb and Zr.

3. The low-temperature liquid phase fuel reforming hydrogen generator of claim 2, characterized in that: the polyacid is a supramolecular compound composed of polyacid molecules and organic molecules, and the supramolecular compound has the formula ( The chemical formula shown in II) or (III):

[(C ₁₉ H ₁₈ N ₃ ) ₂ H][PMo ₁₂ O ₄₀ ] (II); (ppy) ₄ H ₆ [SiW ₁₂ O ₄₀ ] (III).

4. The low-temperature liquid phase fuel reforming hydrogen generator of claim 2, characterized in that: the acidic solution in the reformer is one or more of non-oxidizing organic acids and non-oxidizing inorganic acids. ;

The molar concentration of hydrogen ions in the acidic solution is 10_ ⁴ ~ K^mol/L.

5. The low-temperature liquid phase fuel reforming hydrogen generator according to claim 1, characterized in that: the fuel in the reformer is one or a mixture of several types of methanol, formaldehyde and formic acid.

6. The low-temperature liquid phase fuel reforming hydrogen generator according to claim 1, characterized in that: the low-voltage power supply is a part of the electric energy output by the fuel cell that is supplied to the electrolysis chamber of the reformer through a power converter. Power supply, the voltage of the electrolysis is 0.2 ~ 0.4V.

7. The low-temperature liquid phase fuel reforming hydrogen generator according to claim 1, characterized in that: the system controller includes a pressure sensor, a temperature sensor, a safety valve, a catalyst solution concentration test sensor, and a S temperature test sensor. An organic complete system of fuel reaction chamber auxiliary heating system, micro electric regulating valve, micro pump and reaction vessel.

8. The low-temperature liquid phase fuel reforming hydrogen generator according to claim 7, characterized in that: the auxiliary heating system is provided with fuel; the fuel and air are burned inside the auxiliary heating system to generate heat.

9. The low-temperature liquid phase fuel reforming hydrogen generator of claim 1, characterized in that: the heat exchanger includes multiple groups of heat exchange tubes;

The heat exchanger cools down the high-temperature low-valence fuel solution with reducing properties output from the fuel reaction chamber and supplies it to the electrolysis chamber for use, and preheats the low-temperature high-valency catalyst solution output from the electrolysis chamber before adding it. to the fuel reaction chamber to improve the energy efficiency of the entire reformer system; the heat exchanger also absorbs the heat released during the operation of the fuel cell to the reformer system to maintain a constant temperature during the operation of the fuel cell. properties to make the fuel cell system work at its best.

10. The low-temperature liquid phase fuel reforming hydrogen generator of claim 1, characterized in that: the electrolysis chamber includes a cathode plate, an anode plate, a diaphragm, a gas storage chamber, and a low-valent fuel with reducing properties. Solution inlet valve, catalyst solution outlet valve with high valence state, gas outlet valve provided at the positive electrode plate, pressure sensor and temperature sensor.

11. A method for preparing high-purity hydrogen, including the following steps:

Mix the catalyst solution and the fuel solution to obtain a mixed solution;

The mixed solution is subjected to a chemical reaction at a temperature of 20 to 200°C and a pressure of 0.1 to 20 MPa to obtain a low valence fuel solution with reducing properties, carbon dioxide and water; the low valence fuel solution with reducing properties is The valence fuel solution undergoes electrolysis to obtain hydrogen and a high valence catalyst solution.