CN103523750A - Reaction device and method for hydrogen production through photocatalytic water splitting - Google Patents
Reaction device and method for hydrogen production through photocatalytic water splitting Download PDFInfo
- Publication number
- CN103523750A CN103523750A CN201310449999.3A CN201310449999A CN103523750A CN 103523750 A CN103523750 A CN 103523750A CN 201310449999 A CN201310449999 A CN 201310449999A CN 103523750 A CN103523750 A CN 103523750A
- Authority
- CN
- China
- Prior art keywords
- gas
- reaction vessel
- dosing pond
- catalyzer
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a reaction device for hydrogen production through photocatalytic water splitting. The reaction device comprises a carrier gas steel cylinder, a reaction vessel, a gas metering pool and an infrared counter, wherein the carrier gas steel cylinder, the reaction vessel and the gas metering pool are connected sequentially; the carrier gas steel cylinder is connected with a gas-washing inlet of the reaction vessel through a pressure reducing valve and a flow meter sequentially; a temperature control device is arranged outside the reaction vessel; the gas metering pool comprises a gas metering pool gas charging chamber and a gas metering pool gas discharging chamber, the gas metering pool gas charging chamber is connected with the gas metering pool gas discharging chamber through a V-shaped part and connected with the reaction vessel, and the gas metering pool gas discharging chamber is connected with a gas collection bag; and the infrared counter is used for measuring calibration bubbles produced by the V-shaped part. The invention further discloses a reaction method for hydrogen production through photocatalytic water splitting. The reaction device requires less support equipment, and is simpler, small in occupied space, lower in cost, high in automation degree, low in air-tightness requirement of the device, convenient to operate and maintain and accurate in measurement result.
Description
Technical field
The present invention relates to cleaning new energy-Hydrogen Energy field of Environment Protection, be specifically related to a kind of reaction unit of photolysis water hydrogen, the reaction method that also relates to a kind of photolysis water hydrogen, can be widely used in the experimental study of photocatalysis field, for measuring photochemical catalysis experimental system, produce the activity change of volume and the Real-Time Monitoring catalyzer of gas.
Background technology
At present, the experimental installation of photolysis water hydrogen mainly comprises light-source system, reactive system, gas circulation Controlling System, vacuum system, online gas sampling system, this six large system of chromatographic detection system (gas-chromatography).What whole device was connected successively by pipeline is reactor, the first condensing reflux pipe, gas mixing portion, sampling portion and the second condensing reflux pipe online, also comprise and be attempted by the second condensing reflux pipe and the vacuum between sampling portion online, gas sampling portion is connected with gas-chromatography.The accessory using in device mainly comprises through metal, cooling system, reaction light source (often, for high voltage mercury lamp (UV-light is main) or xenon lamp (visible ray is main), can obtain by additive filter or liquid optical filters the light source of required wave band), vacuum glass pipeline (containing high vacuum stopcock), vacuum pump, precise vacuum table, valve, air pump, condensing reflux pipeline, online sampling system, standard sampling system and the gas-chromatography etc. of system assembling.
Because support equipment in conventional equipment is more, complete assembly more complicated, volume is large, it is many to take up room, and cost is higher; In addition, in device, use more glass material pipeline, safeguard more difficult.For the minimum gas that guarantees to produce, do not reveal, the singularity of gas requires high to the resistance to air loss of device.In experimentation, need under vacuum condition, operate, and the time that need to maintain condition of high vacuum degree up to more than 12 ~ 24 hours, to the vacuum tightness of device, require high.The valve that whole device is used is more, needs to control by the valve of continuous rotation particular design the flow direction of gas in operating process, complex operation step, and level of automation is low.When gas generating amount is larger, the gas in pipeline can circulate not smooth, causes the error of take off data larger.Conventional equipment, before carrying out monitoring catalyst activity experiment, must obtain typical curve simultaneously, and requires high to linear dependence degree.Because complete assembly is complicated, any link all may cause the linear dependence degree of typical curve not reach requirement and cannot carry out experiment below.Testing process detects the reactive behavior of indirect monitoring catalyzer by the concentration of gas-chromatography, and may be subject to the restriction of gas chromatographic detection limit.Therefore there is certain defect in existing conventional experimental installation.
Summary of the invention
Object of the present invention is just to overcome the problem that prior art exists, a kind of reaction unit of photolysis water hydrogen is provided, a kind of reaction method of photolysis water hydrogen is also provided, and matched with devices equipment is few, device is comparatively simple, occupy little space, cost is lower, level of automation is high, less demanding to the resistance to air loss of device, operation and maintenance convenient; Measuring result is accurate; Investigate before the activity experiment of catalyzer, do not need drawing standard curve to demarcate the concrete growing amount of hydrogen, before experiment, set-up procedure is simple; And the hydrogen volume that aerogenesis that can Real-Time Monitoring photolysis water hydrogen partly produces, gets information about the activity change situation of catalyzer by the variation of hydrogen volume.
Object of the present invention can realize by following technical proposal:
A kind of reaction unit of photolysis water hydrogen, comprise carrier gas steel cylinder, also comprise reaction vessel and gas metering pool, reaction vessel comprises gas washing entrance and aerogenesis outlet, carrier gas steel cylinder is connected with gas washing entrance with under meter by reducing valve successively, reaction vessel outer setting is useful on the temperature control unit of controlling reaction vessel interior temperature, reaction vessel seals by quartz glass plate and O type circle, reaction vessel top is provided with light source, gas dosing pond comprises gas dosing pond inlet plenum and gas metering pool exhaust chest, inlet plenum one end, gas dosing pond is provided with gas dosing pond inlet mouth, the other end is connected with V-shape portion one end, the V-shape portion the other end is connected with exhaust chest one end, gas dosing pond, the gas dosing pond exhaust chest the other end is provided with gas dosing pond venting port, aerogenesis outlet is communicated with gas dosing pond inlet mouth by T-valve, gas dosing pond venting port is connected with collection and confinement of gases bag, also comprise for measuring the infrared counting device of the demarcation bubble of V-shape portion generation.
Temperature control unit as above comprises the chuck that is set in reaction vessel outside, chuck comprises cooling liqs outlet and cooling liqs import, cooling liqs outlet is communicated with cooling liqs import by low temperature/constant temperature cooling circulating water machine, in reaction vessel, be placed with magneton, reaction container bottom is provided with magnetic agitation seat.
Temperature control unit as above comprises the water bath that is arranged on reaction vessel outside, is provided with fluid inlet and liquid outlet on water bath, is placed with magneton in reaction vessel, and reaction container bottom is provided with magnetic agitation seat.
A method of carrying out photolysis water hydrogen, comprises the following steps:
Catalyzer as above is titanium oxide class catalyzer or cadmium sulfide composite material class catalyzer or the sulfide-based catalyzer of zinc; Sacrifice agent is organic alcohols sacrifice agent or organic acid sacrifice agent or organic amine catalyzer or inorganic salts catalyzer.
The present invention compared with prior art has following beneficial effect:
Complete assembly support equipment is few, comparatively simple, occupy little space, cost is lower, level of automation is high, less demanding to the resistance to air loss of device, operation and maintenance convenient; Measuring result is accurate; Investigate before the activity experiment of catalyzer, do not need drawing standard curve to demarcate the concrete growing amount of hydrogen, before experiment, set-up procedure is simple; The hydrogen volume that aerogenesis that can Real-Time Monitoring photolysis water hydrogen partly produces, gets information about the activity change situation of catalyzer by the variation of hydrogen volume.
Accompanying drawing explanation
Fig. 1 is the schema of apparatus of the present invention;
Fig. 2 is the structural representation of apparatus of the present invention;
Fig. 3 is the first enforcement figure of reaction vessel;
Fig. 4 is the second enforcement figure of reaction vessel;
Fig. 5 is the third enforcement figure of reaction vessel;
Fig. 6 is the schematic diagram in gas dosing pond;
Fig. 7 is catalyzer hydrogen output figure in embodiment 1;
Fig. 8 is catalyzer hydrogen output figure in embodiment 2;
Fig. 9 is catalyzer hydrogen output figure in embodiment 3;
Figure 10 is catalyzer hydrogen output figure in embodiment 4.
In figure: 1-carrier gas steel cylinder; 2-reducing valve; 3-under meter; 4-the first flexible conduit; 5-gas washing entrance; 6-reaction vessel; 7-light source; 8-low temperature/constant temperature cooling circulating water machine; 9-the second flexible conduit; The import of 10-cooling liqs; The outlet of 11-cooling liqs; 12-the 3rd flexible conduit; 13-magnetic agitation seat; The outlet of 14-aerogenesis; 15-the 4th flexible conduit; 16-T-valve; 17-five weaknesses conduit; 18-gas dosing pond inlet mouth; 19-gas dosing pond venting port; 20-gas dosing pond; 21-infrared counting device; 22-computer; 23-draw point; 24-collection and confinement of gases bag; 25-quartz glass plate; 26-clip; 27-O type circle; 28 single-glasses (top); The outlet of 29-gas washing; 30-double glazing chuck (middle and lower part); 31-magneton; 32-reaction liquid; 33-gas dosing pond inlet plenum; 34-liquid; 35-produces the V-shape portion of bubble; 36-gas dosing pond exhaust chest; 37-water bath; 38-fluid inlet; 39-liquid outlet.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, and protection scope of the present invention is not limited by the following examples.
A whole set of photodissociation water experimental installation is characterised in that and comprises 4 main parts, as Fig. 1, specifically comprises: the gas washing part of (1) rare gas element; (2) the aerogenesis part of photolysis water hydrogen; (3) measure portion of gas; (4) the collection part of gas.Compare with conventional experimental installation, the present invention has mainly omitted the airtight recycle system, vacuum extractor and the gas-chromatography detection system of conventional equipment, and operating process does not need the valve that constantly rotates particular design to control gas.The present invention mainly transforms the measure portion of gas, adopted gas dosing pool device, the hydrogen that aerogenesis partly produces can promote gas and at the V-shape portion in gas dosing pond, produce the bubble of fixed volume, the side that bubble is connected with gas dosing pond exhaust chest by V-shape portion, by infrared counting device, the number of bubble is measured, can be obtained in real time intuitively the active situation of catalyzer.
As the further of said apparatus technical scheme improved and supplemented, apparatus of the present invention also comprise following technical scheme:
Described complete assembly, specifically comprise: carrier gas steel cylinder 1, reducing valve 2, under meter 3, reaction vessel 6(is gas washing entrance 5 wherein, aerogenesis outlet 14, cooling liqs import 10, cooling liqs outlet 11), light source 7, low temperature/constant temperature cooling circulating water machine 8, magnetic agitation seat 13, T-valve 16, gas dosing pond 20(is gas dosing pond inlet mouth 18 wherein, gas dosing pond inlet plenum 33, produce the V-shape portion 35 of bubble, gas dosing pond exhaust chest 36, gas dosing pond venting port 19), infrared counting device 21, computer 22, draw point 23, collection and confinement of gases bag 24, flexible conduit (4, 9, 12, 15, 17).Magneton is positioned in reaction vessel, and reaction vessel is positioned on magnetic agitation seat, opens magnetic agitation switch, and the magneton in reaction vessel starts stirring work under magneticaction.
use model:b11-2 rotating speed digital display constant temperature blender with magnetic force Shanghai Si Le Instrument Ltd..
Described complete assembly, as Fig. 2, its concrete mode of connection is characterised in that: carrier gas steel cylinder 1 is connected with reducing valve 2, reducing valve 2 is connected with under meter 3, under meter 3 is connected with the first flexible conduit 4, the first flexible conduit 4 is connected with the gas washing entrance 5 on reaction vessel 6 tops, gas is derived by the aerogenesis outlet 14 on reaction vessel top, aerogenesis outlet 14 is connected with the 4th flexible conduit 15, the 4th flexible conduit 15 is connected with T-valve 16, T-valve 16 is connected with five weaknesses conduit 17, five weaknesses conduit 17 is connected with the gas dosing pond inlet mouth 18 in gas dosing pond 20, gas is by gas dosing pond 20 to gas dosing pond venting port 19, gas dosing pond venting port 19 is connected with draw point 23, draw point 23 is connected with collection and confinement of gases bag 24.The top of reaction vessel 6 covers with quartz glass plate 25, and side can be fixed with 3 ~ 4 clips, and the wherein use of 1 clip of take is example, and clip 26 clamps the edge of the edge of quartz glass plate 25, O type circle 27 and reaction vessel 6.The bottom of reaction vessel 6 is placed on magnetic agitation seat 13.Light source 7 use lifting tables support, and make the effective light spot of light source vertically by quartz glass plate 25.Low temperature/constant temperature cooling circulating water machine 8 is connected with the cooling liqs import 10 of reaction vessel 6 bottoms, and the cooling liqs outlet 11 at reaction vessel 6 middle parts is connected with low temperature/constant temperature cooling circulating water machine 8, and cooling working medium forms circulation.Infrared counting device 21 is arranged on gas dosing pond 20 1 sides, and infrared counting device 21 is connected with computer 22.
The aerogenesis part of photolysis water hydrogen, for reaching the object of temperature control, reaction vessel can be jacketed type reaction vessel, as Fig. 3; Can also adopt single-glass formula reaction vessel and water bath, as Fig. 4, Fig. 5.In Fig. 3, reaction vessel device specifically comprises: reactor vessel wall top is single-glass 28, and middle and lower part is double glazing chuck 30; O type circle 27 on reaction vessel edge, reactor vessel wall side is with 4 place's interfaces, and top is with the gas washing entrance 5 and aerogenesis outlet 14 of rare gas element, and middle and lower part is with cooling liqs import 10 and cooling liqs outlet 11; The other end of gas washing entrance 5 is gas washing outlet 29.In Fig. 4 and Fig. 5, reaction vessel specifically comprises: the gas washing entrance of rare gas element 5 and aerogenesis outlet 14, and the two can be at homonymy, also can be at heteropleural; Water bath specifically comprises: fluid inlet 38, liquid outlet 39.Single-glass formula reaction vessel is identical with jacketed type reaction vessel with the concrete mode of connection of water bath.
The aerogenesis part of photolysis water hydrogen, as Fig. 3 ~ 5, specifically comprises in reaction vessel during photolysis water hydrogen reaction: magneton 31 and reaction liquid 32,1/3 of the general no more than reaction vessel volume of volume of reaction liquid.
The measure portion of gas, as Fig. 6, gas dosing pool device specifically comprises: V-shape portion 35, the gas dosing pond exhaust chest 36 of gas dosing pond inlet mouth 18, gas dosing pond inlet plenum 33, liquid 34, generation bubble, gas dosing pond venting port 19.
The collection part of gas, as Fig. 2, specifically comprises: collection and confinement of gases bag 24.
The gas washing part of rare gas element, its specific works mode is characterised in that: before photolysis water hydrogen reaction, need to carry out twice gas washing operation.The object of gas washing is to remove a small amount of air being mixed with in reaction liquid (comprising water, catalyzer and sacrifice agent) for the first time, concrete operation step is: regulating three-way valve makes it to communicate with atmosphere, regulate reducing valve, rare gas element enters in reaction liquid by gas washing entrance, the gas washing outlet of reducing valve, under meter, flexible conduit, rare gas element successively, gas is emptying to T-valve place by the outlet of reaction vessel aerogenesis, flexible conduit, the gas washing time is 20 ~ 40min, to remove the air in reaction liquid; The object of gas washing is to remove reaction vessel top, connects the air existing in flexible conduit and gas dosing pond for the second time, and concrete operation step is: regulate glass three-way valve, make it to communicate with conduit, draw point communicates with atmosphere.Regulate reducing valve, as previously mentioned, rare gas element passes to T-valve, through flexible conduit, enters gas dosing pond, and emptying from draw point, the gas washing time is 20 ~ 40min.After gas washing completes, close carrier gas steel cylinder, in reaction vessel top, top, gas dosing pond and pipeline, be full of rare gas element, system is in normal pressure equilibrium state.
The aerogenesis part of photolysis water hydrogen, its specific works mode is characterised in that: when add reaction liquid (comprising water, catalyzer and sacrifice agent) and magneton in reaction vessel, top adopting quartz glass plate covers, side adopts 3 ~ 4 clips by reaction vessel, O type circle and silica glass board clamping, with gas leakage prevention.Reaction liquid, under the magnetic agitation effect and light source radiation of magneton, produces hydrogen, and the hydrogen producing exports derivation by aerogenesis.Because light source irradiates after reaction liquid, can make its temperature raise, in order to guarantee the non-volatile water vapour that becomes of water in reaction liquid, adopt cooling recirculation system, fluid temperature in reaction vessel is maintained to 20 ~ 30 ℃ of room temperatures, and concrete operation step is: the cooling working medium in low temperature/constant temperature cooling circulating water machine is imported to the chuck of reaction vessel by flexible conduit, from cooling liqs outlet, flow out, by flexible conduit, again import low temperature/constant temperature cooling circulating water machine, form refrigeration cycle.
Aerometry part, its specific works mode is characterised in that: due to the effect of pressure difference, the hydrogen producing forces gas to pass through liquid, and (liquid can be water, oil or other liquid), at the V-shape portion in gas dosing pond, produce the bubble (Application Range of bubble volume is 0.03 ~ 0.05mL) of fixed volume, the concrete volume of gas dosing bubble that pond produces can be through process of manufacture accurate calibration, the side that bubble is connected with gas dosing pond exhaust chest by V-shape portion, by infrared counting device, the number of bubble is measured, when infrared counter and computer coupling, the volume that can Real-Time Monitoring produces hydrogen.
Collection and confinement of gases part, its specific works mode is characterised in that: gas imported in collection and confinement of gases bag, standby.
Utilize above-mentioned experimental installation, the experimental implementation that can carry out, concrete technical scheme is as follows:
In reaction vessel (volume is 400 ~ 500mL), add a certain amount of catalyzer (catalyzer is titanium oxide class catalyzer or cadmium sulfide composite material class catalyzer or the sulfide-based catalyzer of zinc), water and sacrifice agent (organic alcohols sacrifice agent or organic acid sacrifice agent or organic amine catalyzer or inorganic salts catalyzer), the cumulative volume of reaction liquid accounts for 1/4 ~ 1/3 of reaction vessel volume, catalyzer, water and sacrifice agent three's mass ratio range is 1:(184 ~ 3200): (20 ~ 190), for catalyzer is effectively disperseed, before reaction, need ultrasonic 1 ~ 3min(to use model: KQ-2200DA Fauna of Kunshan, Jiangsu Shu Mei table type numerical control ultrasonic cleaner, ultrasonic power: 80w), cover quartz glass plate, side with 3 ~ 4 clips by reaction vessel, O type circle and silica glass board clamping.In low temperature/constant temperature cooling circulating water machine, add appropriate cooling working medium, cooling working medium is flowed into the double-jacket of reaction vessel from the cooling liqs import of reaction vessel middle and lower part, from cooling liqs outlet, flow out to low temperature/constant temperature cooling circulating water machine, form refrigeration cycle, temperature range is 20 ~ 30 ℃.The two mode of operation of single-glass formula reaction vessel and water bath is identical with jacketed type reaction vessel.Light source used is xenon lamp or high voltage mercury lamp light source, and regulating the distance range of light source and reaction vessel plane of illumination is 4 ~ 8cm.
Regulating three-way valve makes it to communicate with atmosphere, regulate reducing valve, rare gas element enters in reaction liquid by gas washing entrance, the gas washing outlet of reducing valve, under meter, flexible conduit, rare gas element successively, gas is emptying to T-valve place by the outlet of reaction vessel aerogenesis, flexible conduit, the gas washing time is 20 ~ 40min, to remove the air in reaction liquid; The object of gas washing is to remove reaction vessel top, connects the air existing in flexible conduit and gas dosing pond for the second time, and concrete operation step is: regulate glass three-way valve, make it to communicate with flexible conduit, draw point communicates with atmosphere.Regulate reducing valve, as previously mentioned, rare gas element passes to T-valve, through flexible conduit, enters gas dosing pond, and emptying from draw point, the gas washing time is 20 ~ 40min.After gas washing completes, close carrier gas steel cylinder, in reaction vessel top, top, gas dosing pond and pipeline, be full of rare gas element, system is in normal pressure equilibrium state.
Open light source, magnetic stirring apparatus and low temperature/constant temperature cooling circulating water machine, make catalyzer keep suspended state, temperature in reaction vessel maintains 20 ~ 30 ℃ of room temperatures, reaction liquid starts to react and produce hydrogen, because gas dosing pond is initially located in the normal pressure equilibrium state that is full of rare gas element, the hydrogen producing can promote gas and at the V-shape portion in gas dosing pond, produce the bubble (Application Range of bubble volume is 0.03 ~ 0.05mL) of fixed volume, the side that bubble is connected with gas dosing pond exhaust chest by V-shape portion, by infrared counting device, the number of bubble is measured, when infrared counter and computer coupling, can draw the hydrogen volume curve that (t) changes (v) in time, obtain in real time the active situation of catalyzer.Last gas rises to exhaust chest by the bottom in gas dosing pond, after venting port and draw point, finally adopts collection and confinement of gases bag to collect, standby.
When whole system is reacted to 3min, in gas dosing pond, just having can be observed bubble occurs, produce hydrogen speed fast, along with proceeding of reaction, in gas dosing pond, continue to produce a large amount of bubbles, when illumination 3.5h, photocatalysis Decomposition aqueous glycerin solution hydrogen output reaches the highest, and hydrogen volume is 48.01mL, and hydrogen output is large, in residing system, the catalytic activity of catalyzer is good.By infrared counting device, record the number of bubble, can directly obtain the volume of hydrogen, by drawing hydrogen volume-time curve, can get information about the activity change situation of catalyzer, in addition, before experiment, not need drawing standard curve, setup time is short, and process is simple; Experimentation operates under condition of normal pressure, simple and easy to do, to operator require lowly, be easy to automatization Control and Application and promote.
When whole system is reacted to 2.5min, in gas dosing pond, just having can be observed bubble occurs, along with proceeding of reaction, in gas dosing pond, continue to produce a large amount of bubbles, when illumination 2h, photocatalysis Decomposition aqueous formic acid hydrogen output reaches the highest, hydrogen volume is 65.08mL, and it is fast that system is produced hydrogen speed, and the consumption time is short, in residing system, the catalytic activity of catalyzer is good.By infrared counting device, record the number of bubble, can directly obtain the volume of hydrogen, by drawing hydrogen volume-time curve, can get information about the activity change situation of catalyzer, in addition, before experiment, not need drawing standard curve, setup time is short, and process is simple; Experimentation operates under condition of normal pressure, simple and easy to do, to operator require lowly, be easy to automatization Control and Application.
When whole system is reacted to 1min, in gas dosing pond, just can be observed bubble and occurred, along with proceeding of reaction, in gas dosing pond, continue to produce a large amount of bubbles, when illumination is during to 4h, photocatalysis Decomposition triethylamine aqueous solution hydrogen output reaches the highest, hydrogen volume is 335.2mL, and at follow-up 8h, the product hydrogen activity of catalyzer does not have decay substantially, and it is fast that system is produced hydrogen speed, the consumption time is short, in residing system, the catalytic activity of catalyzer is high, good stability.By infrared counting device, record the number of bubble, can directly obtain the volume of hydrogen, by drawing hydrogen volume-time curve, can get information about the activity change situation of catalyzer, in addition, before experiment, not need drawing standard curve, setup time is short, and process is simple; Experimentation operates under condition of normal pressure, simple and easy to do, to operator require low; For the large system of hydrogen output, overcome the large shortcoming of conventional photodissociation water measurement device error, be easy to automatization Control and Application.
When whole system is reacted to 20s, in gas dosing pond, just can be observed bubble and occurred, along with proceeding of reaction, in gas dosing pond, continue to produce a large amount of bubbles, when illumination is during to 8h, photocatalysis Decomposition aqueous sodium carbonate hydrogen output reaches the highest, and hydrogen volume is 620.3mL; From 2h-11h, the hydrogen output of system is all more than 100mL, and the hydrogen output of system is large, and the catalytic activity of catalyzer is high, and the time length is long.By infrared counting device, record the number of bubble, can directly obtain the volume of hydrogen, by drawing hydrogen volume-time curve, can get information about the activity change situation of catalyzer, in addition, before experiment, not need drawing standard curve, setup time is short, and process is simple; Experimentation operates under condition of normal pressure, simple and easy to do, to operator require low; For the large system of hydrogen output, overcome the large shortcoming of conventional photodissociation water measurement device error, be easy to automatization Control and Application.
Except specific embodiment, titanium oxide class catalyzer can also be: the B that 1. adulterates, the K of Cr
2la
2ti
3o
10; 2. the K of Ag adulterates
2la
2ti
3o
10; 3. the TiO of Gd adulterates
2; 4. the TiO of Ru adulterates
2; 5. the TiO of Bi adulterates
2; 6. the K of doped Ce
2la
2ti
3o
10; 7. the SrTiO of Co adulterates
3; Cadmium sulfide composite material class catalyzer can also be: 1. CdS-carbon nano tube compound material; 2. CdS-K
2ti
4-xpb
xo
9matrix material; 3. CdS-graphene composite material; The sulfide-based catalyzer of zinc can also be: the Cd of the B that 1. adulterates
0.5zn
0.5s; 2. the Cd of doped with Mg
0.5zn
0.5s; 3. AgInZn
7s
9; 4. Zn
0.9cu
0.4s; 5. ZnIn
2s
4; The sacrifice agent of organic alcohols can also be: 1. methyl alcohol; 2. ethanol; 3. ethylene glycol; 4. propyl alcohol; 5. butanols; The sacrifice agent of organic acid can also be: 1. acetic acid; 2. propionic acid; 3. oxalic acid; 4. butyric acid; The sacrifice agent of organic amine can also be: 1. diethylamine; 2. trolamine; 3. diethanolamine; 4. tri-isopropanolamine; The sacrifice agent of inorganic salts can also be: 1. S-WAT; 2. sodium sulphite; 3. sodium phosphate.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or supplement or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Claims (5)
1. the reaction unit of a photolysis water hydrogen, comprise carrier gas steel cylinder (1), it is characterized in that, also comprise reaction vessel (6) and gas metering pool (20), reaction vessel (6) comprises gas washing entrance (5) and aerogenesis outlet (14), carrier gas steel cylinder (1) is connected with gas washing entrance (5) with under meter (3) by reducing valve (2) successively, reaction vessel (6) outer setting is useful on the temperature control unit of controlling reaction vessel interior temperature, reaction vessel (6) is by quartz glass plate (25) and O type circle (27) sealing, reaction vessel (6) top is provided with light source (7), gas dosing pond (20) comprises gas dosing pond inlet plenum (33) and gas metering pool exhaust chest (36), gas dosing pond inlet plenum (33) one end is provided with gas dosing pond inlet mouth (18), the other end is connected with V-shape portion one end, the V-shape portion the other end is connected with gas dosing pond exhaust chest (36) one end, gas dosing pond exhaust chest (36) the other end is provided with gas dosing pond venting port (19), aerogenesis outlet (14) is communicated with gas dosing pond inlet mouth (18) by T-valve (16), gas dosing pond venting port (19) is connected with collection and confinement of gases bag (24), also comprise for measuring the infrared counting device of the demarcation bubble of V-shape portion generation.
2. the reaction unit of a kind of photolysis water hydrogen according to claim 1, it is characterized in that, described temperature control unit comprises the chuck that is set in reaction vessel (6) outside, chuck comprises cooling liqs outlet (11) and cooling liqs import (10), cooling liqs outlet (11) is communicated with cooling liqs import (10) by low temperature/constant temperature cooling circulating water machine (8), in reaction vessel (6), be placed with magneton (31), reaction vessel (6) bottom is provided with magnetic agitation seat (13).
3. the reaction unit of a kind of photolysis water hydrogen according to claim 1, it is characterized in that, described temperature control unit comprises the water bath (37) that is arranged on reaction vessel (6) outside, on water bath (37), be provided with fluid inlet (38) and liquid outlet (39), in reaction vessel (6), be placed with magneton (31), reaction vessel (6) bottom is provided with magnetic agitation seat (13).
4. utilize device described in claim 1 to carry out a method for photolysis water hydrogen, it is characterized in that, comprise the following steps:
Step 1, in the reaction vessel of 400 ~ 500mL, add catalyzer, water and sacrifice agent, the cumulative volume of the reaction liquid in reaction vessel accounts for 1/4 ~ 1/3 of reaction vessel volume, catalyzer, water and sacrifice agent three's mass ratio range: 1:184 ~ 3200:20 ~ 190;
Step 2, utilize ultrasonic cleaner to carry out ultrasonic 1 ~ 3min, ultrasonic power is 80w, with dispersed catalyst;
Step 3, cover quartz glass plate, side with 3 ~ 4 clips by reaction vessel, O type circle and silica glass board clamping, in low temperature/constant temperature cooling circulating water machine, add cooling working medium, cooling working medium circulation is flowed in chuck, controlling temperature range is 20 ~ 30 ℃;
Step 4, to select light source be xenon lamp or high voltage mercury lamp light source, and regulating light source and the distance range of the interior liquid plane of illumination of reaction vessel is 4 ~ 8cm;
Step 5, regulating three-way valve make it to communicate with atmosphere, regulate reducing valve, rare gas element enters in the reaction liquid in reaction vessel by reducing valve, under meter successively, and rare gas element is emptying via T-valve place by the aerogenesis outlet of reaction vessel, and the gas washing time is 20 ~ 40min;
Step 6, carry out gas washing for the second time, regulating three-way valve, makes aerogenesis outlet communicate with gas dosing pond inlet mouth, and air outlet, gas dosing pond communicates with atmosphere by draw point, and the gas washing time is 20 ~ 40min;
Step 7, open light source, magnetic stirring apparatus and low temperature/constant temperature cooling circulating water machine, make catalyzer keep the temperature in suspended state and reaction vessel to maintain 20 ~ 30 ℃ of room temperatures, reaction liquid starts to react and produce hydrogen, because gas dosing pond is initially located in the normal pressure equilibrium state that is full of rare gas element, the hydrogen producing can promote gas and at the V-shape portion in gas dosing pond, produce the bubble of fixed volume, the side that bubble is connected with gas dosing pond exhaust chest by V-shape portion, by infrared counting device, the number of bubble is measured, obtain in real time the active situation of catalyzer, last gas rises to exhaust chest by the bottom in gas dosing pond, after venting port and draw point, the final collection and confinement of gases bag that adopts is collected, standby.
5. the method for photolysis water hydrogen according to claim 4, is characterized in that, described catalyzer is titanium oxide class catalyzer or cadmium sulfide composite material class catalyzer or the sulfide-based catalyzer of zinc; Sacrifice agent is organic alcohols sacrifice agent or organic acid sacrifice agent or organic amine catalyzer or inorganic salts catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310449999.3A CN103523750B (en) | 2013-09-27 | 2013-09-27 | Reaction device and method for hydrogen production through photocatalytic water splitting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310449999.3A CN103523750B (en) | 2013-09-27 | 2013-09-27 | Reaction device and method for hydrogen production through photocatalytic water splitting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103523750A true CN103523750A (en) | 2014-01-22 |
| CN103523750B CN103523750B (en) | 2015-04-01 |
Family
ID=49926177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310449999.3A Active CN103523750B (en) | 2013-09-27 | 2013-09-27 | Reaction device and method for hydrogen production through photocatalytic water splitting |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103523750B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226224A (en) * | 2014-07-28 | 2014-12-24 | 北京泊菲莱科技有限公司 | Photocatalytic hydrogen production system and hydrogen production method |
| CN105565268A (en) * | 2016-02-01 | 2016-05-11 | 四川中投亿星新能源科技有限公司 | Synthetic hydrogen gas preparation device |
| CN107063922A (en) * | 2017-02-27 | 2017-08-18 | 湖北洛克泰克仪器有限公司 | A kind of full-automatic Biochemical Methane Potential test system |
| WO2020087425A1 (en) * | 2018-10-30 | 2020-05-07 | 顾士平 | Hydrogen cycle-based solar hydrogen production, storage and application system |
| CN111137854A (en) * | 2020-01-16 | 2020-05-12 | 江西理工大学 | Device for photocatalytic hydrogen production |
| CN111366675A (en) * | 2018-12-25 | 2020-07-03 | 中国科学院武汉物理与数学研究所 | System and method for determining optimal value of water adsorption amount of unit photocatalyst in photocatalytic reaction |
| CN111701552A (en) * | 2020-06-16 | 2020-09-25 | 北京阳光凯特科技有限公司 | Multifunctional photochemical reaction experimental device |
| CN113697769A (en) * | 2021-08-27 | 2021-11-26 | 山东大学 | Hydrogen production method based on heat-assisted photocatalytic system |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1245531A1 (en) * | 2000-05-15 | 2002-10-02 | Yosohiro Sugie | Hydrogen gas generating method |
| EP1019316B1 (en) * | 1998-05-05 | 2004-03-24 | Shec Labs - Solar Hydrogen Energy Corporation | Process for the production of hydrogen by thermal decomposition of water |
| EP1905735A1 (en) * | 2005-07-20 | 2008-04-02 | Hitachi Maxell, Ltd. | Hydrogen-generating material and process for producing hydrogen-generating material |
| CN101597026A (en) * | 2009-07-03 | 2009-12-09 | 西安交通大学 | The biomass supercritical water gasification hydrogen production System and method for that focusing solar energy drives |
| CN101920934A (en) * | 2010-03-21 | 2010-12-22 | 刘之政 | Method for decomposing water and device thereof |
| CN102285638A (en) * | 2011-05-25 | 2011-12-21 | 华东理工大学 | Visible light catalytic hydrogen production reactor |
| CN102646349A (en) * | 2012-04-25 | 2012-08-22 | 哈尔滨工业大学 | Photocatalytic gas preparation demonstration system |
| CN102651086A (en) * | 2011-02-28 | 2012-08-29 | 大连海兰德维通信技术有限公司 | Counting device, counting method and infrared detection system |
| CN102874752A (en) * | 2012-10-31 | 2013-01-16 | 乌鲁木齐人人康空气净化技术有限公司 | Solar energy photocatalysis water decomposing hydrogen making machine |
| CN203474447U (en) * | 2013-09-27 | 2014-03-12 | 湖北洛克泰克仪器有限公司 | Reaction device for hydrogen production by water photolysis |
-
2013
- 2013-09-27 CN CN201310449999.3A patent/CN103523750B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1019316B1 (en) * | 1998-05-05 | 2004-03-24 | Shec Labs - Solar Hydrogen Energy Corporation | Process for the production of hydrogen by thermal decomposition of water |
| EP1245531A1 (en) * | 2000-05-15 | 2002-10-02 | Yosohiro Sugie | Hydrogen gas generating method |
| EP1905735A1 (en) * | 2005-07-20 | 2008-04-02 | Hitachi Maxell, Ltd. | Hydrogen-generating material and process for producing hydrogen-generating material |
| CN101597026A (en) * | 2009-07-03 | 2009-12-09 | 西安交通大学 | The biomass supercritical water gasification hydrogen production System and method for that focusing solar energy drives |
| CN101920934A (en) * | 2010-03-21 | 2010-12-22 | 刘之政 | Method for decomposing water and device thereof |
| CN102651086A (en) * | 2011-02-28 | 2012-08-29 | 大连海兰德维通信技术有限公司 | Counting device, counting method and infrared detection system |
| CN102285638A (en) * | 2011-05-25 | 2011-12-21 | 华东理工大学 | Visible light catalytic hydrogen production reactor |
| CN102646349A (en) * | 2012-04-25 | 2012-08-22 | 哈尔滨工业大学 | Photocatalytic gas preparation demonstration system |
| CN102874752A (en) * | 2012-10-31 | 2013-01-16 | 乌鲁木齐人人康空气净化技术有限公司 | Solar energy photocatalysis water decomposing hydrogen making machine |
| CN203474447U (en) * | 2013-09-27 | 2014-03-12 | 湖北洛克泰克仪器有限公司 | Reaction device for hydrogen production by water photolysis |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226224A (en) * | 2014-07-28 | 2014-12-24 | 北京泊菲莱科技有限公司 | Photocatalytic hydrogen production system and hydrogen production method |
| CN105565268A (en) * | 2016-02-01 | 2016-05-11 | 四川中投亿星新能源科技有限公司 | Synthetic hydrogen gas preparation device |
| CN107063922A (en) * | 2017-02-27 | 2017-08-18 | 湖北洛克泰克仪器有限公司 | A kind of full-automatic Biochemical Methane Potential test system |
| WO2020087425A1 (en) * | 2018-10-30 | 2020-05-07 | 顾士平 | Hydrogen cycle-based solar hydrogen production, storage and application system |
| CN111366675A (en) * | 2018-12-25 | 2020-07-03 | 中国科学院武汉物理与数学研究所 | System and method for determining optimal value of water adsorption amount of unit photocatalyst in photocatalytic reaction |
| CN111366675B (en) * | 2018-12-25 | 2021-06-11 | 中国科学院武汉物理与数学研究所 | System and method for determining optimal value of water adsorption amount of unit photocatalyst in photocatalytic reaction |
| CN111137854A (en) * | 2020-01-16 | 2020-05-12 | 江西理工大学 | Device for photocatalytic hydrogen production |
| CN111137854B (en) * | 2020-01-16 | 2024-02-20 | 江西理工大学 | Device for producing hydrogen by photocatalysis |
| CN111701552A (en) * | 2020-06-16 | 2020-09-25 | 北京阳光凯特科技有限公司 | Multifunctional photochemical reaction experimental device |
| CN111701552B (en) * | 2020-06-16 | 2022-04-01 | 北京阳光凯特科贸有限公司 | Multifunctional photochemical reaction experimental device |
| CN113697769A (en) * | 2021-08-27 | 2021-11-26 | 山东大学 | Hydrogen production method based on heat-assisted photocatalytic system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103523750B (en) | 2015-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103523750B (en) | Reaction device and method for hydrogen production through photocatalytic water splitting | |
| CN203474447U (en) | Reaction device for hydrogen production by water photolysis | |
| CN103674156B (en) | A kind of metering method utilizing laboratory micro gas-metering device | |
| CN103927921B (en) | Hydrate Multi-functional analog experimental system under microbial action | |
| CN110231314B (en) | Online monitoring device for activated sludge | |
| CN101162222B (en) | Tester for testing the performance of new material degrading tail gas | |
| CN107098467A (en) | A kind of built-in anaerobic membrane bioreactor of integral type | |
| CN101773767A (en) | Internal circulation closed type CO2 film photocatalytic reduction reaction device and reduction method thereof | |
| CN201161189Y (en) | Multifunctional photocatalysis reactor | |
| CN203525676U (en) | Gas-liquid double-cycle reaction device for preparing glyoxylic acid by using oxygen oxidation method | |
| CN113567514A (en) | Intelligent sodium ion analyzer device with full-automatic online calibration function and online calibration method | |
| CN212882440U (en) | High-refractive-index phenyl silicone resin synthesis device | |
| CN205995345U (en) | A kind of medicament preparing tank of waste recovery containing chromium | |
| CN104226224B (en) | A kind of photocatalysis hydrogen production system and hydrogen production process | |
| CN203658271U (en) | Multi-channel rapid detecting system for aminodithioformic acid ester pesticide residue | |
| CN203642986U (en) | Metering device of laboratory trace gas | |
| CN206121410U (en) | Flue gas purification system | |
| CN204924838U (en) | Gas absorption appearance is synthesized to active carbon | |
| CN204779420U (en) | Phenol recycle device | |
| CN204389460U (en) | Photoelectrocatalysis carbon dioxide reduction reaction analyzes detection system | |
| CN204058368U (en) | A kind of intermittent type catalytic cracking experimental installation | |
| CN216549623U (en) | Device for producing hydrogen by reforming methanol and water through homogeneous catalysis | |
| CN215574929U (en) | Test device for simulating canister protecting time against steam | |
| CN104759245A (en) | Chemical reaction kettle external-circulating-type digital-display remote-transmission pH meter device | |
| CN221351075U (en) | Anaerobic sludge methane production rate measuring device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |