CN1962413A - Method for producing hydrogen gas and methanol using solar energy - Google Patents
Method for producing hydrogen gas and methanol using solar energy Download PDFInfo
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- CN1962413A CN1962413A CNA2005100450589A CN200510045058A CN1962413A CN 1962413 A CN1962413 A CN 1962413A CN A2005100450589 A CNA2005100450589 A CN A2005100450589A CN 200510045058 A CN200510045058 A CN 200510045058A CN 1962413 A CN1962413 A CN 1962413A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a manufacturing method of hydrogen carbinol through solar energy, which comprises the following steps: 1. preparing steam through solar energy; 2. making and separating calcium iodide; 3. hydrolyzing calcium iodide at middle temperature; preparing hydriodic acid; 4. making hydrogen; recycling iodine; 5. refining hydrogen; 6. sintering hydriodic acid; 7. recycling iodine and oxygen; 8. purifying water; 9. adopting hydrogen from front eight steps as raw material to synthesize carbinol. The photolytic pond to prepare hydrogen can be light-transmission flat-pattern container within lead net.
Description
Affiliated technical field
The present invention relates to sun power utilization and chemical field, particularly a kind of method of utilizing the solar energy production hydrogen gas and methanol that sun power is changed into chemical energy, realization suitability for industrialized production hydrogen gas and methanol.Wherein also comprise the sun power photodissociation device that this method is used.
Background technology
As everyone knows, world today's energy dilemma.Conventional energy resources---coal, oil, Sweet natural gas belong to non-renewable energy, and be exhausted day by day.Utilize oil, Sweet natural gas not satisfy the needs of growing motor vehicle far away for the motor-driven oil of raw material production, people are seeking the substitute of motor-driven oil now, and wherein the simplest is exactly methyl alcohol.Methyl alcohol is liquid fuel, good utilisation, the good storage, and alternative to gasoline is again basic chemical raw materials simultaneously, social value is huge.Hydrogen is geseous fuel, good utilisation, stores easily not as good as methyl alcohol, also is basic chemical raw materials, can be used as the energy, and lot of superiority is arranged.Sun power is the green regenerating energy, and is inexhaustible, without cease with it, and safely cleaning is pollution-free; Disadvantage is bad storage.Take sun power to become the chemical energy mode and can solve storage problem, utilize the solar energy production hydrogen gas and methanol to can be used as the breach.
Summary of the invention
In order to solve the problem that sun power is difficult for storage, the invention provides a kind of method of utilizing the solar energy production hydrogen gas and methanol, the mode of taking sun power to be transformed into chemical energy solves the approach that stores sun power, realizes suitability for industrialized production hydrogen and methyl alcohol with sun power; Also comprise the sun power photodissociation device that this method is used.
The technical solution adopted for the present invention to solve the technical problems is:
Utilize the method for solar energy production hydrogen gas and methanol, comprise following operation:
1. sun power system water vapour: prepare water vapour with solar energy collector, send into the vapour case and store; From the water vapour of vapour case air outlet output, enter in it by the inlet mouth of vaporizer I bottom, become water of condensation to flow out behind the heating calcium iodide solution from the water outlet of vaporizer I bottom, return heat collector.
2. CaI
2Preparation with separate: the unloading phase of production, add iodine, calcium oxide in the etch-proof salt manufacturing tube of sealing, and add distilled water by water tank, stir with stirrer, reaction at normal temperatures generates calcium iodide, generates water-fast calcium iodate simultaneously.After whizzer or filtration method separation, make calcium iodide solution advance liquid feeding tank, the calcium iodate solid is sent into calcining furnace.Its reaction equation:
CaO+H
2O＝Ca(OH)
2
6I
2+6Ca(OH)
2＝5CaI
2+Ca(IO
3)
2↓+6H
2O
The unloading phase after, from the intermediate product of a plurality of links of flow process, in the salt manufacturing tube, continue to keep the carrying out that generates calcium iodide and calcium iodate reaction;
3. CaI
2Hydrolysis system HI: with the calcium iodide solution in the liquid case, sent in it by vaporizer I top fluid inlet after preheating, through the 1. described water vapour heating of money, hydrogen iodide is produced in reaction under 42 ℃～250 ℃ temperature, generates alkali formula calcium iodide simultaneously in vaporizer I.Its reaction equation:
Hydrogen iodide gas is emitted from the air outlet at vaporizer I top, is entered by the inlet mouth of vaporizer II bottom, in vaporizer II, after water-cooled, becomes hydroiodic acid HI solution, is flowed out by the liquid outlet of vaporizer II bottom, enters photolytic cell.Alkali formula calcium iodide suspension flows out from the liquid outlet of vaporizer I bottom, sends into the salt manufacturing tube.In the salt manufacturing tube, stir through stirrer, generate calcium iodide with Iod R.Its reaction equation:
6I
2+12Ca(OH)I＝11CaI
2+Ca(IO
3)
2↓+6H
2O
4. photodissociation HI makes H
2Reclaim I
2: enter hydroiodic acid HI solution in it by photolytic cell bottom fluid inlet, with the plumbous or silver reaction in the photolytic cell, photodissociation under the sunlight in photolytic cell is advanced in transmission again generates hydrogen and iodine simultaneously.Hydrogen is emitted by the photolytic cell top exit, and water is emitted by its underpart outlet.Its reaction equation:
Pb+2HI＝PbI
2+H
2↑ 2Ag+2HI＝2AgI+H
2↑
After gas and liquid have been put in the outlet of photolytic cell, the calcium iodide solution from the liquid case is entered from the fluid inlet bottom the photolytic cell.The iodine that calcium iodide solution dissolving photodissociation generates generates six calcium iodides; The hexaiodo calcium solution flows out from the outlet of photolytic cell top, enters the salt manufacturing tube.In the fluid inlet and the upper and lower outlet of photolytic cell, photodissociation hydroiodic acid HI and two steps of recovery iodine are to control automatically or Artificial Control by switch.Its reaction equation: CaI
2+ 2I
2=CaI
6
5. refining H
2: after hydrogen is emitted from photolytic cell, enter in it by the inlet mouth of I bottom, absorption tower; The absorption agent aqua calcis is entered by I top, absorption tower fluid inlet, in the I of absorption tower, absorb hydrogen iodide remaining in the hydrogen, iodine gas after, flow out by the liquid outlet of absorption tower I bottom; Hydrogen is emitted by the air outlet at I top, absorption tower, enters the hydrogen gas tank.
6. calcine Ca (IO
3)
2: with isolated calcium iodate in the salt manufacturing tube, send in the corrosion resistant calcining furnace,, generate calcium oxide, iodine and oxygen through 540 ℃～550 ℃ high-temperature calcinations.Its reaction equation:
Send into the ashing tube after calcium oxide is come out of the stove, generate calcium hydroxide with the water that adds the ashing tube and enter the salt manufacturing tube.
7. reclaim I
2And O
2: by oxygen and iodine gas that the calcining furnace air outlet emits, the inlet by condenser I enters in it together, by water cooling, becomes liquid, solid after the iodine air cooling but, is attached on the tube wall; Oxygen is still gaseous state, is emitted by condenser I top exit.After the two separated, oxygen was entered in it by the inlet mouth of II bottom, absorption tower.The absorption agent aqua calcis is entered by II top, absorption tower fluid inlet, in the II of absorption tower, absorb iodine gas remaining in the oxygen after, flow out by the liquid outlet of II bottom, absorption tower.The oxygen that purifies is emitted by the air outlet at II top, absorption tower, enters the oxygen gas tank.
After condenser I emits oxygen, make from the calcium iodide solution of liquid case inlet to enter from condenser I; Behind the calcium iodide solution dissolving iodine, generate six calcium iodides, the hexaiodo calcium solution flows out from the top outlet of condenser I, enters the salt manufacturing tube.Reclaiming oxygen and reclaim two steps of iodine, is to finish by automatic control of switch or Artificial Control at condenser I entrance and exit.
8. water purification: enter water coolant in it by the water-in on vaporizer II top, in cooling hydrogen iodide gas, become water vapour, air outlet by vaporizer II top emits, enter among the condenser II for the preheating of calcium iodide solution, return water tank through being condensed into distilled water, the purifying waste water of water tank sent into the salt manufacturing tube again and replenished.Impurity in the water coolant is discharged by the water outlet of vaporizer II bottom.
After above-mentioned hydrogen production process started, the resultant that returns the salt manufacturing tube continued reaction, and continues photodissociation hydrogen manufacturing in the sun.After producing hydrogen, also can continue subsequent processing:
9. synthesizing methanol: the hydrogen of producing with above-mentioned operation is raw material, makes it and carbon dioxide mix, enters synthetic tower by compressor compresses, reacts synthesizing methanol in synthetic tower.Its reaction equation:
Above-mentioned reaction all belongs to the general chemistry reaction, and its quantitative relationship is determined in this not explanation one by one by equation.
The technical solution adopted for the present invention to solve the technical problems can also be:
In the method for utilizing the solar energy production hydrogen gas and methanol, the preferred temperature of producing hydrogen iodide in vaporizer I is 127～160 ℃.The calcium iodide strength of solution is answered＞1mol.dm in the liquid case
-3The water vapour that solar energy collector is produced send the turbine driven set generating earlier, is the calcining furnace heating with the electric energy that produces by electric furnace; And when no sunlight,, keep photolysis for the electric light source power supply that high brightness LED is formed.Also available is the calcining furnace heating from hydrogen.The carbonic acid gas that production methyl alcohol is used is to make absorption agent with highly basic and aqua calcis in the absorption tower, absorbs carbon dioxide in air, decomposes to obtain carbonic acid gas again.
The photodissociation device that the present invention is used, promptly photolytic cell is that a upper surface is transparent glass, has the plumbous net parallel with transparent glass, bottom and periphery to be that the plate container of anticorrosive housing, its upside have upper outlet, downside that fluid inlet and outlet are down arranged in it.Mesh wire diameter 〉=0.1mm, the galvanized wire spacing 〉=0.3mm of its plumbous net, plumbous net is 1～3 layer.Photolytic cell also can be combined as a whole with heat collector, and promptly photolytic cell is a transparent glass at last, its base plate, and heat collector is following, and making not, photolytic sunlight is transmitted on the heat collector cartridge.The photodissociation device can also be made up of the row's Circular glass pipe that is planar alignment, and the upper/lower terminal of Glass tubing is connected with drain pipe, liquid-inlet pipe respectively, and sensitive surface is laid plumbous net in the Glass tubing.
The invention has the beneficial effects as follows:
1. contribution of the present invention is to utilize sun power that a kind of approach is provided with chemical process, promptly when utilizing the sun power chemical effect, also utilize its heat effect, with water and carbonic acid gas is raw material, realize the suitability for industrialized production hydrogen gas and methanol by chemical reaction, the chemical energy that makes sun power become the easy storage of user is a conventional energy resources, can replace coal, oil, Sweet natural gas etc.Economic benefit and social benefit are very huge.
2. the methyl alcohol of this method production reduces by 20% at least than the methyl alcohol cost with coal production.
3. the hydrogen that utilizes this law production can synthesize a series of organism with carbonic acid gas as industrial chemicals, can change the raw material mix of Chemical Manufacture.Social value is very obvious.
Description of drawings
Accompanying drawing is the process flow sheet that the present invention utilizes the method for solar energy production hydrogen gas and methanol
Among the figure: 1-salt manufacturing tube, 2-calcining furnace, 3-condenser, 4-condenser, 5-vaporizer, 6-vaporizer, 7-photolytic cell, 8-absorption tower, 9-absorption tower, 10-ashing tube, 11-moisture trap, 12-heat collector, 13-vapour case, 14-water tank, 15-liquid case, 16-gas tank.Condenser I, II are condenser (3), (4); Vaporizer I, II are vaporizer (5), (6); Absorption tower I, II are absorption tower (8), (9).
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
Overall plan of the present invention: be to utilize sun power that water is resolved into hydrogen and oxygen; Then with hydrogen and the synthetic a series of organic compound of carbonic acid gas, for example: methyl alcohol, ethanol, methyl ether, acetate, formaldehyde etc.
2H
2O＝2H
2+O
2
Embodiment 1: utilize solar energy production hydrogen
The one, produces the ultimate principle of hydrogen: the reaction of water being resolved into hydrogen and oxygen can not be carried out by spontaneous forward, but mainly with chemical process water is become easy photolytic compound by following four processes, with the wherein more difficult pyrolytic compound of photolysis, finish a hydrogen manufacturing circulation, final realization response forward carries out.
1) manufacturing of salt: 6I
2+ 6Ca (OH)
2=5CaI
2+ Ca (IO
3)
2↓+6H
2O
2) cracking of water:
3) discharge hydrogen:
4) discharge oxygen:
The 2nd, produces the main production process of hydrogen:
The master operation of producing hydrogen comprises: 1. sun power prepares water vapour; 2. the preparation of salt with separate; 3. the preparation of the medium temperature hydrolyzation of calcium iodide solution and hydroiodic acid HI; 4. the recovery of the preparation of hydrogen and iodine; 5. hydrogen is refining; 6. the calcining of calcium iodate; 7. the recovery of iodine and oxygen; 8. water purification.
The 3rd. produce the technical process of hydrogen and the explanation of each master operation:
Accompanying drawing illustrates the Production Flow Chart that the present invention utilizes solar energy production hydrogen.Its flow process and operation are as follows:
1. sun power prepares water vapour:
Heat the generation water vapour of purifying waste water with solar energy collector (12), concentrate and send into vapour case (13) storage; Water vapour from the output of vapour case (13) air outlet, enter by vaporizer (5) bottom inlet mouth by pipeline, form with water of condensation behind the heating calcium iodide solution flows out from vaporizer (5) bottom water outlet, after the low-temperature end by vapour case (13), is returned in it by heat collector (12) lower water inlet.
At present, it is proven technique that solar water heater utilizes sun power, and it is to adopt plate solar heater to produce hot water.Because CaI
2Solution evaporation needs 134 ℃, the water vapour of 3 bar absolute pressures, and temperature is relatively low, and is higher slightly than solar water actuator temperature, so adopt flat-plate solar heat collector.
The solar energy collector section is a rectangle.Be transparent cover above, material is general with low iron glass.The centre is a cartridge, and its effect is to absorb the solar radiation that sees through cover and change heat energy into, passes to the working-medium water that wherein flows through, and by working-medium water heat is conducted then.The unglazed chalkboard paint of the general brushing of absorber surface.Material is generally used metal.Cartridge can be made into various multi-form, and its cross section can be a shape such as circle, flat.Under-filled heat-insulating material.Both sides and bottom are the protection outer containers.
Because the water vapour of temperature in producing, so the solar energy collector cover adopts layer glass, spacing 10mm.Cartridge adopts the good aluminium that conducts heat, and working-medium water adopts distilled water.Inside is evacuated, and outer container adopts the steel plate materials of good seal performance.
2. salt CaI
2Preparation with separate:
1) salt CaI
2Preparation:
The unloading phase of production, add iodine, calcium oxide in the etch-proof salt manufacturing tube (1) of sealing, and add distilled water by water tank (14), stir with stirrer, reaction at normal temperatures generates calcium iodide, generates water-fast calcium iodate simultaneously.Its reaction equation:
CaO+H
2O＝Ca(OH)
2
6I
2+6Ca(OH)
2＝5CaI
2+Ca(IO
3)
2↓+6H
2O
The unloading phase after, from the intermediate product of a plurality of links of flow process, in salt manufacturing tube (1), continue to keep the carrying out that generates calcium iodide and calcium iodate reaction.These intermediate products are mainly from 5 links:
At first from the next CaI of photolytic cell (7)
6Solution and the CaI that comes from condenser (3)
6Solution is promptly used CaI
2Solution absorption I
2Generate, enter salt manufacturing tube (1).Secondly, enter salt manufacturing tube (1) from the effusive Ca in vaporizer (5) bottom (OH) I suspension.Water tank (14) continues to add distilled water to salt manufacturing tube (1).At last, the CaO that comes out from calcining furnace (2) makes milk of lime by ashing tube (10), enters salt manufacturing tube (1).Wherein, flow into Ca (OH) I and the I of salt manufacturing tube (1) by vaporizer (5) bottom liquid outlet
2Reaction.Its reaction equation:
6I
2+12Ca(OH)I＝11CaI
2+Ca(IO
3)
2↓+6H
2O
Preparation salt CaI
2Purpose be CaI
2Medium temperature hydrolyzation is produced HI.Preparation salt Ca (IO
3)
2Purpose be oxygen to be composed store away, pyrolytic decomposition is emitted oxygen, finishes the circulation of water of decomposition.
Alkali and halogen reaction generate two kinds of salt and belong to the chemical reaction that carries out easily, get final product at normal temperatures, and react completely.Because wherein a kind of salt is water insoluble, be easy to two kinds of salt are separated.Because iodide ion is easily by the oxidation of airborne oxygen institute, so must be prepared in the container salt manufacturing tube (1) of sealing.Salt manufacturing tube (1) will adopt etch-proof container.The CaI that makes
2Strength of solution should reach 1mol.dm
-3More than, otherwise that later reaction is carried out is too slow.
Above reactant stirs with stirrer in salt manufacturing tube (1), can react rapidly.Because of being swift in response fully, the continuous adding of reactant can not influence CaI
2The separation of solution is even the thing that responds is sneaked into CaI
2Do not influence follow-up reaction in the solution yet.
2) salt CaI
2And Ca (IO
3)
2Separation:
Finish at salt manufacturing tube (1) internal reaction, form CaI
2Solution and Ca (IO
3)
2Suspension.Owing to need I in the solution
2Excessive a little, and I
2Metal is corrosive, separates so employing has etch-proof whizzer.Also available other separation method makes CaI
2And Ca (IO
3)
2Separate, as filtration method.CaI after the separation
2It is standby that solution advances liquid feeding tank (15), and the calcium iodate solid is sent into calcining furnace (2).
3. the preparation of the medium temperature hydrolyzation of calcium iodide and hydroiodic acid HI:
With the calcium iodide solution in the liquid case (15), after preheating, send into by vaporizer (5) top fluid inlet, through the 1. described water vapour heating of money, hydrogen iodide is produced in hydrolysis under 42 ℃～250 ℃ temperature, generates alkali formula calcium iodide simultaneously in vaporizer (5).Its reaction equation:
Hydrogen iodide gas is emitted from vaporizer (5) air outlet, top, is entered by the inlet mouth of vaporizer (6) bottom, in vaporizer (6), after water-cooled, becomes hydroiodic acid HI solution, is flowed out by vaporizer (6) bottom liquid outlet, advances photolytic cell (7).Alkali formula calcium iodide suspension flows out from vaporizer (5) bottom liquid outlet, sends into salt manufacturing tube (1).In salt manufacturing tube (1), generate calcium iodide with Iod R, as described in 2. money.
The purpose of preparation hydroiodic acid HI is to react releasing hydrogen gas with it with silver or lead.The purpose of selecting calcium iodide for use is its easy hydrolysis, and＞42 ℃ just can be hydrolyzed.Reaction can be chosen in 42～250 ℃ of temperature ranges and carry out.Because HI constant boiling solution boiling point is 127 ℃, in order to react completely and acceleration, preferred range is 127～160 ℃, and heating steam this moment is equivalent to 2～5 bar absolute pressures approximately.The hydrolysis of calcium iodide is generally carried out in standard pan, because this process has hydroiodic acid HI to participate in, so vaporizer adopts anticorrosive, generally selects stainless steel for use.
From the HI mixed gas that vaporizer (5) air outlet, top emits, contain HI gas, water vapour, a small amount of iodine gas and hydrogen.The HI mixed gas enters vaporizer (6), and effusive phlegma is 1 bar absolute pressure, enters photolytic cell (7).Thick water enters vaporizer (6) as water coolant, and the heat that has absorbed the HI mixed gas becomes water vapour, flows out vaporizer (6) air outlet, top by top and emits, and dense water impurity is discharged from the bottom.
4. the recovery of the preparation of hydrogen and iodine:
1) preparation of hydrogen:
Enter hydroiodic acid HI solution in it by photolytic cell (7) bottom fluid inlet,, advance photodissociation under the sunlight of photolytic cell (7) in transmission again simultaneously, generate hydrogen and iodine with the plumbous or silver reaction in the photolytic cell (7).Hydrogen is emitted by the outlet of photolytic cell (7) top, and water is emitted by its underpart outlet.Photodissociation HI makes H
2Reaction equation:
Pb+2HI＝PbI
2+H
2↑ 2Ag+2HI＝2AgI+H
2↑
2) recovery of iodine:
After gas and liquid have been put in the outlet of photolytic cell (7), make from the calcium iodide solution of liquid case (15) bottom fluid inlet to enter from photolytic cell (7); The iodine that calcium iodide solution dissolving photodissociation generates generates six calcium iodides, and the hexaiodo calcium solution flows out from the top outlet of photolytic cell (7), enters salt manufacturing tube (1).In the fluid inlet of photolytic cell (7), outlet up and down, photodissociation hydroiodic acid HI and two steps of recovery iodine are to control automatically or Artificial Control by switch.Its reaction equation:
CaI
2+2I
2＝CaI
6
Preparation hydrogen carries out in photolytic cell (7).The photodissociation unit operation is not discussed in the Essential Chemistry engineering.The photodissociation unit operation belongs to new projects, at this detailed description.
If directly pyrolysis HI gas is produced H
2, need temperature higher.If directly photodissociation HI gas is produced H
2, required light wavelength is in ultraviolet ray range, so the indirect method of taking.
Produce H with Ag or Pb and HI solution reaction
2, use photolysis AgI or PbI again
2Because Ag is a precious metal, so adopt Pb.PbI
2The photodissociation maximum wavelength is 494.9 nanometers, in green range.Because Pb and HI solution reaction generate the PbI that is difficult for reacting on the Pb surface
2Protective film is so Pb and HI solution reaction are produced H
2, must need very big Pb surface-area.With the sunlight decomposed substance all is to carry out at material surface, and material is very thick to be difficult for photodissociation.H can be produced by Pb and HI solution reaction in comprehensive above-mentioned two aspects under rayed
2For the surface-area that increases Pb adopts the Pb net.Pb net Pb filament diameter is more little, and surface-area is big more.Consider physical strength, the Pb filament diameter selects 0.1mm, and Pb twine spacing is selected 0.3mm, is easy to printing opacity, passes through liquid.
The structure of photolytic cell (7): for upper surface is the plate container of transparent glass, it receives the optional circle in transverse section or the rectangle of illumination, 1～3 layer on interior dress Pb net.The employing glass of circular cross section; The rectangle section, light transmission part, top glass, the peripheral base anticorrosive, as: plastics, stainless steel, all use glass good.Photolytic cell (7) is if select the rectangle section for use, and its internal space height is to decide by amount of liquid, generation amounts of hydrogen.Be generally 1 bar absolute pressure, the internal space height is greater than 10mm.It is tilting that photolytic cell (7) generally has stent support to meet light, and downside is established fluid inlet, outlet down, and upside is established upper outlet.
Photolytic cell (7) also can be made up of row's circle cross section Glass tubing of planar alignment, the edge is subjected to the light bottom surface to lay plumbous net in Glass tubing, each Glass tubing upper/lower terminal is communicated with liquid-inlet pipe, drain pipe respectively, establishes fluid inlet, outlet down on the liquid-inlet pipe, establishes upper outlet on the drain pipe.Its structure is similar to solar energy vacuum tube water heater.
During photodissociation HI, H is emitted in the HI solution and the reaction of Pb net surface that enter photolytic cell (7)
2, the Pb net surface forms PbI
2Thin layer.The rayed that sees through from top glass lid is at PbI
2The surface, PbI
2Be broken down into Pb and I
2, it is online that Pb stays Pb, I
2It is online to be attached to Pb.Reaction finishes, H
2Emit from photolytic cell (7) simultaneously with liquid.
Reclaim the method for iodine: because I
2Be soluble in iodide solution, so adopt CaI
2Solution dissolves I
2After photolytic cell (7) has been put gas and liquid, CaI from liquid case (15)
2Solution injects photolytic cell (7), uses CaI
2Solution dissolving I
2, with CaI
6The solution form is emitted from photolytic cell (7), enters salt manufacturing tube (1).
H
2Preparation and recovery I
2Two steps are in the fluid inlet and the upper and lower outlet of photolytic cell (7), generally are to be magnetic valve with switch, control automatically by programmable controller.
5. hydrogen is refining:
After hydrogen is emitted from photolytic cell (7), enter in the tower by the bottom inlet mouth of absorption tower (8); The absorption agent aqua calcis is entered by top, absorption tower (8) fluid inlet, in absorption tower (8), absorb hydrogen iodide remaining in the hydrogen, iodine gas after, flow out by absorption tower (8) bottom liquid outlet.Hydrogen is emitted by air outlet, top, absorption tower (8), by moisture trap (11) dehumidifying, enters hydrogen gas tank (16).
The hydrogen that comes out from photolytic cell (7) contains impurity, mainly is HI gas, I
2Gas and water vapour also have other impurity, according to different purposes, must remove them.
1) HI gas and H
2The removing of gas: because HI, I
2Easily and Ca (OH)
2So reaction is with Ca (OH)
2Solution is good as absorption agent with saturated solution.Select for use turbulent contact absorber as absorption equipment.
2) dehumidifying of hydrogen: the dehumidifying of hydrogen is a routine techniques, no longer narration.
Other impurity takes correlation method to handle in the hydrogen.Purified hydrogen is stored in the gas tank (16) after the removal of impurities.
6. the calcining of calcium iodate:
With isolated calcium iodate in the salt manufacturing tube (1), send in the corrosion resistant calcining furnace (2), through 540 ℃～550 ℃ high-temperature calcinations, generate calcium oxide, iodine and oxygen.Its reaction equation:
The purpose of calcining calcium iodate mainly is to reclaim iodine.Calcining is classical unit operation.The calcining calcium iodate adopts rotary calcining stove (2).Because I
2The calcining furnace stove plate that is corrosive adopts stainless steel stove plate.Temperature in is 550 ℃, and temperature out is less than 200 ℃.
Calcium iodate can transport with conveyor, also can adopt other mode of transport.
The calcining calcium iodate adopts hydrogen to act as a fuel.The reason that adopts hydrogen to make fuel is that calcining temperature is higher, can be greater than 540 ℃, and hydrogen fuel is simple to operate.If use solar cooker, facility complexity, price height, complicated operation, sun power efficient is very low.Also can adopt chemical process to make Ca (IO
3)
2Be transformed into the lower material of temperature, but very bother.Employing is made the theoretical basis of fuel from hydrogen producing, is that the required theoretical heat energy of calcination process only accounts for 19% of the required theoretical heat energy of water of decomposition.Avoid the high temperature of sun power like this and collect, take the middle temperature of sun power to collect, facility, operate all simply, the sun power utilising efficiency is also higher.
The unslaked lime that the calcining back generates is sent into ashing tube (10), and the water reaction with being flowed into by photolytic cell (7) water outlet in the ashing tube (10) generates calcium hydroxide, enters salt manufacturing tube (1).The gas of emitting after the calcining enters next procedure.Behind the combustion of hydrogen, the exhaust temperature of emitting is higher, should recovery waste heat.
7. the recovery of iodine and oxygen:
By oxygen and iodine gas that the calcining furnace air outlet emits, the inlet by condenser (3) enters in it together, by water cooling, becomes liquid, solid after the iodine air cooling but, is attached on the tube wall, and oxygen is still gaseous state, is emitted by condenser (3) top exit; After the two separates, oxygen is entered in it by bottom, absorption tower (9) inlet mouth, the absorption agent aqua calcis is entered by top, absorption tower (9) fluid inlet, after in absorption tower (9), absorbing iodine gas remaining in the oxygen, flow out by bottom, absorption tower (9) liquid outlet, the oxygen that purifies is emitted by air outlet, top, absorption tower (9), enters the oxygen gas tank.
After condenser (3) is emitted oxygen, make from the calcium iodide solution of liquid case (15) inlet to enter from condenser (3); Behind the calcium iodide solution dissolving iodine, generate six calcium iodides, the hexaiodo calcium solution flows out from the top outlet of condenser (3), enters salt manufacturing tube (1).Reclaiming oxygen and reclaim two steps of iodine, is by switch control or Artificial Control automatically at the entrance and exit of condenser (3).
Condenser adopts cold water to cool off.Turbulent contact absorber is adopted on the absorption tower, absorption agent Ca (OH)
2Saturated solution is better, mainly is to reclaim remaining iodine gas.The dehumidifying back is stored in gas tank as product oxygen.
Reclaiming iodine and the oxygen two steps entrance and exit in condenser (3), generally is to adopt magnetic valve, controls automatically by programmable controller.
8. water purification:
Enter its interior water coolant by vaporizer (6) top water-in, in cooling hydrogen iodide gas, become water vapour, air outlet by vaporizer (6) top emits, enter in the condenser (4) for the preheating of calcium iodide solution, return water tank (14) through being condensed into distilled water, the purifying waste water of water tank (14) sent into salt manufacturing tube (1) again and replenished.Impurity in the water coolant is discharged by vaporizer (6) bottom water outlet.
Water is the basic raw material of producing hydrogen, must use Purified Water in the production.The vitriol that contains in the water is harmful to system, and sulfate radical and lead ion generate lead sulfate.The one, lead sulfate is difficult to be decomposed, and causes lead loss to increase; The 2nd, it is deposited on fouling on the tube wall easily.Adopt distillation method to produce Purified Water in this flow process.
Water purification method:
1) with filtering settling process except that the mechanical impurity in anhydrating.
2) with vaporizer water is become water vapour: the water of removing mechanical impurity enters vaporizer (6), is used for the middle temperature HI mixed gas of flash-pot (5) to heat, and becomes water vapour and flows out, and makes the HI mixed gas be cooled to liquid simultaneously.Vaporizer (6) adopts etch-proof standard pan.
3) water vapour becomes water by condenser: the water vapour that comes out from vaporizer (6) is condensed into water by condenser (4).It is stand-by to enter water tank (14) as Purified Water.
Embodiment 2:
The photodissociation device that utilizes the solar energy production hydrogen gas and methanol to use, be photolytic cell (7), be combined as a whole with solar energy collector (12), be that photolytic cell (7) is descending at last, heat collector (12), the base plate of photolytic cell (7) is a transparent glass, parallel with heat collector (12) top panel transparent glass and have insulated room every.The two combines, and makes the cartridge that can not the photolytic sunlight enters heat collector (12) become heat energy, increases operation rate.
Embodiment 3:
In the method for utilizing the solar energy production hydrogen gas and methanol, the water vapour that solar energy collector (12) is produced, input turbine driven set generating earlier, and then enter in the vaporizer (5).The electric energy that generating set is produced is calcining furnace (2) heat supply by electric furnace, the calcining calcium iodate.And, when no sunlight, be the electric light source power supply that high brightness LED is formed, keep photolysis, uninterruptedly carry out down to whole flow process.
Embodiment 4: utilize solar energy production methyl alcohol
Utilize the general planning of solar energy production methyl alcohol: utilize the hydrogen of solar energy production, with the carbonic acid gas that different methods is produced, the two mixes back synthesizing methanol in synthetic tower.Its reaction equation:
The one, produces the Production Flow Chart of methyl alcohol:
Utilize the solar energy production hydrogen gas system to obtain qualified hydrogen; Utilize calcining furnace that decomposition of limestone is become unslaked lime and carbonic acid gas, obtain qualified carbonic acid gas through the water wash udst separation; Behind qualified hydrogen and carbon dioxide mix, by entering synthetic tower after the compressor compresses, synthesizing methanol under catalyzer and suitable temperature, pressure.To synthetic methyl alcohol separate, purification obtains qualified methanol product.
The 2nd, produces the master operation of methyl alcohol:
Master operation comprises: the 1. production of hydrogen; 2. the production of carbonic acid gas and purification; 3. methyl alcohol is synthetic and refining.Wherein, 1. the production of hydrogen is same as the previously described embodiments, is mature technology with the catalyzer synthesizing methanol in synthetic tower 3., no longer narration.What stress is that this synthesis system is more suitable for environment protection.
The production of carbonic acid gas and purification: its mode of production has following three kinds:
1) utilize carbonic acid gas that fossil oil or organic compound combustion generate through collection and purification as unstripped gas.
2) with the Wingdale be raw material, obtain unslaked lime and carbonic acid gas through calcining, carbonic acid gas is made unstripped gas through purification, and unslaked lime is for paying product.
3) utilize absorption agent, absorb carbon dioxide in air, desorb obtains carbonic acid gas again, through purifying as unstripped gas.This is a kind of permanent method.Can adopt different absorption agents and corresponding absorption equipment.For example use highly basic Na (OH) or K (OH), with Ca (OH)
2Together as absorption agent, equipment generally adopts the standard absorption tower.With Na (OH) and Ca (OH)
2As absorption agent is example, and its reaction equation is:
Na(OH)+CO
2＝Na
2CO
3
Ca(OH)
2+Na
2CO
3＝CaCO
3↓+Na(OH)
Calcined limestone produces unslaked lime and carbonic acid gas is a routine techniques, utilizes solar energy production hydrogen to make fuel at this, and is very convenient.The unslaked lime of producing is useful in solar energy production hydrogen process.
Continuous production when solving no sunlight can solve by following measure: 1. strengthen solar energy collector and vapour case capacity, increase storage vapour amount; 2. photodissociation can replace daylight with the electric light source irradiation of green wavelength, for example: adopt high efficiency high brightness LED to form electric light source.
Claims (10)
1. method of utilizing the solar energy production hydrogen gas and methanol comprises following operation:
1. use solar energy collector (12) system water vapour, send into vapour case (13); Water vapour from the output of vapour case (13) air outlet is entered in it by vaporizer (5) bottom inlet mouth, becomes water of condensation to flow out from vaporizer (5) bottom water outlet behind the heating calcium iodide solution, returns heat collector (12);
2. the unloading phase of production, add iodine, calcium oxide in the etch-proof salt manufacturing tube (1) of sealing, and add distilled water by water tank (14), stir with stirrer, reaction at normal temperatures generates calcium iodide, generates water-fast calcium iodate simultaneously; After whizzer or filtration method separation, make calcium iodide solution advance liquid feeding tank (15), the calcium iodate solid is sent into calcining furnace (2); Its reaction equation:
CaO+H
2O＝Ca(OH)
2
6I
2+6Ca(OH)
2＝5CaI
2+Ca(IO
3)
2↓+6H
2O
The unloading phase after, from the intermediate product of a plurality of links of flow process, in salt manufacturing tube (1), continue to participate in the reaction that generates calcium iodide and calcium iodate;
3. with the calcium iodide solution in the liquid case (15), sent in it by vaporizer (5) top fluid inlet after preheating, through the 1. described water vapour heating of money, hydrogen iodide is produced in reaction under 42 ℃～250 ℃ temperature, generates alkali formula calcium iodide simultaneously in vaporizer (5); Its reaction equation:
Hydrogen iodide gas is emitted from vaporizer (5) air outlet, top, is entered by the inlet mouth of vaporizer (6) bottom, in vaporizer (6), after water-cooled, becomes hydroiodic acid HI solution, is flowed out by vaporizer (6) bottom liquid outlet, advances photolytic cell (7); Alkali formula calcium iodide suspension flows out from vaporizer (5) bottom liquid outlet, sends into salt manufacturing tube (1); In salt manufacturing tube (1), stir through stirrer, generate calcium iodide with Iod R; Its reaction equation:
6I
2+12Ca(OH)I＝11CaI
2+Ca(IO
3)
2↓+6H
2O
4. enter hydroiodic acid HI solution in it by photolytic cell (7) bottom fluid inlet,, advance photodissociation under the sunlight of photolytic cell (7) in transmission again simultaneously, generate hydrogen and iodine with the plumbous or silver reaction in the photolytic cell (7); Hydrogen is emitted by the outlet of photolytic cell (7) top, and water is emitted by its underpart outlet; Its reaction equation:
Pb+2HI＝PbI
2+H
2↑ 2Ag+2HI＝2AgI+H
2↑
After gas and liquid have been put in the outlet of photolytic cell (7), make from the calcium iodide solution of liquid case (15) bottom fluid inlet to enter from photolytic cell (7); The iodine that calcium iodide solution dissolving photodissociation generates generates six calcium iodides, and the hexaiodo calcium solution flows out from the top outlet of photolytic cell (7), enters salt manufacturing tube (1); In the fluid inlet of photolytic cell (7), outlet up and down, photodissociation hydroiodic acid HI and two steps of recovery iodine are to control automatically or Artificial Control by switch; Its reaction equation:
CaI
2+2I
2＝CaI
6
5. after hydrogen is emitted from photolytic cell (7), enter in it by bottom, absorption tower (8) inlet mouth; The absorption agent aqua calcis is entered by top, absorption tower (8) fluid inlet, in absorption tower (8), absorb hydrogen iodide remaining in the hydrogen, iodine gas after, flow out by absorption tower (8) bottom liquid outlet; Hydrogen is emitted by air outlet, top, absorption tower (8), enters hydrogen gas tank (16);
6. with isolated calcium iodate in the salt manufacturing tube (1), send in the corrosion resistant calcining furnace (2),, generate calcium oxide, iodine and oxygen through 540 ℃～550 ℃ high-temperature calcinations; Its reaction equation:
Send into ashing tube (10) after calcium oxide is come out of the stove, generate calcium hydroxide, enter salt manufacturing tube (1) with the water that adds in the tube (10);
7. the oxygen and the iodine gas of emitting by the calcining furnace air outlet, the inlet by condenser (3) enters in it together, by water cooling, becomes liquid, solid after the iodine air cooling but, is attached on the tube wall, and oxygen is still gaseous state, is emitted by condenser (3) top exit; After the two separates, oxygen is entered in it by bottom, absorption tower (9) inlet mouth, the absorption agent aqua calcis is entered by top, absorption tower (9) fluid inlet, after in absorption tower (9), absorbing iodine gas remaining in the oxygen, flow out by bottom, absorption tower (9) liquid outlet, the oxygen that purifies is emitted by air outlet, top, absorption tower (9), enters the oxygen gas tank;
After condenser (3) is emitted oxygen, make from the calcium iodide solution of liquid case (15) inlet to enter from condenser (3); Behind the calcium iodide solution dissolving iodine, generate six calcium iodides, the hexaiodo calcium solution flows out from the top outlet of condenser (3), enters salt manufacturing tube (1); Reclaiming oxygen and reclaim two steps of iodine, is by switch control or Artificial Control automatically at the entrance and exit of condenser (3);
8. enter its interior water coolant by vaporizer (6) top water-in, in cooling hydrogen iodide gas, become water vapour, emit by vaporizer (6) air outlet, top, enter in the condenser (4) for the preheating of calcium iodide solution, return water tank (14) through being condensed into distilled water, salt manufacturing tube (1) is sent in purifying waste water of water tank (14) again; Impurity in the water coolant is discharged by vaporizer (6) bottom water outlet;
Said process returns the resultant sustained reaction of salt manufacturing tube and photodissociation hydrogen manufacturing under illumination after starting;
Perhaps, after producing hydrogen, continue subsequent processing:
9. the hydrogen of producing with above-mentioned operation is raw material, makes it and carbon dioxide mix, enters synthetic tower by compressor compresses, reacts synthesizing methanol in synthetic tower; Its reaction equation:
2. the method for utilizing the solar energy production hydrogen gas and methanol according to claim 1 is characterized in that: the preferred range of producing hydrogen iodide in the said vaporizer (5) is 127～160 ℃.
3. the method for utilizing the solar energy production hydrogen gas and methanol according to claim 1 is characterized in that: the calcium iodide solution in the said liquid case (15), its concentration＞1mol.dm
-3
4. the method for utilizing the solar energy production hydrogen gas and methanol according to claim 1 is characterized in that: the water vapour that said solar energy collector (12) is produced, supply with earlier the turbine driven set generating, after enter vaporizer (5); The electric energy that generating set produces is calcining furnace (2) heating and calcining calcium iodate by electric furnace; And when no sunlight,, keep photolysis for the electric light source power supply that high brightness LED is formed.
5. the method for utilizing the solar energy production hydrogen gas and methanol according to claim 1 is characterized in that: said calcining furnace (2) is with the homemade combustion of hydrogen heating of this law.
6. the method for utilizing the solar energy production hydrogen gas and methanol according to claim 1, it is characterized in that: the used carbonic acid gas of said production methyl alcohol, be to make absorption agent with highly basic and aqua calcis in the absorption tower, absorb carbon dioxide in air, decomposition obtains carbonic acid gas again; Its chemical equation:
Na (OH)+CO
2=Na
2CO
3Or K (OH)+CO
2=K
2CO
3
Ca (OH)
2+ Na
2CO
3=CaCO
3↓+Na (OH) or
Ca(OH)
2+K2CO
3＝CaCO
3↓+K(OH)
7. the photodissociation device that the method for utilizing the solar energy production hydrogen gas and methanol according to claim 1 is used, it is characterized in that: it is that a upper surface is transparent glass, has the plumbous net parallel with transparent glass, bottom and periphery to be that the plate container of anticorrosive housing, its upside have upper outlet, downside that fluid inlet and outlet are down arranged in it; Claim photolytic cell (7) again.
8. the photodissociation device that the method for utilizing the solar energy production hydrogen gas and methanol according to claim 7 is used is characterized in that: the mesh wire diameter 〉=0.1mm of said plumbous net, and twine spacing 〉=0.3mm, the number of plies of plumbous net is 1～3 layer.
9. the photodissociation device that the method for utilizing the solar energy production hydrogen gas and methanol according to claim 7 is used, it is characterized in that: it and solar energy collector (12) are combined as a whole, promptly photolytic cell at last, solar energy collector (12) down; The base plate of photolytic cell is a transparent glass, and is parallel with the transparent glass of heat collector (12) top panel, and has at interval.
10. the photodissociation device that the method for utilizing the solar energy production hydrogen gas and methanol according to claim 1 is used, it is characterized in that: it is made up of the row's circle cross section Glass tubing that is planar alignment, be laid with plumbous net in the Glass tubing, the upper/lower terminal of each Glass tubing is connected with drain pipe, liquid-inlet pipe respectively, fluid inlet, outlet are down arranged on the liquid-inlet pipe, upper outlet is arranged on the drain pipe.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830443A (en) * | 2010-04-14 | 2010-09-15 | 清华大学 | Process for purifying sulfuric acid phase and hydriodic acid phase in iodine-sulfur cycle |
| CN101423190B (en) * | 2007-10-31 | 2011-06-29 | 孔庆全 | Method for making hydrogen and oil by using solar |
| CN104193584A (en) * | 2014-08-04 | 2014-12-10 | 广东合即得能源科技有限公司 | Manufacturing process of methanol |
| CN104192797A (en) * | 2014-06-27 | 2014-12-10 | 桂林浩新科技服务有限公司 | Hydrogen production device with self-stirring cage |
| CN106252719A (en) * | 2015-06-12 | 2016-12-21 | 丰田自动车株式会社 | The manufacture method of lithium compositions and the manufacture method of sulfide solid electrolyte material |
| CN113563159A (en) * | 2021-08-27 | 2021-10-29 | 陕西润中清洁能源有限公司 | Process and device for preparing methanol from water gas |
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2005
- 2005-11-09 CN CN200510045058A patent/CN100581989C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423190B (en) * | 2007-10-31 | 2011-06-29 | 孔庆全 | Method for making hydrogen and oil by using solar |
| CN101830443A (en) * | 2010-04-14 | 2010-09-15 | 清华大学 | Process for purifying sulfuric acid phase and hydriodic acid phase in iodine-sulfur cycle |
| CN101830443B (en) * | 2010-04-14 | 2011-06-15 | 清华大学 | Process for purifying sulfuric acid phase and hydriodic acid phase in iodine-sulfur cycle |
| CN104192797A (en) * | 2014-06-27 | 2014-12-10 | 桂林浩新科技服务有限公司 | Hydrogen production device with self-stirring cage |
| CN104192797B (en) * | 2014-06-27 | 2016-05-04 | 丁专生 | A kind of device for producing hydrogen with certainly stirring cage |
| CN104193584A (en) * | 2014-08-04 | 2014-12-10 | 广东合即得能源科技有限公司 | Manufacturing process of methanol |
| CN106252719A (en) * | 2015-06-12 | 2016-12-21 | 丰田自动车株式会社 | The manufacture method of lithium compositions and the manufacture method of sulfide solid electrolyte material |
| CN106252719B (en) * | 2015-06-12 | 2018-03-23 | 丰田自动车株式会社 | The manufacture method of lithium composition and the manufacture method of sulfide solid electrolyte material |
| CN113563159A (en) * | 2021-08-27 | 2021-10-29 | 陕西润中清洁能源有限公司 | Process and device for preparing methanol from water gas |
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