CN101423190B - Method for making hydrogen and oil by using solar - Google Patents

Method for making hydrogen and oil by using solar Download PDF

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CN101423190B
CN101423190B CN2007101140019A CN200710114001A CN101423190B CN 101423190 B CN101423190 B CN 101423190B CN 2007101140019 A CN2007101140019 A CN 2007101140019A CN 200710114001 A CN200710114001 A CN 200710114001A CN 101423190 B CN101423190 B CN 101423190B
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electric field
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CN101423190A (en
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孔庆全
孟海芳
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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
    • 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
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    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention provides a method used for preparing hydrogen and oil by utilizing solar energy, the process flow of which mainly comprises the following procedures: (1) steam is prepared by utilizing the solar energy; (2) salt is prepared and dehydrated; (3) potassium iodate is sintered; (4) oxygen is recovered; (5) potassium iodide solution is hydrolyzed and hydriodic acid is prepared; (6) hydrogen is prepared and iodine is recovered; (7) hydrogen is refined; (8) water is purified; and (9) fuel oil is synthesized and refined by the CO2 conversion and Fischer-Tropsch synthesis process of the H2 prepared in the previous steps and CO2. The hydrolysis of the solutions such as potassium iodide and the like is realized by an electric field decomposer. The device consists of a sealing pipe, two groups of electric field electrodes and a separation plate. The method utilizes the thermal effect and the chemical effect of the sunlight simultaneously, uses the water and CO2 as raw materials to generate hydrogen and fuel oil by chemical reaction, leads the solar energy to be changed into chemical energy which is convenient for use and easy for storage, reduces the cost by at least 30 percent compared with oil produced from coal, provides a new way for solving the energy resource problem, and has huge economic benefits and social benefits.

Description

Utilize the method for solar hydrogen making and oil
Technical field
The present invention relates to sun power utilization and chemical field, particularly a kind of method of utilizing solar hydrogen making and oil that sun power is changed into chemical energy, realization suitability for industrialized production hydrogen and oil fuel.
Background technology
As everyone knows, the world today is owing to energy dilemma, and severe energy problem becomes the outstanding problem that the whole world is paid close attention to day by day, is brought up to unprecedented height by government.The world energy sources utilization has developed into the dangerous phase of the energy by energy dilemma.Conventional energy resources---coal, oil, Sweet natural gas etc. belong to non-renewable energy, and be exhausted day by day.Petroleum resources do not satisfy growing motor vehicle needs at all, and the war of world's contention oil in rapid succession.People produce motor-driven oil with other method, and one of them is exactly " coal becomes oil ".Though can solve the matter of great urgency, but still be to go around in circles in conventional energy resources, meaning is limited.Sun power is the green regenerating energy, and is inexhaustible, without cease with it, and safely cleaning is pollution-free; Disadvantage is not to be easy for Motor vehicles.Therefore utilize sun power system oil huge as the breach meaning of energy utilization.
China's " Gazette of Patent for Invention " disclosed the patent application that title is " method of utilizing the solar energy production hydrogen gas and methanol ", its application number: 200510045058.9, publication number: CN1962413A on 05 16th, 2007.Its objective is: 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.Its master operation 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; 9. synthesizing methanol.But there is following shortcoming: the 1. calcining temperature height of calcium iodate, need 540 ℃ of decomposition, power consumption is high, efficient is low.2. the calcium iodide hydrolysis is heated with combustion of hydrogen, and is wasteful.3. make CO 2With NaOH and Ca (OH) 2Absorb airborne CO 2After, need calcining CaCO 3, power consumption is high, efficient is low.4. can not make oil fuel, as gasoline and diesel oil etc., be directly used in Motor vehicles.
Summary of the invention
For the problem that the part operation that solves existing solar energy production hydrogen and methanol process needs high-temperature calcination, the big efficient of power consumption is low and can not be directly used in motor vehicle as oil fuel, the invention provides a kind of method of utilizing solar hydrogen making and oil, the mode that it takes sun power to be transformed into chemical energy solves the approach that stores sun power, utilizes solar industry production hydrogen and oil fuel.
The technical solution adopted for the present invention to solve the technical problems is:
Utilize the method for solar hydrogen making and oil, comprise following operation:
1. utilize sun power system water vapour: produce water vapour with solar energy collector, send the vapour case to store; From the water vapour of vapour case output, enter Heating K I and KIO by vaporizer I middle part inlet mouth 3Be condensed into water behind the solution, flow out, return solar energy collector from vaporizer I bottom water outlet.
2. the preparation of salt and dehydration: the unloading phase of production, in the protection against corrosion salt manufacturing tube of sealing, add I 2, KOH, and add distilled water by water tank, stir with stirrer, reaction at normal temperatures generates KI, generates KIO simultaneously 3After the reaction, KI and KIO 3Solution advances liquid feeding tank.Its reaction equation:
6KOH+3I 2＝5KI+KIO 3+3H 2O
The unloading phase after, from the intermediate product of flow process four processes, enter the salt manufacturing tube and continue to keep and generate KI and KIO 3Reaction; They are: the KI of photolytic cell 3Solution or KI 3And KIO 3The remaining liq of solution, decomposing H I, electricity divide KOH solution that device produces, by the distilled water of water tank supply.Wherein, KI 3Solution is the I that generates with KI solution decomposing H I 2Generate; KI 3And KIO 3Solution is with KI and KIO 3The I that solution absorption decomposing H I generates 2Generate.
By effusive KI of liquid case and KIO 3After solution is sent into the condenser preheating, enter vaporizer I and heat by water vapor; The effusive suspension of vaporizer I bottom liquid outlet separates with the protection against corrosion whizzer; Isolated KI and KIO 3Solid.
3. the calcining of Potassium Iodate: with isolated KI of whizzer and KIO 3Solid is sent in the corrosion resistant calcining furnace, through 100 ℃～250 ℃ temperature calcinings, generates KI and O 2Its reaction equation:
Figure S2007101140019D00021
Sending into salt tube after KI comes out of the stove is mixed into KI solution with the liquid water that is flowed out entering salt tube by vaporizer II, enters the electric field splitter; The O that calcining generates 2Reclaim.
4. the recovery of oxygen: the O that emits by calcining furnace 2, entering from II bottom, absorption tower, absorption agent KOH solution is entered by II top, absorption tower, absorbs O 2Middle remaining I 2Behind the gas, flow out the O of purification by II bottom, absorption tower liquid outlet 2Emit by air outlet, II top, absorption tower, enter O 2Gas tank stores.
5. the preparation of the hydrolysis of liquor kalii iodide and hydroiodic acid HI: this operation is finished in the electric field splitter.
The electric field splitter, be called for short electricity and divide device, constitute by sealed tube, the two pairs of electric field electrodes, spacer plate etc.A liquid inlet I, inlet II are respectively established in vertical two ends of sealed tube; Two pairs of electric field electrodes: the anodal II of the anodal I of pair of electrodes, negative pole I and another counter electrode, negative pole II lay respectively at the vertical both sides external of sealed tube, longitudinally every limit is a pair of.Two pairs the electric field electrode pole plate is parallel with the sealed tube centerline direction, polarity is opposite, forms two opposite ion split movement districts of direction of an electric field in sealed tube: A district, B district; Spacer plate is between A district, B district, and is vertical with direction of an electric field, and the middle part in the sealed tube is divided into two ion mixing zones: C district, D district; C district, D district have liquid exit I, outlet II separately respectively.
Divide an inlet I of device to enter from the KI solution of changing the salt tube by electricity; Simultaneously, distilled water divides another relative inlet II of device to enter from electricity; Divide under positive and negative two effect of electric field of device at electricity to be hydrolyzed, generate HI solution and KOH solution.Its reaction equation:
Figure S2007101140019D00022
Figure S2007101140019D00023
K ++OH -＝KOH I -+H +＝HI
The KOH solution that generates divides the outlet I of device to flow out from electricity, enters the salt manufacturing tube; The HI solution that generates divides device outlet II to flow out from electricity, enters photolytic cell.
6. the recovery of the preparation of hydrogen and iodine: divide the HI solution of device from electricity, enter,, advance photodissociation under the sunlight of photolytic cell in transmission again simultaneously, generate H with the plumbous or silver reaction in the photolytic cell by photolytic cell bottom fluid inlet 2And I 2H 2Emitted by the outlet of photolytic cell top, water is emitted by lower part outlet.Its reaction equation:
Pb+2HI＝PbI 2+H 2↑ 2Ag+2HI＝2AgI+H 2↑
Figure S2007101140019D00031
Figure S2007101140019D00032
After gas and liquid have been put in the outlet of photolytic cell, make from the KI solution of changing the salt tube, enter the I that the dissolving photodissociation generates from photolytic cell bottom fluid inlet 2And the KI that generates 3Solution flows out from the top outlet of photolytic cell, enters the salt manufacturing tube.Its reaction equation:
KI+I 2＝KI 3
Perhaps, make KI and KIO from the liquid case 3Solution enters the I that the dissolving photodissociation generates from photolytic cell bottom fluid inlet 2And the KI that generates 3And KIO 3Solution flows out from the top outlet of photolytic cell, enters the salt manufacturing tube; At this moment, only be fit to the reaction of silver with HI solution.
Photodissociation HI solution and recovery I 2Two steps in the fluid inlet of photolytic cell, outlet up and down, are to control automatically or Artificial Control by switch.
7. hydrogen is refining: H 2After emitting from photolytic cell, enter by I bottom, absorption tower; Absorption agent KOH solution is entered by I top, absorption tower, absorbs H 2Middle remaining HI, I 2After, discharge by absorption tower I bottom; H 2Emit by I top, absorption tower, enter H 2Gas tank stores.
8. water purification: the water of removing mechanical impurity is entered by vaporizer II top water-in, and the water vapour heating of air outlet, origin flash-pot I top becomes water vapour, emits from air outlet, vaporizer II top, enters to be KI and KIO 3In the condenser of solution preheating, enter water tank through being condensed into distilled water, the distilled water of water tank is sent into the salt manufacturing tube again.Impurity in the water is discharged by vaporizer II bottom water outlet.
After said process started, the intermediate product that returns the salt manufacturing tube continued reaction and photodissociation hydrogen manufacturing under illumination.After producing hydrogen, also can continue subsequent processing:
9. oil is synthetic and refining: the H that produces with above-mentioned operation 2Be raw material, with CO 2Mix, synthesize, produce oil fuel by carbonic acid gas conversion, Fischer-Tropsch (F-T).The total chemical equation and the operation of synthetic oil:
Figure S2007101140019D00033
1) produces CO 2
2) carbonic acid gas conversion: with the H that produces 2And CO 2Be raw material,, produce F-T synthetic needed qualified " synthetic gas " by the carbonic acid gas conversion process, that is: its volume fraction be 80～85%, n (H 2The ratio of)/n (CO) is no less than 0.5 H 2With the CO mixture; Carbonic acid gas transformationreation formula is:
Figure S2007101140019D00034
This is reflected under the effect of catalyzer and carries out in synthetic tower, is the reaction of reversible, heat absorption, constancy of volume; Select the proper handling condition: the upper limit of extract operation temperature increases transformation efficiency, discharges after water vapour is removed in cooling generating gas, recirculation enters system and proceeds the carbonic acid gas conversion, impel balance to move right, adjust the composition of gasification product, reach the synthetic requirement of F-T with qualified " synthetic gas ";
3) F-T is synthetic: qualified " synthetic gas " sent into reactor carries out F-T and synthesize, under catalyst action by H 2Generate aliphatic hydrocarbon with CO.Synthetic at this said F-T, comprise improved F-T synthesis method, be the MFT synthesis method.F-T synthesizes the primitive reaction formula:
Figure S2007101140019D00041
The F-T synthetic product is produced finished product oil fuel through product separation, product purification.
The technical solution adopted for the present invention to solve the technical problems can also be:
In the method for utilizing solar hydrogen making and oil, the Potassium Iodate calcination process is with 100 ℃～250 ℃ water vapour Heating K I and the KIO of vapour case output in calcining furnace 3Solid generates KI and O 2
In the recovery of iodine, use KI and KIO 3Solution dissolving I 2The time, with the silver-plated wire netting of hydroiodic acid HI reaction.
The CO that in the synthetic and refining step of oil, uses 2, be in the absorption tower, to make absorption agent with strong base solution, absorb airborne CO 2Generate subcarbonate, electricity consumption divides device decomposition subcarbonate to produce then.
In the synthetic and refining step of oil, the catalyzer of using in the carbonic acid gas conversion is with Fe 2O 3For main body, with Cr 2O 3Be the multicomponent Fe-Cr series catalyzer of main additive, temperature is 350～550 ℃, and pressure is 0.7～3.0Mpa; The catalyzer of using during F-T is synthetic is a Fe-series catalyst, and synthesis temperature is 220～340 ℃, and pressure is 0.7～3.0Mpa, requires (the CO+H in the unstripped gas 2) volume fraction is 80～85%, the utilization in the unstripped gas than, be n (H 2)/n (CO) ratio is 0.5～3, and adopting recycle ratio is 2～3.
The invention has the beneficial effects as follows:
1. Potassium Iodate calcining and decomposing temperature is 100 ℃～250 ℃, and far below 540 ℃ of decomposition temperatures of calcium iodate, it is low to consume energy, and can use the water vapour thermal degradation of solar energy collector.2. potassiumiodide hydrolysis electric field splitter, technology is simple and convenient.3. make CO 2With electric field splitter hydrolysis subcarbonate, simple and convenient.4. the carbonic acid gas conversion---the reversed reaction of the carbon monodixe conversion in the ammonia synthesis technology, with the 3rd step of the Fischer-Tropsch method technology of the non-direct liquefaction of coal---Fischer-Tropsch is synthetic to combine, and makes with H 2And CO 2For raw material production oil fuel becomes possibility.5. utilize sun power with chemical process, utilize the heat and the chemical effect of sun power simultaneously, with water and CO 2For raw material through chemical reaction produces oil, solve the vehicle fuel oil problem.Reduce at least 30% than the cost that produces oil with coal, provide new way for solving the energy, economic benefit and social benefit are huge.
Description of drawings
Fig. 1 is the process flow sheet that the present invention utilizes solar hydrogen making.
Fig. 2 is the structural representation front view of the electric field splitter used of the present invention.
Fig. 3 is that G among Fig. 2 is to view.
Fig. 4 is that F among Fig. 2 is to one of view.
Fig. 5 is that F among Fig. 2 is to two of view.
Fig. 6 is Fischer-Tropsch synthesis process basic procedure and product block diagram.
Fig. 7 is an Arge fixed bed Fischer-Tropsch synthesis process schema.
Fig. 8 is the ultimate principle FB(flow block) of MFT method.
Among the figure: 1-salt manufacturing tube, the 2-calcining furnace, the 3-electricity divides device, the 4-condenser, the 5-vaporizer, the 6-vaporizer, the 7-photolytic cell, the 8-absorption tower, the 9-absorption tower, 10-ization salt tube, the 11-moisture trap, the 12-heat collector, 13-vapour case, the 14-water tank, 15-liquid case, the 16-gas tank, the 301-sealed tube, 302-electric field positive pole, 303-electric field negative pole, 304-electric field positive pole, 305-electric field negative pole, the 306-spacer plate, the 601-reactor, the 602-wax separator, the 603-heat exchanger, the 604-watercooler, the 605-watercooler, the 606-separator; E I1-liquid inlet, E I2-liquid inlet, E 01-liquid exit, E 02-liquid exit; Wax-wax, the hot condensate of HCR-, CCR-cryocondensation thing, CR-condensate, 0-Oxd-organic oxygen compound, VP-water vapour, WS-feedwater, CW-water coolant; Vaporizer I, II, promptly vaporizer 5,6; Absorption tower I, II are absorption tower 8,9; Liquid inlet I, II, i.e. liquid inlet E I1, E I2Liquid exit I, II, i.e. liquid exit E 01, E 02Electric field anodal I, II, promptly the electric field positive pole 302,304; Electric field negative pole I, II, promptly the electric field negative pole 303,305.
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
Global schema: utilize sun power that water is resolved into hydrogen and oxygen; And then with hydrogen and carbonic acid gas synthetic oil.Said oil is the abbreviation of oil fuel such as gasoline, diesel oil.
Figure S2007101140019D00051
Embodiment 1: utilize solar energy production hydrogen
The one, ultimate principle: water is resolved into hydrogen and oxygen, mainly realize by four chemical reaction processes.
1) manufacturing of salt: 6KOH+3I 2=5KI+KIO 3↓+3H 2O
2) cracking of water:
Figure S2007101140019D00053
3) discharge hydrogen:
Figure S2007101140019D00054
4) discharge oxygen:
The 2nd, produces the master operation of hydrogen:
Comprise: 1. utilize sun power to prepare water vapour; 2. the preparation of salt and dehydration; 3. the calcining of Potassium Iodate; 4. the recovery of oxygen; 5. the preparation of the hydrolysis of liquor kalii iodide and hydroiodic acid HI; 6. the recovery of the preparation of hydrogen and iodine; 7. hydrogen is refining; 8. water purification.
The 3rd. produce the technical process of hydrogen and the explanation of each master operation:
Fig. 1 illustrates operation and the flow process that the present invention utilizes solar energy production hydrogen.
1. utilize sun power to prepare water vapour:
Heat the generation water vapour of purifying waste water with solar energy collector 12, concentrate and send into 13 storages of vapour case.Water vapour from the output of vapour case 13 air outlets enters Heating K I and KIO by pipeline by calcining furnace 2 bottom inlet mouths 3Flow out from air outlet, calcining furnace 2 top behind the solid, enter Heating K I and KIO by vaporizer 5 middle part inlet mouths by pipeline 3Form with water of condensation behind the solution flows out from vaporizer 5 bottom water outlets, after the low-temperature end by vapour case 13, is returned in it by heat collector 12 lower water inlets.
Solar energy collector 12 adopts plate solar heater.Because KIO 3Solid decomposes greater than 100 ℃ of temperature the time, and temperature is relatively low, but than hot water temperature's height of solar water heater output.
Because of needs are produced middle temperature steam, so the solar energy collector cover adopts layer glass, spacing 10mm, and with low iron glass.Cartridge the conduct heat good circle or the aluminium of flat cross section, the surface is coated with unglazed chalkboard paint.Working-medium water adopts distilled water.Inside vacuumizes, and the outer container stopping property will be got well and the filling heat-insulating material.
2. the preparation of salt and dehydration:
1) preparation of salt potassiumiodide and Potassium Iodate:
The unloading phase of production, in the etch-proof salt manufacturing tube 1 of sealing, add I 2, KOH, and add distilled water by water tank 14, stir with stirrer, reaction at normal temperatures generates KI, generates the less KIO of solubleness simultaneously 3KI and KIO that reaction generates 3Solution advances liquid feeding tank 15.Its reaction equation:
6KOH+3I 2＝5KI+KIO 3+3H 2O
The unloading phase after, enter salt manufacturing tube 1 from the intermediate product of flow process four processes, continue to keep generating KI and KIO 3Reaction:
A. by the distilled water of water tank 14 to 1 supply of salt manufacturing tube.
B. in photolytic cell 7, decompose the reaction of potassiumiodide and carry out the remaining liq that the back emits from photolytic cell 7.
C. from the I of photolytic cell 7 2, promptly use KI+KIO 3Solution absorption I 2The KI that forms 3+ KIO 3Solution.
D. the KOH solution of producing from electric field splitter 3.
The purpose of preparation salt KI is to make KI solution divide at electricity that hydrolysis generates HI in the electric field of device 3.Preparation salt KIO 3Purpose be oxygen to be composed to store away to decompose produce oxygen, finish the circulation of water of decomposition.
Highly basic and halogen reaction generate two kinds of salt and belong to the chemical reaction that easily carries out, and can react and react completely under the normal temperature.Because two kinds of salt are all water-soluble, only KIO 3Solubleness is less, so difficulty is separated the two.
Easily oxidized in air because of iodide ion, must in closed container, prepare.Salt manufacturing tube 1 is used anticorrosion container.The KI strength of solution that makes should reach 2mol.dm -3More than, otherwise carry out too slow with afterreaction.
2) dehydration of salt potassiumiodide and Potassium Iodate:
KI and KIO in the generation of salt manufacturing tube 1 internal reaction 3Two kinds of solution enter condenser 4 simultaneously, after enter vaporizer 5, by the steam-heated cal(l)andria of coming out from calcining furnace 2; Water in the solution generates water vapour and discharges from the top exit of vaporizer 5, enters vaporizer 6 as heating steam.From the effusive suspension of vaporizer 5 bottom liquid outlets, separate with etch-proof whizzer.KI after the separation and KIO 3Solid is sent into calcining furnace 2; The steam that comes out from calcining furnace 2 is cooled to water and returns heat collector 12 through 13 preheatings of vapour case.
3. the calcining of Potassium Iodate:
With vaporizer 5 isolated KI and KIO 3Solid is sent in the corrosion resistant calcining furnace 2, and the temperature calcining through 100 ℃～250 ℃ generates KI and O 2Its reaction equation:
Figure S2007101140019D00071
Calcining KIO 3Purpose mainly be to emit O 2, obtain KI simultaneously.Calcining KIO 3Adopt the rotary calcining stove.Because I 2Be corrosive, calcining furnace stove plate adopts stainless steel.KI and KIO 3Solid can transport with conveyor.Because calcining KIO 3Temperature be not very high, so can adopt water vapour heating to replace the fuel calcining.Used water vapour is provided by solar energy collector, enters calcining furnace 2 from vapour case 13 air outlets, Heating K I and KIO 3Behind the solid, discharge and enter vaporizer 5.
The KI evolution salt tube 10 that calcining back generates is mixed into KI solution with liquid water by vaporizer 6 entering salt tubes 10 and advances electricity branch device 3.The O that calcining generates 2Enter O 2Recovery process.
4. the recovery of oxygen:
The O that emits by calcining furnace 2 air outlets 2, 9 bottom inlet mouths enter from the absorption tower, and absorption agent KOH solution is entered by absorption tower 9 top fluid inlets, absorbs O in absorption tower 9 2Middle remaining I 2Behind the gas, flow out the O of purification by absorption tower 9 bottom liquid outlets 2Emit by air outlet, 9 top, absorption tower, after dehumidifying, enter O 2Gas tank.Turbulent contact absorber is adopted on the absorption tower, and absorption agent is better with rare KOH solution, mainly is to reclaim remaining iodine gas.The dehumidifying back is stored in gas tank as product oxygen.
5. the preparation of the hydrolysis of liquor kalii iodide and hydroiodic acid HI:
The purpose of preparation hydroiodic acid HI is to react releasing hydrogen gas with it with silver or lead.Hydroiodic acid HI is produced by the potassiumiodide hydrolysis.The total reaction equation of KI hydrolysis:
KI+H 2O＝KOH+HI
The KI salt that to be highly basic generate with acid can not direct hydrolysis, must use additive method.The present invention realizes that the hydrolysis of KI carries out in electric field splitter 3.The reaction equation of KI hydrolysis:
Figure S2007101140019D00072
K ++OH -＝KOH I -+H +＝HI
Electric field splitter 3, abbreviation electricity divide device, are to move to electric field negative pole bending skew according to particle positively charged in electric field, and the principle that electronegative particle motion is offset to anodal bending is made.
Divide the structure of device 3 at electricity shown in Fig. 2～5.Constitute by sealed tube 301, two pairs of electric field electrodes, spacer plates 306.Respectively there is a liquid inlet E at sealed tube 301 vertical two ends I1, E I2The positive pole 302 of a pair of electric field electrode, negative pole 303 are positioned at sealed tube 301 vertical both sides external with another positive pole 304 to electric field electrode, negative pole 305, and longitudinally every limit is a pair of; Two pairs the electric field electrode pole plate is parallel with sealed tube 301 medullary rays, polarity is opposite, forms two opposite ion split movement districts of direction of an electric field in sealed tube 301: A district, B district; Spacer plate 306 is between A district, B district, and is vertical with direction of an electric field, the middle part in the sealed tube 301 is divided into two ion mixing zones: C district, D district; There is liquid exit E in the C district 01, there is liquid exit E in the D district 02
The optional circle in the transverse section of sealed tube 301, as Fig. 4, or rectangle, as Fig. 5.Material adopts anticorrosives such as glass, plastics, Tao Ci.Electricity divides two liquid inlet E of device 3 I1, E I2With the flat shower nozzle of chewing serves as preferred; Flat width≤the 1mm that chews of shower nozzle, the flat length direction of chewing is vertical with direction of an electric field.Make solution and water inject the height of jet width≤1mm, height of jet≤positive/negative plate with the jet of long narrow bar shaped section.
Electric field adopts uniform electric field, and strength of electric field generally is no more than air breakdown strength of electric field: 1 * 10 6V/m.The field intensity of liquor kalii iodide fluerics is generally hanged down an order of magnitude than the field intensity in water jet district.Because water is weak electrolyte, must improve field intensity.Two kinds of electric charges of C, D ion mixing zone only otherwise string gets final product mutually.
Working process: the KI solution jet is by E I1Mouth enters the A district, is K +With I -The motion separate zones, K +, I -Motion between electric field anodal 302 and negative pole 303, K +To negative pole 303 bendings, I -To anodal 302 bendings, then, K +Enter the C district, I -Enter the D district.Simultaneously, water jet is by E I2Mouth enters the B district, is H 3O +With OH -The motion separate zones, H 3O +, OH -Motion between electric field anodal 304 and negative pole 305, respectively to negative pole 305, anodal 304 bendings, then, OH -Enter the C district, H 3O +Enter the D district.Enter the K in ion mixing zone, C district +And OH -Mix generating KOH solution, by outlet E 01Discharge.Enter the I in ion mixing zone, D district -And H 3O +Mix generating HI solution, by outlet E 01Discharge.
In the whole production flow process, from the KI solution of changing salt tube 10 by inlet E I1Enter the A district that electricity divides device 3; From water tank 14 effusive distilled water by the inlet E I2Enter the B district that electricity divides device 3.The KOH solution that hydrolysis generates divides the outlet E of device 3 from electricity 01Flow out, enter salt manufacturing tube 1; The HI solution that generates divides device 3 another outlet E from electricity 02Flow out, enter photolytic cell 7.
6. the recovery of the preparation of hydrogen and iodine:
1) preparation of hydrogen: divide HI solution that device 3 comes out to enter in it by electricity,, under transmission enters the sunlight of photolytic cell 7, decompose again simultaneously, generate H with the plumbous or silver reaction in the photolytic cell 7 by the fluid inlet of photolytic cell 7 bottoms 2And I 2H 2Emitted by the outlet of photolytic cell 7 tops, enter absorption tower 8, water is emitted by its underpart outlet, enters salt manufacturing tube 1.Photodissociation HI makes H 2Reaction equation:
P b+2HI＝P bI 2+H 2↑ 2A g+2HI＝2A gI+H 2↑
Figure S2007101140019D00081
Figure S2007101140019D00082
2) recovery of iodine:
After gas and liquid have been put in the outlet of photolytic cell 7, make KI and KIO from liquid case 15 3Solution enters from the bottom fluid inlet of photolytic cell 7; The iodine that KI solution dissolving photodissociation generates generates potassium triiodide, KI 3And KIO 3Solution flows out from the top outlet of photolytic cell 7, enters salt manufacturing tube 1.Its reaction equation:
KI+I 2＝KI 3
Photodissociation hydroiodic acid HI system H 2With reclaim two steps of iodine, in the fluid inlet of photolytic cell 7, outlet up and down, be to be magnetic valve by switch, by programmable controller control automatically, also can Artificial Control.
Preparation hydrogen carries out in photolytic cell 7.If direct pyrolysis HI gas system H 2Need temperature higher; If direct photodissociation HI gas system H 2, required light wavelength is in ultraviolet ray range, so the indirect method of taking, that is: employing A gOr P bProduce H with the HI solution reaction 2, use photolysis A again gI or P bI 2Because A gBe precious metal, can preferentially adopt P bP bI 2The photodissociation maximum wavelength is 494.9 nanometers, in green range.Because P bWith HI solution reaction, P bThe surface generates the P that is difficult for reacting bI 2Protective film, in addition, it is to carry out at material surface that sunlight decomposes, so for increasing P bSurface-area adopts P bNet.P bThe net mesh wire diameter selects 0.1mm, and spacing is selected 0.3mm, is easy to printing opacity, passes through liquid.
Photolytic cell 7 structures: for upper surface is the plate container of transparent glass, it receives the optional circle in transverse section or the rectangle of illumination, interior dress P b1～3 layer on net.It is tilting that photolytic cell 7 is met light by stent support, and downside is established fluid inlet, outlet down, and upside is established upper outlet.
Photolytic cell 7 can be made up of the circle cross section Glass tubing of planar alignment, and along being subjected to the light bottom surface to lay plumbous net, each Glass tubing upper/lower terminal is communicated with the liquid inlet and outlet pipe respectively in Glass tubing.Structure likelihood blank pipe water-heater.
Photolytic cell can be integrated with solar energy collector and improve the sunlight utilization ratio, and promptly photolytic cell is descending at last, heat collector, and the base plate of photolytic cell is a transparent glass, parallel with collector panels glass and have insulated room every.
Reclaim the method for iodine: because I 2Be soluble in iodide solution, so adopt KI solution to dissolve I 2Recovery method has two kinds:
A. if adopt pure KI solution to dissolve I 2, then after photolytic cell 7 has been put gas and liquid,, use KI injecting photolytic cell 7 from the KI solution of changing salt tube 10 2Solution dissolving I 2, with KI 3The solution form is emitted from photolytic cell 7, enters salt manufacturing tube 1.Its shortcoming is the capacity that increases vaporizer 5 and calcining furnace 2, and complex procedures, its advantage are to adopt inexpensive plumbous net.
B. if adopt KI and KIO 3Solution dissolves I 2, make the photolytic cell cisco unity malfunction owing to the lead ion in iodate ion and the photolytic cell 7 generates undissolved lead iodate easily.Must adopt A gNet could works better.Its shortcoming is A gBe precious metal, advantage is the capacity that need not increase vaporizer 5 and calcining furnace 2, after photolytic cell 7 has been put gas and liquid, KI and the KIO from liquid case 15 3Solution injects the I that photolytic cell 7 usefulness KI solution dissolving photodissociation generates 2, with KI 3And KIO 3The solution form is emitted from photolytic cell 7, enters salt manufacturing tube 1.In order to overcome the expensive shortcoming of silver-colored valency, adopt silver-plated wire netting, its parameter is identical with plumbous net.Another advantage that adopts silver-plated wire netting is that to have overcome lead be the drawback of toxic substance.This example serves as preferred with second kind of method that reclaims iodine, promptly adopts silver-plated wire netting.
7. hydrogen is refining:
After hydrogen is emitted from photolytic cell 7, enter in the tower by the bottom inlet mouth on absorption tower 8; The absorption agent potassium hydroxide solution is entered by absorption tower 8 top fluid inlets, in absorption tower 8, absorb hydrogen iodide remaining in the hydrogen, iodine gas after, flow out by absorption tower 8 bottom liquid outlets.Hydrogen is emitted by air outlet, 8 top, absorption tower, by moisture trap 11 dehumidifying, enters hydrogen gas tank 16.
The H that comes out from photolytic cell 7 2Impure, mainly be HI, I 2Gas and water vapour.Because HI, I 2Easy and KOH reacts, so make absorption agent with KOH solution.Turbulent contact absorber is generally selected on absorption tower 8 for use.Be stored in the gas tank 16 stand-by by the purified hydrogen after removal of impurities, the dehumidifying.
8. water purification:
Water is to produce H 2Basic raw material, must use Purified Water.Sulfur acid salt pair system is harmful in the water, and sulfate radical and lead ion generate the difficult lead sulfate that decomposes easy fouling.This flow process adopts distillation legal system Purified Water:
1) with filtering settling process, removes the mechanical impurity in anhydrating.
2) vaporizer becomes water vapour to water: the water of removing mechanical impurity is entered by vaporizer 6 top water-ins makes water coolant in it, becomes water vapour and emitted by the air outlet at vaporizer 6 tops when cooling comes the middle temperature steam of flash-pot 5.Impurity in the water coolant is discharged by vaporizer 6 bottom water outlets.
3) water vapour of emitting from air outlet, vaporizer 6 top is condensed into water by condenser 4, enters water tank 14, and is stand-by as Purified Water.Vaporizer 6 adopts etch-proof standard pan.
In order to keep photolysis when the no sunlight, whole flow process uninterruptedly to be carried out, can make light source with high brightness LED.Strengthen capacity, the increase storage vapour amount of solar energy collector and vapour case simultaneously.
Embodiment 2: utilize solar energy production oil
General planning: the H that utilizes solar energy production 2With CO 2Pass through CO 2Conversion, the synthetic oil of producing of Fischer-Tropsch.
The one, utilizes the technical process of solar energy production oil:
1. utilize sun power system H 22. utilize highly basic to absorb airborne CO 2, hydrolysis system CO 23. with H 2And CO 2Mix, by the carbonic acid gas transformationreation, produce qualified " synthetic gas "; 4. synthesize by Fischer-Tropsch, and synthetic product separation, purification are obtained oil fuel.Total chemical equation of synthetic oil:
Figure S2007101140019D00101
The master operation that the 2nd, produces oil:
1. the production of hydrogen: utilize solar energy production hydrogen by embodiment 1 described operation.
2. the production of carbonic acid gas: utilize strong base solution to make absorption agent, in the standard absorption tower, absorb airborne CO 2, generate subcarbonate, decompose subcarbonate then and make CO 2, make unstripped gas through purification.
The present invention decomposes subcarbonate system CO 2Method, be that electricity consumption divides device, realizes by positive and negative two electric field actions.Make CO 2Make unstripped gas through purification.The electricity that uses divides identical that device and hydrolysis KI use.Absorption agent can adopt different alkali.For example: make absorption agent with NaOH or KOH, its reaction equation is:
NaOH+CO 2=NaHCO 3Or KOH+CO 2=KHCO 3
Figure S2007101140019D00102
Or
Figure S2007101140019D00103
H 2CO 3＝H 2O+CO 2↑
Working process: with NaHCO 3Solution is example.NaHCO 3Solution is divided the E of device 3 by electricity I1Mouth enters the A district, under electric field action, and Na +To 303 bendings of electric field negative pole, enter C district, HCO 3 -To anodal 302 bendings of electric field, enter the D district.Simultaneously, water is divided the E of device 3 by electricity I2Mouth enters the B district, under electric field action, and OH -Ion to anodal 304 bendings of electric field, enter C district, H 3O +Ion to 305 bendings of electric field negative pole, enter the D district.Enter the Na in C district +And OH -Be combined into NaOH solution, by outlet E O1Discharge.Enter the HCO in D district 3 -And H 3O +Be combined into H 2CO 3Solution is by outlet E O2Discharge.The H that discharges 2CO 3Solution is because CO 2Solubleness in water is little, generates CO immediately 2, after collection and purification, be stored in CO 2Stand-by in the gas tank.
3. oil is synthetic and refining: total chemical equation of synthetic oil:
The different chemical equation of correspondence when synthesizing different hydrocarbon.
With H 2And CO 2For raw material production oil adopts Fischer-Tropsch (F-T) synthetic.In Fischer-Tropsch was synthetic, required " synthetic gas " was H 2Mixture with CO.Therefore must at first use H 2And CO 2Produce qualified " synthetic gas ".Produce synthetic gas and adopt the carbonic acid gas conversion.
1) producing of synthetic gas:
Because the hydrogen that synthetic oil needs and the volume fraction of carbon monoxide mixtures are 80-85%, n (H 2The ratio of)/n (CO) is no less than 0.5, so adjust the composition of unstripped gas by this requirement.
A. carbonic acid gas conversion process: so-called carbonic acid gas conversion is to make CO 2With H 2In the presence of suitable temperature, pressure and catalyzer, react, generate CO with volume.The reaction formula of carbonic acid gas conversion:
Figure S2007101140019D00112
This is reflected in the synthetic tower and carries out, and has the characteristics of reversible, heat absorption, constancy of volume, according to these characteristics, can select suitable operational condition, impels balance to move right.
Transformationreation must have the existence of catalyzer.Service temperature must remain within the activity of such catalysts temperature range.Though the change as for pressure does not have influence to balance, pressurize can make CO, H 2Collision opportunity between the O molecule increases, and reaction is quickened, and reduces catalyst levels, thereby improves throughput.For example working pressure is increased to 2.0MPa from normal pressure, throughput can increase 3.9 times.
B. the selection of technical process:
Adopt the medium temperature transformation process in the carbonic acid gas conversion process.The general fixed-bed reactor that use in the production.The hts catalyst of widespread use is with Fe 2O 3Be main body, with Cr 2O 3Multicomponent Fe-Cr series catalyzer for main additive.Homemade its model of Fe-Cr series hts catalyst is B104, B106, B109 etc.Because the carbonic acid gas transformationreation is thermo-negative reaction, improves temperature and can increase transformation efficiency, so the upper limit of 350-550 ℃ of extract operation temperature.Because pressure is to the almost not influence of the balance of transformationreation, but from the kinetics angle analysis, pressurization can improve speed of response because transformation catalyst add depress higher than activity under the normal pressure, so extract operation pressure 0.7-3.0Mpa.If temperature of reaction is 550 ℃, (CO+H in the synthetic gas 2) volume fraction is 80%, H in the reaction gas then 2/ CO 2Ratio is 2, n (H in the synthetic gas 2)/n (CO) ratio is 3.If n (H in the synthetic gas 2)/n (CO) ratio is less than 3, then must improve temperature of reaction or discharges after water vapour is removed in cooling generating gas, and recirculation enters system, proceeds the carbonic acid gas conversion.After the carbonic acid gas conversion, removing water vapour through cooling becomes qualified synthetic gas.Synthetic gas enters the Fischer-Tropsch synthesis procedure.
2) Fischer-Tropsch is synthetic:
Nineteen twenty-three, F.Fischer and H.Tropsch CO and H 2Synthetic gas is synthesizing aliphatic hydrocarbon on the Fe-series catalyst under normal pressure, be fischer-tropsch (F-T) synthesis method afterwards.Its flow process and product are as shown in Figure 6.
A. Fischer-Tropsch composition principle:
A. Fischer-Tropsch synthesizes primitive reaction: be to add H by CO 2Generate aliphatic hydrocarbon.Its chemical equation:
Figure S2007101140019D00121
The industrial iron catalyst of using.Fischer-Tropsch synthetic significant process parameter except catalyst property, also has the n (H of temperature, pressure, synthetic gas 2)/n (CO) ratio, recycle ratio etc.
B. catalyzer: the catalyzer of used for Fischer-Tropsch synthesis mainly contains iron, cobalt, nickel, ruthenium etc., has only iron catalyst to be used for industrial production at present.The optimum reaction condition of iron catalyst is a temperature T: 200～350 ℃, and pressure P: 1～3MPa.Active well catalyzer is pressed into 220～240 ℃ of temperature of reaction in fixed bed.Iron catalyst adds potassium (as K 2CO 3) activation, for synthetic low molecule product, can under comparatively high temps (320～340 ℃), carry out.The used catalyzer of ebullated bed or air flow bed is by magnetite and fusing assistant fusing, reduces with hydrogen then and makes.It active less, and intensity height.
B. type of reactor: Fischer-Tropsch is synthetic to be strong exothermal reaction, and every generation 1kg hydrocarbon is heat release 10.9MJ approximately, so reactor need be got rid of selectivity the best that a large amount of reaction heat makes reaction, catalyzer is the longest work-ing life, produces most economical.The reactor that uses has fixed-bed reactor, air flow bed reactor and paste state bed reactor.
C. Fischer-Tropsch synthesis process condition:
A. temperature: temperature depends primarily on selected catalyzer.Active high catalyzer, the synthetic temperature range is lower.The optimum synthesising temperature of Fe-series catalyst is 220～340 ℃.In suitable temperature range, improve temperature of reaction and help the generation of low-boiling products, generate otherwise help the high boiling point product.
B. pressure: pressure not only influences activity of such catalysts and life-span, also influences the composition and the productive rate of product.Fe-series catalyst is adopted normal pressure synthesis, and its active low life-span is short, general requirement pressure 0.7～3.0MPa.
C. unstripped gas is formed: (CO+H in the unstripped gas 2) height of volume fraction influences synthesising reacting speed.Its volume fraction of general requirement is 80-85%.
N (H in the unstripped gas 2The direction that the height influence reaction of)/n (CO) ratio is carried out.N (H 2)/n (CO) ratio can not utilize the catalyst carbon deposition inactivation less than 0.5.
H in the unstripped gas 2Ratio n (the H that reacts with CO 2)/n (CO) is called utilization ratio or consumption rate, and this value is 0.5-3, is usually less than unstripped gas n (H 2The ratio of components of)/n (CO).
Improve n (H in the unstripped gas 2)/n (CO) ratio and reaction pressure can improve n (H 2The utilization ratio of)/n (CO).The circulation of employing tail gas makes n (H 2The utilization ratio of)/n (CO) is more near n (H in the unstripped gas 2)/n (CO) ratio of components, thus higher product productive rate obtained.Fe-series catalyst adopts recycle ratio to be 2～3, to be the volume ratio of circulation gas and fresh feed gas at present.
D. Fischer-Tropsch synthesis process flow process:
A. the Arge of South Africa SASOL factory fixed bed synthesis technique flow process is an exemplary, as shown in Figure 7.
Can produce products such as gasoline, diesel oil and wax class.Be the example explanation with this technology below:, obtain n (H through the carbonic acid gas conversion 2)/n (CO) ratio is 1.7 qualified synthetic gas.Fresh synthesis gas and circulation gas are compressed to 2.45MPa and send into Arge reactor 601 with 1: 2.3 mixed.Synthetic gas is heated to 150～180 ℃ earlier in heat exchanger 603, enter beds again and carry out building-up reactions.Each reactor 601 is equipped with 40m 3Particle is the precipitated iron catalyst of 2～5mm, and it consists of: n (Fe): n (Cu): n (K 2O): n (SiO 2)=100: 5: 5: 25.Reaction tubes is outer takes away reaction heat by boiled water WS generation water vapour VP.The beginning temperature is 220～235 ℃, and it is 245 ℃ that operational cycle Mo allows top temperature.The product that autoreactor 601 comes out is sloughed paraffinic hydrocarbon Wax through wax separator 602 earlier, after enter heat exchanger 603 and carry out heat exchange with unstripped gas, tell hot condensate liquid HCR in its bottom, enter watercooler 604, watercooler 605 again, cool and isolate the condensate CR that comprises light oil and water by water coolant CW.In order to prevent the organic acid etching apparatus, use among the alkali NaOH and acidic components in the cold oil.It is cold oil, water and organic oxygen compound (H that the condensate CR that obtains in separator 606 isolates cryocondensation thing CCR 2O﹠amp; O-Oxd).The residual air that watercooler 605 is discharged is tail gas, and a part is made circulation gas, and all the other send oil-absorption tower to reclaim C 3And C 4Hydro carbons.Synthetic method the results are shown in Table 1.
B. it is synthetic that Mining Group coal in Yanzhou is made the Fischer-Tropsch of oil tech indirectly, compared new improvement with Arge fixed bed synthesis technique: its Fischer-Tropsch synthesis unit is divided into two-stage, product all is paraffin and condensation product, secondary Fischer-Tropsch synthetic unstripped gas is an one-level Fischer-Tropsch synthetic tail gas, two synthesis unit tail gas circulations; Secondary Fischer-Tropsch synthetic tail gas enters C 3-C 5Reclaim the unit and cool back ending gas C by the degree of depth 3Above component, two-stage Fischer-Tropsch synthetic paraffin and condensation product enter refinery unit together and produce oil.Be present domestic best technology.
C. improved F-T method: the subject matter that the F-T method exists is the sintetics complexity, poor selectivity.Thereby, the industrialization of plyability Application of Catalyst and improved F-T method has appearred.Improving the F-T method is MFT (Modifild F-T) method.Its ultimate principle flow process as shown in Figure 8, synthetic method the results are shown in Table 1.
The compressed preheating of synthetic gas 1: 3 by volume mixes with circulation gas, enters the process furnace convection zone and is preheated to 240～270 ℃, sends into first stage reactor under pressure 2.5MPa, carries out the synthin reaction under the iron catalyst effect.One section resultant of reaction enters one section interchanger, with 330 ℃ second-stage reaction tail gas heat exchange to 295 ℃, advances the process furnace radiation section again and is heated to 350 ℃, send second stage reactor, carries out the reaction of hydrocarbon molecules sieve upgrading under pressure 2.45MPa, generates gasoline.The second-stage reaction product is through one section interchanger, circulation gas interchanger, water cooler cooling, and through gas-liquid separator separates, phlegma oil-feed water separator is isolated raw gasline and advanced storage tank, after send distillation tower cutting gas-liquid cut.The tail gas of gas-liquid separator after interchanger heats up, the ammonia cooler cooling, goes out gasoline fraction by gas-liquid separator separates earlier, directly send the treated gasoline storage tank.
Because the present invention is with purified H 2And CO 2Be raw material, pass through CO 2Conversion makes qualified synthetic gas, adopt again coal become the step of the 3rd in the oily technology, F-T synthesis method synthesizing aliphatic hydrocarbons, separate fuel-displaced, thereby, do not have the sulfur-bearing catalyzer poison, do not need coal to become and remove sulfide technology in the oily technology.
If expecting diesel oil is main product, can adopt the coal of Shandong Yanzhou Mining Group to make F-T synthesis method in the oil tech indirectly.If expecting gasoline is main product, can adopts and improve the F-T method, be the MFT method.
Embodiment 3: in the water-deficient area, use this law to utilize solar hydrogen making and oil, used water can adopt the air water-intaking technology to solve.Air water-intaking generally adopts deliquescent agent, for example: CaCl 2, KOH, NaOH etc., absorb airborne steam, heat deliquescent agent then and obtain distilled water.Air water-intaking also can adopt other technologies, for example imitative beetle air water-intaking technology.
Table 1:F-T synthetic method and result
Project F-T method (Arge) The MFT method
Catalyst temperature/℃ pressure/MPa unstripped gas n (H 2)/n (CO) recycle ratio CO transformation efficiency/% H 2Transformation efficiency/% product yield (massfraction)/% methane ethylene-ethane propylene propane butylene butane gasoline (C 5-C 12) diesel oil (C 13-C 18) heavy oil (C 19-C 30) wax (C 31More than) Precipitated iron 220-255 2.5-2.6 1.7-2.5 1.5-2.5 60-80 5.0 0.2 2.4 2.0 2.8 3.0 2.2 22.5 15.0 23.0 18.0 Precipitated iron/ZSM-5 230/300 2.5/2.5 2 1.6 88.0 70.4 6.6 18.4 75.0 about 0

Claims (7)

1. one kind is utilized solar hydrogen making and oily method, comprises following operation:
1. utilize sun power system water vapour: produce water vapour with solar energy collector (12), send vapour case (13) to store; Enter Heating K I and KIO from the water vapour of vapour case (13) output by vaporizer I (5) middle part inlet mouth 3Become water of condensation behind the solution, flow out, return by solar energy collector (12) water-in from vaporizer I (5) bottom water outlet; Or advance calcining furnace (2) from the water vapour that vapour case (13) is exported and heat, advance vaporizer I (5) heating again;
2. the preparation of salt and dehydration: the unloading phase of production, in the protection against corrosion salt manufacturing tube (1) of sealing, add I 2, KOH, and add distilled water by water tank (14), stir with stirrer, reaction at normal temperatures generates KI, generates KIO simultaneously 3After the reaction, KI and KIO 3Solution advances liquid feeding tank (15); Its reaction equation:
6KOH+3I 2＝5KI+KIO 3+3H 2O
The unloading phase after, enter salt manufacturing tube (1) from the intermediate product of flow process four processes, continue to keep generating KI and KIO 3Reaction; They are: the KI of photolytic cell (7) 3Solution or KI 3And KIO 3The KOH solution that the remaining liq of solution, decomposing H I, electric field splitter (3) are produced, by the distilled water of water tank (14) supply; Wherein, KI 3Solution is the I that generates with KI solution dissolving decomposing H I 2Generate KI 3And KIO 3Solution is with KI and KIO 3The I that solution dissolving decomposing H I generates 2Generate;
By effusive KI of liquid case (15) and KIO 3After solution is sent into condenser (4) preheating, enter vaporizer I (5) and heat by water vapor; The effusive suspension of vaporizer I (5) bottom liquid outlet separates with the protection against corrosion whizzer, isolates KI and KIO 3Solid;
3. the calcining of Potassium Iodate: with isolated KI and KIO 3Solid is sent in the corrosion resistant calcining furnace (2), through 100 ℃～250 ℃ temperature calcinings, generates KI and O 2Its reaction equation:
Figure FSB00000420261500011
Sending into salt tube (10) after KI comes out of the stove, with flow out by vaporizer II (6), the liquid water of entering salt tube (10) is mixed into KI solution, enters electric field splitter (3); The O that calcining generates 2Reclaim;
4. the recovery of oxygen: the O that emits by calcining furnace (2) 2, entering from absorption tower II (9) bottom, absorption agent KOH solution is entered by absorption tower II (9) top, absorbs O 2Middle remaining I 2Behind the gas, flow out the O of purification by absorption tower II (9) bottom liquid outlet 2Emit by absorption tower II (9) air outlet, top, enter O 2Gas tank stores;
5. the preparation of the hydrolysis of liquor kalii iodide and hydroiodic acid HI: this operation is finished in electric field splitter (3);
Electric field splitter (3) is called for short electricity and divides device, comprises sealed tube (301), the two pairs of electric field electrodes, spacer plate (306); A liquid inlet (E is respectively established at vertical two ends of sealed tube (301) I1, E I2); The positive and negative electrode of two pairs of electric field electrodes lays respectively at the vertical both sides external of sealed tube (301), longitudinally every limit is a pair of; Two pairs the electric field electrode pole plate is parallel with sealed tube (301) centerline direction, polarity is opposite, forms two opposite ion split movement districts of direction of an electric field in sealed tube (301): A district, B district; Spacer plate (306) is between A district, B district, and is vertical with direction of an electric field, the middle part in the sealed tube (301) is divided into two ion mixing zones: C district, D district; C district, D district have liquid exit (E separately respectively 01, E 02);
Inlet (the E that divides device (3) from the KI solution of changing salt tube (10) by electricity I1) enter; Simultaneously, distilled water divides another relative inlet (E of device (3) from electricity I2) enter; Divide under the positive and negative two groups of effect of electric field of device (3) at electricity to be hydrolyzed, generate HI solution and KOH solution; Its reaction equation:
Figure FSB00000420261500021
Figure FSB00000420261500022
K ++OH -＝KOH I -+H +＝HI
The KOH solution that generates divides the outlet (E of device (3) from electricity 01) flow out, enter salt manufacturing tube (1); The HI solution that generates divides another outlet of device (3) (E from electricity 02) flow out, enter photolytic cell (7);
6. the recovery of the preparation of hydrogen and iodine: divide the HI solution of device (3) from electricity, enter,, advance photodissociation under the sunlight of photolytic cell (7) in transmission again simultaneously, generate H with the plumbous or silver reaction in the photolytic cell (7) by photolytic cell (7) bottom fluid inlet 2And I 2H 2Emitted by the outlet of photolytic cell (7) top, water is emitted by lower part outlet; Its reaction equation:
Pb+2HI＝PbI 2+H 2↑ 2Ag+2HI＝2AgI+H 2↑
Figure FSB00000420261500023
Figure FSB00000420261500024
After gas and liquid have been put in the outlet of photolytic cell (7), make from the KI solution of changing salt tube (10), enter the I that the dissolving photodissociation generates from photolytic cell (7) bottom fluid inlet 2And the KI that generates 3Solution flows out from the top outlet of photolytic cell (7), enters salt manufacturing tube (1); Its reaction equation:
KI+I 2＝KI 3
Perhaps, make KI and KIO from liquid case (15) 3Solution enters the I that the dissolving photodissociation generates from photolytic cell (7) bottom fluid inlet 2Generate KI 3And KIO 3Solution flows out from the top outlet of photolytic cell (7), enters salt manufacturing tube (1); At this moment, only be fit to the reaction of silver with HI solution; Reaction equation is the same;
Photodissociation HI solution and recovery I 2Two steps in the fluid inlet of photolytic cell (7), outlet up and down, are to control automatically or Artificial Control by switch;
7. hydrogen is refining: H 2After emitting from photolytic cell (7), enter by absorption tower I (8) bottom; Absorption agent KOH solution is entered by absorption tower I (8) top, absorbs H 2Middle remaining HI, I 2After, discharge by absorption tower I (8) bottom; H 2Emit by absorption tower I (8) top, enter H 2Gas tank (16) stores;
8. water purification: the water of removing mechanical impurity is entered by vaporizer II (6) top water-in, and the water vapour heating of origin flash-pot I (5) air outlet, top becomes water vapour, emits from vaporizer II (6) air outlet, top, enters to be KI and KIO 3In the condenser of solution preheating (4), enter water tank (14) through being condensed into distilled water, the distilled water of water tank (14) is sent into salt manufacturing tube (1) again; Impurity in the water is discharged by vaporizer II (6) bottom water outlet;
After said process started, the intermediate product that returns salt manufacturing tube (1) continued reaction and photodissociation hydrogen manufacturing under illumination; Perhaps, after producing hydrogen, continue subsequent processing:
9. oil is synthetic and refining: the H that produces with above-mentioned operation 2Be raw material, with CO 2Mix, synthesize, produce oil fuel by carbonic acid gas conversion, Fischer-Tropsch (F-T); The total chemical equation and the operation of synthetic oil:
Figure FSB00000420261500025
1) produces CO 2
2) carbonic acid gas conversion: with the H that produces 2And CO 2Be raw material,, produce F-T synthetic needed qualified " synthetic gas " by the carbonic acid gas conversion process, that is: its volume fraction be 80～85%, n (H 2The ratio of)/n (CO) is no less than 0.5 H 2With the CO mixture; Carbonic acid gas transformationreation formula is:
Figure DEST_PATH_FSB00000470418600011
This is reflected under the effect of catalyzer and carries out in synthetic tower, is the reaction of reversible, heat absorption, constancy of volume; Select the proper handling condition: the upper limit of extract operation temperature increases transformation efficiency, discharges after water vapour is removed in cooling generating gas, recirculation enters system and proceeds the carbonic acid gas conversion, impel balance to move right, adjust the composition of gasification product, reach the synthetic requirement of F-T with qualified " synthetic gas ";
3) F-T is synthetic: qualified " synthetic gas " sent into reactor carries out F-T and synthesize, under the effect of catalyzer by H 2Generate aliphatic hydrocarbon with CO; F-T synthesizes the primitive reaction formula:
Figure DEST_PATH_FSB00000470418600012
The F-T synthetic product is produced finished product oil fuel through product separation, product purification.
2. the method for utilizing solar hydrogen making and oil according to claim 1 is characterized in that: in the calcination process of said 3. Potassium Iodate, and calcining KI and KIO in calcining furnace (2) 3Solid generates KI and O 2, be with 100 ℃～250 ℃ water vapour of vapour case (13) output, enter calcining furnace (2) Heating K I and KIO by pipeline 3Solid; Then, enter vaporizer I (5), Heating K I and KIO from calcining furnace (2) air outlet, top 3Solution is discharged by vaporizer I (5) top and is entered the water that vaporizer II (6) adds the heat extraction mechanical impurity, is condensed into water, discharges entering salt tube (10) by vaporizer II (6) bottom water outlet.
3. the method for utilizing solar hydrogen making and oil according to claim 1, it is characterized in that: in the hydrolyzing process of said 5. liquor kalii iodide, used electricity divides the liquid inlet (E of device (3) I1, E I2) the flat shower nozzle of chewing of employing; Flat width≤the 1mm that chews of shower nozzle, the flat length direction of chewing is vertical with direction of an electric field.
4. the method for utilizing solar hydrogen making and oil according to claim 1 is characterized in that: in the recovery process of said 6. iodine, with KI and KIO 3The I that solution dissolving photodissociation generates 2The time, the silver with the reaction usefulness of hydroiodic acid HI is plated on the wire netting, promptly uses silver-plated wire netting.
5. the method for utilizing solar hydrogen making and oil according to claim 1 is characterized in that: in the synthetic and refining step of said 9. oil, and used CO 2Be in the absorption tower, to make absorption agent, absorb airborne CO with strong base solution 2Generate supercarbonate, electricity consumption divides device (3) decomposition supercarbonate to produce then; Described highly basic is NaOH, KOH; When electricity consumption divided device to decompose, bicarbonate solution, water were divided two inlet (E of device (3) respectively by electricity I1, E I2) enter A district, B district, be decomposed into alkalimetal ion, HCO 3 -With H 3O +, OH -Ion, under electric field action, alkalimetal ion, OH -Enter the C district, be combined into alkaline solution, by outlet (E 01) discharge; HCO 3 -, H 3O +Enter the D district, be combined into H 2CO 3Solution is by another outlet (E 02) discharge; The H that discharges 2CO 3Solution is because CO 2Solubleness in water is little and decompose, and generates CO 2Emit; Wherein, it is as follows to make the reaction equation of absorption agent with NaOH, KOH:
NaOH+CO 2=NaHCO 3Or KOH+CO 2=KHCO 3
Figure FSB00000420261500041
Or
Figure FSB00000420261500042
H 2CO 3＝H 2O+CO 2↑。
6. the method for utilizing solar hydrogen making and oil according to claim 1 is characterized in that: in the synthetic and refining step of said 9. oil, the catalyzer of using in the carbonic acid gas conversion is with Fe 2O 3For main body, with Cr 2O 3Be the multicomponent Fe-Cr series catalyzer of main additive, temperature is 350～550 ℃, and pressure is 0.7～3.0MPa; The catalyzer of using during F-T is synthetic is a Fe-series catalyst, and synthesis temperature is 220～340 ℃, and pressure is 0.7～3.0MPa, requires (the CO+H in the unstripped gas 2) volume fraction is 80～85%, the utilization in the unstripped gas than, be n (H 2)/n (CO) ratio is 0.5～3, and adopting recycle ratio is 2～3.
7. the method for utilizing solar hydrogen making and oil according to claim 1 is characterized in that: said water, and adopt the air water-intaking technology to obtain in the water-deficient area, that is: absorb airborne steam with deliquescent agent, heat deliquescent agent then and obtain distilled water.
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CN1554569A (en) * 2003-12-25 2004-12-15 吴佶伟 System and its device for producing hydrogen and oxygen using solar energy
US20060013765A1 (en) * 2004-07-14 2006-01-19 The Boeing Company Method for producing hydrogen gas by steam methane reforming using solar energy
CN1962413A (en) * 2005-11-09 2007-05-16 孔庆全 Method for producing hydrogen gas and methanol using solar energy
CN101037187A (en) * 2007-03-20 2007-09-19 高永祥 Device for preparing hydrogen/water gas by employing solar energy

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CN1554569A (en) * 2003-12-25 2004-12-15 吴佶伟 System and its device for producing hydrogen and oxygen using solar energy
US20060013765A1 (en) * 2004-07-14 2006-01-19 The Boeing Company Method for producing hydrogen gas by steam methane reforming using solar energy
CN1962413A (en) * 2005-11-09 2007-05-16 孔庆全 Method for producing hydrogen gas and methanol using solar energy
CN101037187A (en) * 2007-03-20 2007-09-19 高永祥 Device for preparing hydrogen/water gas by employing solar energy

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