CN1554569A - System and its device for producing hydrogen and oxygen using solar energy - Google Patents

Abstract

The system for producing hydrogen and oxygen by utilizing solar energy has solar heat collector to provide heat; hydrogen producing adsorption bed, where water vapor is reacted to produce hydrogen under the catalysis of MO-AB2O4 spinelle type catalyst; and oxygen producing adsorption bed, where salt of alkali metal is heated under the action of active carbon catalyst to release oxygen, with the decomposed CO being used for the reduction of catalyst in hydrogen producing adsorption bed. The present invention also provides the apparatus for producing hydrogen and oxygen by utilizing solar energy. The present invention utilizes solar energy directly and has no environmental pollution.

Description

System and device for preparing hydrogen and oxygen by utilizing solar energy

Technical Field

The invention belongs to the technical field of hydrogen and oxygen manufacturing, and particularly relates to a system and a device for preparing hydrogen and oxygen by utilizing solar energy.

Background

With the increasing exhaustion of natural energy and the further enhancement of environmental awareness of human beings, the development of a new clean energy has attracted the general attention of all human beings, and governments have invested huge amounts of research and development. China governments also pay attention to the fact that many colleges and universities and scientific research institutions have tightened research and development step valves. The development and application of hydrogen energy has become one of the hot spots in the present high-tech field, and the popularization of hydrogen energy technology and the perfect hydrogen fuel supply system have become the inevitable basis for protecting the human environment and the future major energy policy.

On the basis of the traditional hydrogen production, the research on the preparation of cheaper hydrogen energy by new materials and new technologies is carried out. Because of the traditional hydrogen production process such as electrolytic hydrogen production, the hydrogen energy is produced by alkane and hydrocarbon at the expense of conventional energy sources, and the process is called as 'noble energy'. Except for liquid hydrogen used for launching rocket missiles in national defense and military and a part of high-purity hydrogen energy used in the semiconductor industry, most industrial departments and civil departments cannot be used adequately. Although solar photovoltaic power generation, which is technically mature, can produce hydrogen by electrolysis, the cost of a photovoltaic cell cannot be reduced for a while because the photovoltaic cell has no new cheap materials in the near future. Therefore, the solar photovoltaic power generation hydrogen production is difficult to be practical in the near future.

The new hydrogen production technology and device are discussed and searched in various countries at present, and a low-cost feasible device invention is not yet seen. The invention patent application with patent application publication number CN1352323A discloses a method and a device for generating hydrogen by utilizing solar energy and/or wind energy, which consists of a solar cell and/or a wind driven generator, a water electrolysis cylinder, a compressor, an electromagnetic valve, a central control circuit and the like. The electric energy generated by the solar battery and/or the wind driven generator is pressurized and then is added to the water electrolysis cylinder, and the generated hydrogen is pressed into the steel cylinder by the compressor.

The invention patent application of patent application publication No. CN1384044A discloses a hydrogen preparation method and a device thereof, the hydrogen preparation method is to prepare hydrogen by metal aluminum powder and sodium hydroxide aqueous solution in a reactor, the average particle size of the metal aluminum powder is 10mm-10nm, and the weight percentage concentration of the sodium hydroxide aqueous solution is 0.1% -30%; the hydrogen preparing device is constructed and connected in such a way that a liquid storage container is connected with a reactor through a pipeline, an aluminum powder container is connected with the reactor through a pipeline and a valve, an aluminum powder interlayer is arranged in the reactor, the reactor is connected with a hydrogen storage tank through a pipeline, and the reactor is connected with a liquid discharge pipeline provided with a liquid discharge control device.

The invention has the application number of 02110953.2, and the invention patent application named as a household solar intelligent artificial environment system discloses a household solar intelligent artificial environment system, which comprises a solar heat collector, a high-temperature adsorption type air conditioning device, a household device and a circulation pipeline of heat-conducting media, wherein the heat-conducting media are mutually connected with the household device, and the solar heat collector consists of a full-automatic tracking and focusing device, a solar heater and an energy storage device; the focusing light spot of the full-automatic tracking focusing device is reflected to the heat absorption spherical surface of the solar heater; the high-temperature heat-conducting medium heated by the solar heater is input into the energy storage device through a pipeline, the energy storage device outputs the heat-conducting medium to the high-temperature adsorption type air conditioning device or the household device through the pipeline, and the used heat-conducting medium circulates to the solar heater through the pipeline. The upper part of the full-automatic tracking focusing device is provided with a rotary paraboloid condenser with a reflecting mirror surface, and the lower part of the condenser is provided with a rigid steel frame; the lower part of the steel frame is provided with a sun pulley block and a year pulley block according to a certain angle; the sun pulley block and the year pulley block are respectively fixed on a sun guide rail and a year guide rail on the spherical base and slide in the sun guide rail and the year guide rail; the movement distance of the sun pulley block is controlled by the sun guide rail electromagnetic manipulators arranged on two sides of the steel frame so as to control the day rotation of the condensing lens; the moving distance of the year pulley block is controlled by an year guide rail electromagnetic manipulator arranged on the spherical base to control the year rotation of the condensing lens; spherical universal joints are correspondingly arranged in the circumferential direction of the condensing lens; the ball universal joint is arranged in a ball universal joint guide rail on the spherical base and slides; the sliding tracks of the sun pulley block, the year pulley block and the spherical universal joint are all on the spherical base track, and the circle center and the radius of the track are the same; the spherical base is arranged on the support. The condenser lens of the device can be used for focusing and heating, and the temperature of a heat source for focusing and heating is as high as 400-600 ℃. The solar heat collector can output high-temperature media to be used as a heat source.

Disclosure of Invention

The invention provides a system for preparing hydrogen and oxygen by utilizing solar energy to focus and heat to generate high temperature and decomposing water under the action of a catalyst. The system has the advantages of direct solar energy supply, low hydrogen production cost and no environmental pollution.

The invention provides a device for preparing hydrogen and oxygen, which is configured on the basis of a solar heat collector, utilizes the heat of solar energy to prepare the hydrogen and the oxygen, and has the advantages of less device investment and low operation cost.

The reaction principle of the invention is as follows:

the main reaction formula is as follows:

the side reaction formula:

the above reaction proves that both NiO and ZnO can react with Al₂O₃A spinel structure is formed and can therefore be written as general formula: MO-AB₂O₄. In the formula, M can be elementary metal Ni or elementary metal Cu. O is₂Adsorption on NiO is O^-And the adsorption on CuO is O^2-(lattice oxygen), which easily penetrates into the crystal and causes difficulty in desorption. A may be divalent ions such as Zn, Mg, Fe, Mz, Ni, etc., but only Zn and H are contained in the above metals₂Is not adsorbed. B may be trivalent ion such as Fe, Al, Cr, etc., but only Al in the above metals does not adsorb H₂In (1). When the above-mentioned metals and metal oxides are mixed and dissolved, they form three immiscible series of hercynite or aluminium spinel and chromium spinel, so that its general formula can be written as MO-AB₂O₄。

Among the catalysts already put into use, in the production of virtually synthetic ammoniaThe low-shift catalyst of (2) is an application of the catalyst principle. The main agent of the synthetic ammonia low-variation catalyst is CuO, ZnO and Al₂O₃Is a carrier, the general use temperature of the catalyst is between 180 ℃ and 250 ℃, and the catalytic cycle principle is as follows:

the deoxidation of the low shift catalyst utilizes CO to reduce oxygen of the metal oxide into CO₂Reducing CuO to elemental metal Cu, and removing COfrom the gas mixture₂To obtain pure H₂. And a general formula MO-AB₂O₄The hydrogen production principle of the catalyst is the same as that of synthetic ammonia, and CO is generated at the same time₂Recovering and returning the alkali metal salt activated carbon catalyst to the adsorption bed and the alkali metal peroxide (Na)₂O₂) Reaction on alkali metal salt (Na)₂CO₃) And O₂Let H stand for₂O (gas) is decomposed to H₂And O₂Compressed by a compressor and sent to respective storage tanks for application. Considering that the reduction is carried out with CO, there is Ni and CO to react and produce CH₄Therefore, it isIn practice, Cu is preferably used. Therefore, the hydrogen production adsorption bed of the system uses CuO-ZnAl₂O₄A catalyst.

The catalyst used in the oxygen-making adsorption bed of the system is potassium and sodium alkali metal salt, the active carbon is used as a carrier, and the potassium and sodium alkali metal salt is loaded on the active carbon. The activated carbon is accompanied by catalytic activity in the adsorption process, and a complex is caused between the activated carbon and a carrier substance to accelerate the catalytic reaction. In consideration of catalyst cost and low sodium salt cost, the alkali metal sodium salt (Na) is selected₂CO₃) As the catalyst active ingredient.

As shown in fig. 1, the spinel catalyst participates in the reaction, but after a cycle process consisting of several reactions, the catalyst returns to the original state, the reactant becomes a product to complete the hydrogen production reaction, the catalyst can be continuously recycled, and the collected hydrogen is compressed by a compressor and then stored.

As shown in fig. 2, the basic sodium metal salt activated carbon catalyst uses activated carbon as a carrier, and basic metal salt is loaded on the activated carbon. The catalyst reacts under the participation of the catalyst, after the cyclic reaction, the catalyst returns to the original state, the reactant becomes a product, the oxygen generation reaction is finished, and the collected oxygen is stored after being compressed by a compressor.

A system for preparing hydrogen and oxygen by solar energy uses a solar heat collector to provide heat transfer liquid to transfer heat, so that water vapor is in a general formula of MO-AB₂O₄Under the action of spinel catalyst, hydrogen-producing reaction takes place in hydrogen-producing adsorption bed to decompose H₂(ii) a Wherein, M can be simple substance metal Ni or simple substance metal Cu; a can be one of divalent metal ions of Zn, Mg, Fe, Mz and Ni, and B can be one of trivalent metal ions of Fe, Al and Cr; at this time, CO decomposed by heating of the alkali metal salt activated carbon catalyst of the oxygen production adsorption bed is supplied to the catalyst in the hydrogen production adsorption bed for reduction reaction, and CO is discharged₂Is recovered and returned to the oxygen production adsorption bed, so that the active carbon catalyst is returned to the alkali metal salt state to release O₂。

The reaction temperature for preparing hydrogen by the spinel catalyst is 180-250 ℃.

The temperature of the alkali metal salt activated carbon catalyst is 350-400 ℃ when the catalyst is heated and decomposed.

A device for preparing hydrogen and oxygen by utilizing solar energy comprises a solar heat collector, a hydrogen production adsorption bed, an oxygen production adsorption bed, a heat exchanger, a water vapor generator and a conveying pipeline, wherein the solar heat collector heats heat transfer liquid through solar energy focusing, and the generated heat transfer liquid vapor is conveyed to the hydrogen production adsorption bed; a spinel catalyst is arranged in the hydrogen production adsorption bed and reacts with the water vapor generated by the water vapor generator to generate hydrogen; simultaneously, carbon monoxide generated by the oxygen-making adsorption bed is input into the hydrogen-making adsorption bed through different pipelines; reducing the spinel catalyst to release carbon dioxide, and recovering the carbon dioxide to the oxygen-making adsorption bed to react with the alkali metal salt active carbon catalyst to generate alkali metal salt and release oxygen; the hydrogen is compressed and stored in the hydrogen storage tank after heat exchange of the heat exchanger, and the oxygen is compressed and stored in the oxygen storage tank after heat exchange of the heat exchanger.

The hydrogen production adsorption bed and the oxygen production adsorption bed are formed by rolling a steel plate into a rectangle, the section in the vertical direction is a square, the shell of the steel plate is provided with a heat insulation layer, the inner part of the steel plate is a group of whole bodies consisting of a plurality of heating fin coil pipes and a header pipe through a cross beam, a plurality of heat and mass transfer pipes are uniformly arranged between every two rows of heating fin coil pipes, and a plurality of catalysts are filled in the gap parts of the heating fin coil pipes and the heat and mass transfer pipes.

The heating fin coil is formed by welding a coil and a plurality of radiating steel wires.

The heat transfer and transmission pipe is a circular pipe, one end of the pipe is sealed, radiating fins are welded on the pipe in the circumferential direction of the pipe in a mutually perpendicular mode, and a plurality of small holes are formed in the pipe at intervals in the circumferential direction.

The surface of the radiating fin is grooved.

Now, according to the energy consumption structure of the current Chinese family, a rough analysis is carried out, and a 3-5-mouth family hopes to have a trolley and a set of 90-130m²20-30m of a house²The indoor summer can be provided with an air conditioner and a heating system in winter, and the indoor heating system also comprises corresponding household appliances. The trolley needs about 30KW energy consumption every day according to 1 hour (100km) of use, the air conditioner needs about 20-30KW energy consumption every day in average use for 8-10 hours, corresponding household appliances comprise lighting, televisions and cooking need about 10KW, so that 90KW is needed every day actually, and the minimum amount is calculated according to 50 KW. The calorific value of each KW is about 3600KJ, the calorific value of hydrogen is about 142000KJ/Kg (about 40000KJ/Kg of petroleum), and each standard household needs about 1.3-2.3Kg of hydrogen per day. This is a very large consumption in terms of society. It is expected that if 1/10 families in a city use solar energy to produce hydrogen, the total energy saving will be a great favorite number and will be very significant for alleviating urban environmental pollution. This is, of course, a goal to be achieved, and there is yet to be commercialization of fuel cells. According to the prediction of relevant experts, if the production scale of the fuel cell can reach 10⁵The KW/a, the structure of fuel cell in other aspects, and the development and development of new materials haveThe commercialization of fuel cells is expected in the near future, and the demand of hydrogen fuel is increasing at the present time, and the cost of hydrogen production by solar energy is far lower than that of all hydrogen production technologies such as hydrogen production by electrolysis, hydrogen production by coal gasification, hydrogen production by natural gas, hydrogen production by methanol, and the like. Certainly, the solar hydrogen production has the defects (the energy per unit area of the solar energy is not large) and is not suitable for large-scale industrial production, particularly the construction of a large-scale urban hydrogen station, but the solar hydrogen production is used as a household device, and the solution of urban energy consumption by one family is a sensible way for benefiting people and countries.

The invention can also utilize other energy sources as heat sources to produce industrial hydrogen, the cost of the invention is also lower than that of coal gasification hydrogen production, natural gas hydrogen production, electrolysis hydrogen production and methanol hydrogen production, the invention also has no pollution to the environment, provides the cheapest hydrogen energy for the industrial application of hydrogen fuel, ensures that the supply system of the hydrogen fuel is more convenient and more popular, is directly beneficial to the people, really achieves the purpose of reducing the investment or not investing in the state, really creates a clean and environment-friendly environment for human, and realizes that the 21 st century is a real hydrogen energy era.

Drawings

FIG. 1 is a schematic diagram of the reaction principle of spinel type catalyst cycle hydrogen production;

FIG. 2 is a schematic diagram of the basic oxygen production reaction of alkali metal salt recycle;

FIG. 3 is a schematic diagram of the reaction principle of the present invention for producing hydrogen and oxygen by using solar energy cycle;

FIG. 4 is a process flow diagram of the present invention for cyclic hydrogen and oxygen production using solar energy;

FIG. 5 is a schematic diagram of the structure of a hydrogen production adsorption bed apparatus;

FIG. 6 is a schematic view of the internal structure of the adsorbent bed;

FIG. 7 is a schematic view of a heating fin coil configuration in an adsorbent bed;

FIG. 8 is a schematic view of an internal heat and mass transfer tube configuration in an adsorbent bed;

fig. 9 is a sectional view taken along line a-a in fig. 8.

Detailed Description

Fig. 3 is a schematic diagram of the reaction principle of hydrogen and oxygen production by solar energy cycle. The heat is transferred by the heat transfer liquid provided by the solar heat collector, so that the water vapor is in the spinel type catalyst CuO-ZnAl₂O₄Under the action of the hydrogen production, hydrogen production reaction is carried out in the hydrogen production adsorption bed at the temperature of 180-₂. At this time, Na of oxygen-producing adsorption bed₂CO₃The activated carbon catalyst is decomposed when the temperature is heated to 350-400 ℃, and the generated CO is supplied to the catalyst in the hydrogen production adsorption bed for reduction reaction, so that CO is discharged₂Is recovered and returned to the oxygen production adsorption bed, so that the active carbon catalyst is returned to the alkali metal salt state to release O₂。

As shown in figure 4, when the solar heat collector 1 heats the heat transfer liquid in the solar heat transfer liquid heater 2 to be more than 258 ℃, the heat transfer liquid generates steam and is sent to the heat transfer liquid steam storage tank 3 and all the gas paths of the heat transfer liquid, the maximum service temperature of the heat transfer liquid is not more than 350 ℃, and the steam pressure of the heat transfer liquid can reach 547.2kpa at the moment. The heat transfer liquid is particularly excellent in high temperature and low pressure, because the same temperature and the same water vapor pressure are as high as 4000-14800Kpa, the difficulty and the cost are increased for manufacturing equipment, and the whole system of the heat transfer liquid is a fully closed system, so the production environment is clean and safe. Meanwhile, the heating temperature is uniform by combining the heat transfer liquid with the careful design of the adsorption bed, the control precision of the whole reaction system is high, the error of the radial or axial temperature does not exceed +/-3 ℃, the temperature can be increased or decreased at any time according to the process requirement, and the redundant heat can be stored. When the heat transfer liquid steam is input into the adsorption bed 4a, the catalyst in the adsorption bed 4a is heated, the condensate liquid is discharged from the outlet and flows back into the solar heat transfer liquid heater 2 for reheating, and new steam is generated and continuously flows into the steam storage tank 3 and the steam gas circuit thereof. When catalyzing in the adsorption bed 4When the temperature of the agent reaches above 250 ℃, the heat transfer liquid steam in the steam generator 5 heats and evaporates the water in the agent to generate a large amount of steam, and the steam is added into the hydrogen production adsorption bed 4a to react with the catalystHydrogen generation reaction and generation of H₂、H₂After heat exchange by the air heat exchanger 6a, the mixture is sucked into a storage tank by a compressor 7a for standby. When the reaction reached equilibrium, the addition of steam was stopped and the catalyst was alsostopped from heating. At the same time, the oxygen production adsorption bed 4b is heated by the heat transfer liquid vapor, and sodium carbonate (Na) is contained in the catalyst₂CO₃) Decomposition to produce Na₂O₂And CO, wherein the CO is introduced into the hydrogen production adsorption bed 4a from the compressor 7b to perform reduction reaction with the catalyst to generate CO₂The sodium peroxide (Na) in the oxygen-generating adsorption bed 4b and the alkali metal salt activated carbon catalyst in the oxygen-generating adsorption bed 4b are sucked by the compressor 9a₂O₂) Reaction to produce Na₂CO₃And O₂，O₂Is sucked into the storage tank through the air heat exchanger 6b by the compressor 7b for standby. The reaction is exothermic reaction, after the reaction, cold heat transfer liquid in the heat transfer liquid storage tank 12 can be sent into the adsorption bed 4 through the gear pump 11, and after the excessive reaction heat in the adsorption bed 4 is absorbed, the heat exchange is carried out with cold water in the hot water tank 13, so that on one hand, the excessive heat in the adsorption bed 4 can be reduced, and on the other hand, the cold water input by the cold water pipeline 10 can be heated for use.

As shown in fig. 5, when the hydrogen production adsorption bed 4a starts to prepare for hydrogen production, the adsorbed oxygen in the catalyst must be desorbed first, the electromagnetic valves a ', b' are opened, all the other electromagnetic valves are closed, and the solar heat transfer liquid vapor is introduced to heat the catalyst in the adsorption bed 4 a. When the temperature in the system reaches above 250 ℃, the compressor 9a is started, the electromagnetic valve g ' f ' is opened, g and h ' are closed, CO gas is introduced to continuously react with the catalyst, and the generated CO₂The oxygen is sent to the oxygen adsorption bed 4b by the compressor 9a to react with the alkali metal salt active carbon catalyst in the adsorption bed 4b to obtain Na₂CO₃And O₂，O₂And enters the storage tank for standby through a compressor 9 b. When the reaction in the adsorption bed 4a is finished, the electromagnetic valves g ' f ', g and h ' are all closed, the preparation is started to be transferred into hydrogen production, at the moment, the system temperature in the adsorption bed 4a exceeds 250 ℃, so that the temperature is required to be properly reduced, then the gear pump 11 is started, cold heat transfer liquid is introduced into the heat transfer carrier storage tank 12, the electromagnetic valves c ', d ' open b ', a ', c and close, the heat transfer liquid enters the adsorption bed 4, the overhigh heat is taken away, and the operation is carried out in the hot water tank 13And (4) heat exchange. The hot water in the hot water tank can be used for life or used for generating steam in the steam generator. When the temperature in the adsorption bed 4 meets the hydrogen production process requirement, the gear pump 11 stops working, the electromagnetic valves c ' and d ' are closed, the water vapor starts to be introduced at the moment, the electromagnetic valves e ' and e ' are opened, the electromagnetic valves a ', b ' and a ' are opened, the adsorption bed 4a reacts with the catalyst through the water vapor to obtain H₂When the compressor 7a starts to operate, the solenoid valve H 'is turned on g' and H is turned off, and H generated in the adsorption bed 4a₂Sucked by the compressor 7a, heat-exchanged with ambient air by the heat exchanger 6a, and then passed through the H₂And the outlet is used for collection and storage. At this time, O is produced₂The activated carbon catalyst in the adsorption bed 4b needs to be heated by an auxiliary electric heater 8 to ensure that the loaded sodium alkali metal salt is heated to the temperature required by the process, Na₂CO₃Begins to decompose, releases CO for hydrogen production and reduction and Na₂O₂，Na₂O₂Is circulated with CO at one time₂React to produce Na₂CO₃And O₂。

At the same time, the adsorbent bed 4 a' also performs the above-described deoxidation work immediately after the completion of the deoxidation of the adsorbent bed 4 a. Namely, the electromagnetic valves a and b are opened, and a ' and b ' are closed, and the solar heat transfer liquid steam is introduced to heat the catalyst in the adsorption bed 4a '. When the temperature of the system reaches above 250 ℃, the compressor 9a is started, the electromagnetic valves g and f are opened, and the electromagnetic valves h and g' are closed. Introducing CO gas to react with the catalyst continuously to generate CO₂Gas is sent to the oxygen-making adsorption bed 4b through the compressor 9a to react with the activated carbon catalyst in the oxygen-making adsorption bed 4b to obtain Na₂CO₃And O₂，O₂Compressed into a storage tank by a compressor 7b for standby. The oxygen-making adsorption bed 4b is heated to the temperature required by the process by turning on the auxiliary electric heater 8, and Na is added₂CO₃Begin to decompose to obtain Na₂O₂And CO, which is in turn supplied to the hydrogen production adsorbent bed for reduction. When the reaction in the adsorption bed 4a 'is finished, the electromagnetic valves g, f, h and g' are all closed, the temperature in the adsorption bed 4a 'is over 250 ℃, and the temperature also has to be properly reduced, so that the gear pump 11 is started, the cold heat transfer liquid in the heat transfer carrier is introduced, the electromagnetic valves c and d are opened, the electromagnetic valves a, b and c' are closed, and thecold heat transfer liquid enters the heat transfer carrierThe adsorption bed 4 a' takes away the excessive heat and performs heat exchange in the hot water tank 13. When the temperature in the adsorption bed 4a 'reaches the temperature requirement of the hydrogen production process, the gear pump 11 stops working, the electromagnetic valves c and d are closed, steam starts to be introduced at the moment, the electromagnetic valves e and e' are opened, the electromagnetic valves a and b 'are closed, the adsorption bed 4 a' obtains H through the reaction of the steam and the catalyst₂When the compressor 7b starts to operate, the solenoid valve H is turned on, the solenoid valve g is turned off, and H generated in the adsorption bed 4 a' is adsorbed₂Sucked by the compressor 7a, heat-exchanged with ambient air by the heat exchanger 6a, and then discharged from the H₂And (5) discharging, and collecting for later use.

The whole circulation hydrogen and oxygen production is that H is continuously produced by mutually crossing and circulating two groups of hydrogen production adsorption beds and two groups of oxygen production adsorption beds₂And preparation of O₂。

Fig. 6 is a sectional view of the adsorbent bed 4. The adsorption bed 4 is formed by rolling a steel plate into a rectangle, the section in the vertical direction is a square, the shell of the steel plate is provided with a heat-insulating layer 18, and the inner part of the adsorption bed is a group of whole bodies formed by a plurality of heating fin coil pipes 15 through a beam collecting pipe 17. And a plurality of heat transfer and transmission pipes 16 are uniformly arranged between every two rows of heating fin coil pipes 15. In the void part thereof, a catalyst 14 is filled in a plurality, thereby constituting the adsorption bed 4. The function and principle of the device are that when the catalyst needs to be heated or cooled, all heating fin coil pipes 15 in the adsorption bed form a complete and smooth conveying channel, which not only conveys steam (heating) of solar heat transfer liquid, but also can exchange heat of much heat in the bed with a hot water tank through cold heat transfer liquid. The heat and mass transfer tubes in the adsorption bed can allow the steam to pass through the channels and be quickly and uniformly delivered to the interior of the catalyst to take part in the reaction. And allowing the reaction to produce H₂Can be discharged smoothly without obstruction. Production of H₂And preparation of O₂The internal structure principle of the adsorption beds is the same, but the sizes and specifications are respectively selected according to the different densities of the hydrogen production catalyst and the oxygen production catalyst and are matched with each other.

Fig. 7 shows a schematic view of the structure of the heating fin coil 15. The heat-radiating heat-conducting plate is formed by spot welding a coil 19 and a plurality of heat-radiating steel wires 20 to form a group of parts with good heat-conducting effect.

Fig. 8 and 9 are schematic structural views of the heat and mass transfer tube. One end of a steel pipe 16 is sealed, the other end is not sealed, radiating fins 21 are welded on the steel pipe in a mutually perpendicular mode in the circumferential direction of the steel pipe, and grooves 22 are formed in the surfaces of the radiating fins 21, so that the heat transfer efficiency is improved. The tubes are circumferentially spaced apart to define a plurality of apertures 23 which facilitate vapor flow to accelerate the catalyst reaction and also provide a path for hydrogen or oxygen to be exhausted. The pipe ends are sealed and arranged at intervals when the pipe is installed, the steam inlet channel is arranged above the end seal, and the hydrogen or oxygen outlet channel is arranged below the end seal.

The device and the related process flow required in the whole process of solar hot water circulation hydrogen and oxygen production are obtained.

The principle can also be used for simulating industrial production for macroscopic comparison by enlarging scale, and is also suitable for circularly producing hydrogen by decomposing water vapor by other conventional energy sources. Has better advantages no matter the environmental evaluation or the economic evaluation, and the H is prepared according to the circulation of the catalyst decomposing water vapor₂And O₂The principle of (a) is specifically calculated as follows:

a, a basis

Two, calculating

1. Obtaining H from the formula (2)₂The theoretical yield of (2): $\frac{4}{267}=\frac{X}{10.4}$ $X=\frac{4\×10.4}{267}=0.156\mathrm{kg}.$ 2 pieces 0.156 x 2 pieces 0.312kg

2. Obtaining H from the formula (2)₂Theoretical consumption of O (gas): $\frac{4}{36}=\frac{0.156}{X}$ $X=\frac{36\×0.156}{4}=1.4\mathrm{kg},$ 2 pieces 1.4 x 2 pieces 2.8kg

3. Solving the theoretical requirement of CO by the formula (1): $\frac{56}{263}=\frac{X}{10.4}$ $X=\frac{56\×10.4}{263}=2.214\mathrm{kg},$ 2 pieces 2.214 x 2 pieces 4.428kg

4. Determining CO from formula (1)₂The theoretical requirement of (2): $\frac{88}{263}=\frac{X}{10.4}$ $X=\frac{88\×10.4}{263}=3.479\mathrm{kg},$ 2 pieces 3.479 x 2 pieces 6.958kg

5. Obtaining O from the formula (4)₂The theoretical yield of (2): $\frac{88}{32}=\frac{3.479}{X}$ $X=\frac{32\×3.479}{88}=1.256\mathrm{kg},$ 2 pieces 1.256 x 2 pieces 2.53kg

The yield calculated by the above calculation is the yield of one week per cycle, and the yield is set as follows by 10 cycles of 24 hours per day:

production of H₂＝0.312×10＝3.12kg/24h

Production of O₂＝2.53×10＝25.3kg/24h

Third, energy heat balance

The available energy:

setting solar focusing area 6m²800W/m²The thermal efficiency is 60 percent

The solar energy can provide heat value of 6 × 0.8 × 0.6 to 2.88KW/h, the solar energy can provide average sunshine for 9 hours every day, the total heat value of 2.88 × 9 to 25.92KW, and the device adopts the mode of solar energy plus peak-adjusting electricity in consideration of high continuous production efficiency and no influence of natural factors.

(II) energy consumption:

solar hot water circulation H production₂And preparation of O₂The production process of (2) needs to calculate the energy consumption:

1. solar hot water circulation H production₂Required energy consumption:

production of H₂An adsorption bed:

it is known that: the standard design volume of the adsorption bed is 12L; adsorbent bed standard internals volume 4L; standard effective volume of adsorption bed 8L

Catalyst (CuO. ZnAl)₂O₄) The bulk density is 1.2-1.4kg/L, 1.3kg/L on average is taken, and 10.4kg of catalyst can be contained in 8L of effective volume; the specific heat capacity of the catalyst is 0.15Kcal/kg ℃, the reaction temperature is 180 DEG and 250 ℃, and the ambient temperature is 20 ℃ on average.

The weight of steel of the adsorption bed shell is 3kg, and the specific heat capacity of the steel is 0.111kcal/kg ℃.

The weight of the copper pipe of the adsorbent bed internals is 0.75kg, and the specific heat capacity is 0.09kcal/kg ℃.

Heat value conversion formula:

t₀final reaction temperature; t' ═ ambient temperature (or waste heat recovery hot water temperature)

1KJ is equal to 0.239Kcal, 1KW is equal to 3600 KJ:

2 pieces ═ 0.16kw

2 pieces ═ 0.036kw

0.834KW for 2 pieces

Heating heat of the heat transfer liquid; setting: 5kg of heat transfer liquid is needed, the specific heat capacity of the heat transfer liquid is 0.346Kcal/kg ℃, and the weight of steel of equipment of the heat transfer liquid is 2kg

The weight of the steel material of the water vapor generator is 3kg,

the heat consumption of the water vapor is calculated to obtain H per cycle₂Consumption per time H₂2.8kg of O (gas), then(note: here the water temperature t' is in view of the relatively high water temperature for waste heat recovery,can be directly supplied to a steam generator to produce steam

The above-mentioned materials must have calorific value of 0.16+0.036+0.834+0.664+ +0.085+ 0.034-1.813 kw

2. Solar hot water circulation O preparation₂Required energy consumption

It is known that: adsorbent bed Standard design volume 25L

Adsorbent bed Standard internals volume 6.5L

The standard effective volume of the adsorption bed is 18.5L

The bulk density of the alkali metal salt active catalyst is 0.459kg/L, the specific heat capacity is 0.15Kcal/kg ℃, the final reaction temperature is 350 ℃, and the ambient temperature is 20 DEG C

When the decomposition temperature exceeds 350 ℃, an electric heating method is adopted

The weight of steel of the shell of the adsorption bed is 4.85kg, and the specific heat capacity of the steel is 0.111Kcal/kg DEG C

The weight of the copper pipe of the internal part of the adsorption bed is 1.2kg, and the specific heat capacity of the copper material is 0.09Kcal/kg DEG C

The calculation formula is the same as the above formula, wherein 1KJ is 0.239Kcal/kg ℃, and 1kw is 3600 KJ.

Solving the following steps:

2 pieces-0.412 kw

0.082KW

2 pieces-0.978 kw

The heat consumption of the above-mentioned materials is 0.412+0.082+ 0.978-1.472 KW

3. The heat energy once consumed by solar hot water circulation hydrogen and oxygen production:

(1) by making H₂The amount of heat taken away: h₂Weight 3.12kg, H₂Specific heat capacity of 3.47Kcal/kg200 deg.C

By

(2) By the production of O₂Heat quantity taken away O₂Weight 25.3kg, O₂Has a specific heat capacity of 0.25Kcal/kg100 deg.C

Then

Fourthly, summarizing:

1. the method for preparing H in one period of solar hot water circulation from 1+2₂And preparation of O₂The total heat consumption is 1.813kw +1.472kw 3.285kw

Assuming that the total heat removed from these devices per hour is 20%, the 24 hour set of devices must remove heat (3.285 × 20%) x 24h +3.285kw 19.053kw

And 3 is the heat quantity taken away at one time, so 1+2+3 is the total heat quantity consumed 19.053+0.0125+1.102

＝20.16kw

Although the total heat provided by the solar energy is larger than the total consumption (20.16kw), the heat provided by the solar energy is concentrated in the time from 8 am to 5 pm every day, and the rest of the time needs to be supplemented and compensated by conventional electricity or peak shaving electricity.

Because solar energy is influenced by natural factors, the solar energy cannot be continuously produced 24 hours per day, and the energy density per unit area of the solar energy is low, the solar energy is reasonably applied or supplemented as household energy, but the application as industry is limited, so whether the patent technology can be applied to expand industrial production?

And fifthly, the application of the method can enlarge the production scale and simulate the macroscopic comparison of industrial production.

The results of the above calculations are expanded by 2000 times, and the simulation of hydrogen energy and oxygen gas production by electric heating is compared as follows:

1. total energy consumption: 20.16kw × 2000 ═ 40320kw

2. Total H₂Yield: 3.12X 2000 ═ 6240kg

3. Total O₂Yield: 25.3 × 2000 ═ 50600kg

According to the conversion method of the value of the average industrial energy and the like, 50600kg of produced oxygen is converted into energy, and the energy consumption is deducted from the total energy consumption to obtain the actual total energy consumption. The conversion data is as follows: 1m³Oxygen 1kg oxygen, 1m³O₂＝2800Kcal

1KJ＝4.18Kcal 1kw＝3600KJ

Therefore, the calculation is as follows: 50600kgO A method for preparing a pharmaceutical composition₂×2800＝141680000Kcal

141680000Kcal÷4.18＝33894736KJ

33894736÷3600＝9415kw

40320-9415＝30905kw

30905X 0.6 ═ 18543 Yuan when the electric charge is 0.6 Yuan/kwh

18543 ÷ 6240 ═ 2.97 yuan/kgH₂

The calculation results show that the raw material cost (energy consumption) per kg of hydrogen is 2.97 yuan, while the heating value of 1kg of hydrogen is 2.5-3 times that of petroleum, and the raw material cost is obviously low. From the comparison of energy input and output, the hydrogen energy output is 20.8kw per 1kw of energy input, which is obviously a low input-to-output ratio. Hydrogen fuel pollution-free and air combustion produced is H₂And O, the combustion of petrochemical products brings too much pollution, so that the environment and all biospheres are polluted, and too much disaster is brought to human beings. The above simulation calculations and macroscopic comparisons are only to prove that the patent is economically and environmentally feasible for industrial production, and is an aspect of the development of hydrogen fuel.

Claims (10)

1. A system for preparing hydrogen and oxygen by using solar energy is characterized in that: the solar heat collector is used for providing heat transfer liquid to transfer heat, so that the water vapor has a general formula of MO-AB₂O₄Under the action of spinel catalyst, hydrogen-producing reaction takes place in hydrogen-producing adsorption bed to decompose H₂(ii) a Wherein, M can be simple substance metal Ni or simple substance metal Cu; a can be one of divalent metal ions of Zn, Mg, Fe, Mz and Ni, and B can be one of trivalent metal ions of Fe, Al and Cr; at this time, CO decomposed by heating of the alkali metal salt activated carbon catalyst of the oxygen production adsorption bed is supplied to the catalyst in the hydrogen production adsorption bed for reduction reaction, and CO is discharged₂Is recycled and returned to the oxygen-making adsorption bed to return the active carbon catalyst to the alkaliIn the state of a metal salt to release O₂。

2. The system for preparing hydrogen and oxygen by using solar energy according to claim 1, wherein: the spinel catalyst is CuO-ZnAl₂O₄A catalyst.

3. The system for preparing hydrogen and oxygen by using solar energy according to claim 1, wherein: the alkali metal salt active carbon catalyst is Na₂CO₃A catalyst.

4. The system for preparing hydrogen and oxygen by using solar energy according to claim 1, wherein: the reaction temperature for preparing hydrogen by the spinel catalyst is 180-250 ℃.

5. The system for preparing hydrogen and oxygen by using solar energy according to claim 1, wherein: the temperature of the alkali metal salt activated carbon catalyst is 350-400 ℃ when the catalyst is heated and decomposed.

6. The utility model provides an utilize device of solar energy preparation hydrogen and oxygen, includes solar collector, hydrogen manufacturing adsorption bed and oxygen manufacturing adsorption bed, heat exchanger, steam generator, pipeline, its characterized in that: the solar heat collector heats the heat transfer liquid through solar focusing, and the generated heat transfer liquid steam is conveyed to the hydrogen production adsorption bed; a spinel catalyst is arranged in the hydrogen production adsorption bed and reacts with the water vapor generated by the water vapor generator to generate hydrogen; simultaneously, carbon monoxide generated by the oxygen-making adsorption bed is input into the hydrogen-making adsorption bed through different pipelines; reducing the spinel catalyst and releasing carbon dioxide, and recycling the carbon dioxide to the oxygen-making adsorption bed to react with the alkali metal salt active carbon catalyst to generate alkali metal salt and release oxygen; the hydrogen is compressed and stored in the hydrogen storage tank after heat exchange of the heat exchanger, and the oxygen is compressed and stored in the oxygen storage tank after heat exchange of the heat exchanger.

7. The apparatus for preparing hydrogen and oxygen using solar energy according to claim 6, wherein: the hydrogen production adsorption bed and the oxygen production adsorption bed are formed by rolling a steel plate into a rectangle, the section in the vertical direction is a square, the shell of the steel plate is provided with a heat insulation layer, the inner part of the steel plate is a group of whole bodies consisting of a plurality of heating fin coil pipes and a header pipe through a cross beam, a plurality of heat and mass transfer pipes are uniformly arranged between every two rows of heating fin coil pipes, and a plurality of catalysts are filled in the gap parts of the heating fin coil pipes and the heat and mass transfer pipes.

8. The apparatus for preparing hydrogen and oxygen using solar energy according to claim 7, wherein: the heating fin coil is formed by welding a coil and a plurality of radiating steel wires.

9. The apparatus for preparing hydrogen and oxygen using solar energy according to claim 7, wherein: the heat transfer and transmission pipe is a circular pipe, one end of the pipe is sealed, radiating fins are welded on the pipe in the circumferential direction of the pipe in a mutually perpendicular mode, and a plurality of small holes are formed in the pipe at intervals in the circumferential direction.

10. The apparatus for preparing hydrogen and oxygen using solar energy according to claim 9, wherein: the surface of the radiating fin is grooved.

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