CN110357034A - A kind of hydrogen retrieval system and method based on metal hydride - Google Patents
A kind of hydrogen retrieval system and method based on metal hydride Download PDFInfo
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- CN110357034A CN110357034A CN201910658439.6A CN201910658439A CN110357034A CN 110357034 A CN110357034 A CN 110357034A CN 201910658439 A CN201910658439 A CN 201910658439A CN 110357034 A CN110357034 A CN 110357034A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0031—Intermetallic compounds; Metal alloys; Treatment thereof
- C01B3/0047—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof
- C01B3/0057—Intermetallic compounds; Metal alloys; Treatment thereof containing a rare earth metal; Treatment thereof also containing nickel
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention is a kind of hydrogen retrieval system and method based on metal hydride.The system includes hydrogen cylinder, one-level pressure relief valve, gas cylinder valve, hydrogen supply device valve, hydrogen supply device, hydrogen supply device pressure gauge, second depressurized valve, reset valve, hydrogen output stream meter, furnace body pressure gauge, drain tap, exhaust check valve, hydrogen retrieval valve, hydrogen retrieval flowmeter, counterbalance valve, hydrogen retrieval check valve, hydrogen storage device, oil bath, hydrogen storage device pressure gauge, hydrogen reflux check valve, the first threeway, third threeway, the 5th threeway, the 6th threeway.The present invention realizes the recycling of hydrogen in heat treatment process and recycles, and eliminates for hydrogen to be directly discharged into atmosphere and causes security risk, and has very high economic benefit.
Description
Technical field
The invention belongs to hydrogen retrieval technical field, in particular to a kind of metal hydride using two kinds of different platform pressures into
Row hydrogen retrieval and the system and method recycled.
Background technique
Hydrogen is a kind of very strong gas of reproducibility, the protection being widely used in the components annealing process of active metal
Gas, to eliminate oxidative phenomena of the workpiece in annealing process.In addition, it is anti-also chemistry can be participated in using hydrogen as a kind of reaction gas
It answers.Such as common hydrogen atmosphere furnace is mainly passed through High Purity Hydrogen in furnace body one end with certain flow velocity, the other end is straight by hydrogen
In outside atmosphere of running in.On the one hand, a large amount of High Purity Hydrogen is discharged into atmosphere will cause the wasting of resources, increase the heat of workpiece
Processing cost；On the other hand, hydrogen is a kind of inflammable and explosive gas, and aerial explosion limit is 4.0%~75.6%
(volumetric concentration), a large amount of hydrogen, which is directly discharged into air, has very big security risk.
Hydrogen bearing alloy is a kind of metal material that can be realized reversible storage hydrogen under certain condition, and hydrogen is closed by hydrogen storage
Gold is stored in inside metal lattice in a manner of metal hydride after absorbing, and has the advantage that safety is good, hydrogen storage is high-efficient.Hydrogen storage
The bulk density of alloy storage hydrogen even can reach liquid hydrogen density, therefore can realize a large amount of hydrogen in a smaller space
Storage.But hydrogen bearing alloy absorbs and releases hydrogen and generally requires to carry out under the conditions of specific temperature and Hydrogen Vapor Pressure.It is general next
It says, the gas pressure in atmosphere furnace is close with atmospheric pressure, realizes that the recycling of the gas in furnace also needs to maintain furnace inner gas pressure
With gas flow speed stability, the gentle flowed fluctuation of furnace pressure is avoided to negatively affect heat treatment process bring.According to hydrogen bearing alloy
The hydrogen in hydrogen atmosphere furnace is recycled, and realizes that the cycling and reutilization of hydrogen then needs to solve the problems, such as following two aspect: 1) needs
Metal hydride hydrogen supply and hydrogen-storing device are designed, normal pressure atmosphere heat-treatment furnace operating condition is met；2) need to develop hydrogen retrieval and
The circulatory system is realized the automatic cycle of hydrogen under the premise of not changing existing atmosphere furnace heat treatment process, is recycled.
Summary of the invention
The purpose of the present invention is for deficiency present in current techniques, provide a kind of metal hydride hydrogen recovery system and
Method.The system is closed by metal hydride hydrogen supply and hydrogen-storing device and relevant air circuit connection using high platform pressure hydrogen storage
Gold provides hydrogen source gas, absorbs hydrogen by low platform pressure hydrogen bearing alloy after atmosphere furnace, then heats low platform and press hydrogen bearing alloy
Hydrogen can be inversely transferred to high platform pressure hydrogen bearing alloy, the cycling and reutilization of hydrogen in hydrogen atmosphere heat treatment process is realized with this.
The present invention is made up of relevant apparatus, alloy design ingredient and alloy mass and hydrogen needed for atmosphere furnace in hydrogen storage device and hydrogen supply device
The research of relationship between tolerance realizes under the conditions of hydrogen atmosphere the recycling of hydrogen in heat treatment process and recycles, saves
Production cost, improves the safety of hydrogen use process.
The technical solution of the present invention is as follows:
A kind of hydrogen retrieval system based on metal hydride, the system include hydrogen cylinder, one-level pressure relief valve, gas cylinder valve,
Hydrogen supply device valve, hydrogen supply device, hydrogen supply device pressure gauge, second depressurized valve, reset valve, hydrogen output stream meter, furnace body pressure gauge, exhaust
Valve, exhaust check valve, hydrogen retrieval valve, hydrogen retrieval flowmeter, counterbalance valve, hydrogen retrieval check valve, hydrogen storage device, heating device,
Hydrogen storage device pressure gauge, hydrogen reflux check valve, the first threeway, third threeway, the 5th threeway, the 6th threeway；
The hydrogen cylinder is connected by one-level pressure relief valve, gas cylinder valve with one end of third threeway；Third threeway it is another
End is connected by hydrogen supply device valve with hydrogen supply device, and second depressurized valve, reset valve, hydrogen output stream meter are passed through in third threeway third end
It is connected with the air inlet of atmosphere furnace；The gas outlet of atmosphere furnace is connected with one end of the 5th threeway, and the other end of the 5th threeway passes through
In drain tap and exhaust check valve access outside atmosphere, hydrogen retrieval flowmeter, back pressure are successively passed through in the third end of the 5th threeway
Valve, hydrogen retrieval check valve are connect with hydrogen storage device；Hydrogen storage device is placed in heating device；Hydrogen storage device also passes through hydrogen reflux check valve and supplies
Hydrogen device is connected.
The hydrogen supply device is composed in parallel by n hydrogen container, n=1-20, and hydrogen container is provided with high platform pressure hydrogen bearing alloy
Powder, the high voltage platform hydrogen storing alloy powder chemical composition are La1-xCexNi5.2-y-zMnyAlz, wherein x=0.4-0.6, y=
0.2-0.5, z=0.1-0.3 (atomic ratio), preferably La0.5Ce0.5Ni4.7Mn0.3Al0.2；
The hydrogen storage device is composed in parallel by m hydrogen container, m=1-20, and hydrogen container is provided with low platform pressure hydrogen bearing alloy
Powder, the low-voltage plateau hydrogen storing alloy powder chemical composition are La1-uCeuNi5-v-wMnvAlw, wherein u=0.05-0.2, v=
0.3-0.7, w=0.3-0.7 (atomic ratio), preferably La0.9Ce0.1Ni4.1Mn0.5Al0.4；
Heat medium in the heating device is water, conduction oil or heating wire.
Alloyed powder theory gross mass in the hydrogen supply device or hydrogen storage device according in atmosphere furnace use process throughput and
Duration of ventilation determines, is specifically calculated as follows:
Wherein W is required alloy gross mass (kg), and Q is gas flow (L/min), and t is duration of ventilation (min), and ω is storage
The effective hydrogen storage capability of hydrogen alloy (wt.%)；For the hydrogen bearing alloy in hydrogen supply device, effective hydrogen storage capability ω is 30 DEG C of conditions
Lower alloy corresponding hydrogen content under 1MPa hydrogen power in the difference under 0.15MPa hydrogen power between corresponding hydrogen content；It is right
For hydrogen bearing alloy in hydrogen storage device, corresponding hydrogen content under 0.1MPa hydrogen power when effective hydrogen storage capability ω is 30 DEG C of conditions
The difference under hydrogen release to 1MPa hydrogen power between corresponding hydrogen content is heated with alloy.
A kind of hydrogen retrieval method based on metal hydride, the method includes the steps of:
A) it is packed into the fire door for closing atmosphere furnace after workpiece to be processed in atmosphere furnace, keeps hydrogen supply device valve and hydrogen retrieval valve
Door is closed, and hydrogen bottle valve is opened, and opens gas cylinder valve and drain tap, and adjusting reset valve enters hydrogen in furnace, gas stream
Amount is 3-20L/min, and furnace air is discharged in ventilation 10-30min；
B) gas cylinder valve and drain tap are closed, while opening hydrogen supply device valve and hydrogen retrieval valve, system turns by hydrogen supply
Device hydrogen supply, hydrogen absorb storage by the hydrogen bearing alloy in hydrogen storage device after atmosphere furnace；High platform pressure hydrogen storage in hydrogen supply device is closed
The effective working pressure range of gold at room temperature is 0.15-1MPa, and the low platform pressure hydrogen bearing alloy in hydrogen storage device is in room temperature
Under the conditions of suction hydrogen working pressure range be 0.01-0.1MPa；Heat treatment operation needed for then being carried out to atmosphere furnace；
C) when atmosphere heat treatment time and gas flow have been more than hydrogen bearing alloy weight configuration index, the amount of required hydrogen
Greater than the hydrogen storage capability of high platform pressure hydrogen bearing alloy in hydrogen supply device, when the hydrogen pressure in hydrogen supply device is lower than 0.15MPa, pass through switching
Gas cylinder valve and hydrogen supply device valve select to continue with hydrogen cylinder hydrogen supply；Equally, when the pressure in hydrogen storage device reaches 0.1MPa
Show that the low platform pressure hydrogen bearing alloy in hydrogen storage device inhales hydrogen and has reached hydrogen storage capability, passes through switching drain tap and hydrogen retrieval valve
Subsequent hydrogen is discharged in outdoor air；
D) after being heat-treated, gas cylinder valve, hydrogen supply device valve, drain tap, hydrogen retrieval valve and reset valve are closed,
Control control hydrogen storage device heating system is started to warm up with the heating rate of 1-5 DEG C/min, and heating temperature range is 50-250 DEG C, heated
Gas pressure in journey in hydrogen storage device is gradually increasing；When the gas pressure in hydrogen storage device reaches the gas in hydrogen supply device under room temperature
When body pressure, reflux check valve is automatically turned on, and the hydrogen in hydrogen storage device is absorbed after the check valve that flows back by the alloy in hydrogen supply device
Storage；
E) continue heating hydrogen storage device and keep the temperature 10- under Current Temperatures when gas pressure reaches 1MPa in hydrogen storage device
30min keeps the pressure in hydrogen storage device and hydrogen supply device equal, and the hydrogen recycled in hydrogen storage device at this time has been transferred in hydrogen supply device；Then
It closes heating device power supply and can proceed with heat treatment process next time to hydrogen storage device cooled to room temperature.
Substantive distinguishing features of the invention are as follows:
1, the present invention devises a set of metal hydride hydrogen supply and hydrogen-storing device, can satisfy normal pressure atmosphere heat-treatment furnace work
Make condition；
2, hydrogen bearing alloy absorbs and releases hydrogen and needs certain pressure, and atmosphere furnace usually works under normal pressure, if
It counts relevant air circuit connection and proposes thermodynamics and reversible hydrogen storage capacity that hydrogen bearing alloy should meet, meet hydrogen in heat treatment process
So that hydrogen is transferred to hydrogen supply device by hydrogen storage device after the automatic release and absorption, and heat treatment of gas, realizes that recycling for hydrogen is this
One innovative point of invention；The present invention uses two kinds of metal hydrides as hydrogen supply and hydrogen-absorbing material, real in conjunction with suitable gas circuit
Recycling for existing hydrogen is same with novelty.
The beneficial effects of the present invention are:
1, Gao Ping is used at room temperature as hydrogen absorption and storage medium using two kinds of hydrogen bearing alloys with different platform pressure
Platform presses hydrogen bearing alloy to provide hydrogen, absorbs hydrogen by low platform pressure hydrogen bearing alloy after circulation, then heats low platform pressure hydrogen storage and closes
Gold makes hydrogen be automatically transferred to high platform hydrogen bearing alloy, realize under the conditions of hydrogen atmosphere in heat treatment process the automatic recycling of hydrogen and
It recycles, avoids the waste of hydrogen resources；
2, existing hydrogen atmosphere heat treatment process is will to be directly discharged into atmosphere from the hydrogen being discharged in furnace, using this hair
The hydrogen retrieval system and method for bright offer realizes the recycling of hydrogen in heat treatment process and recycles, and eliminates hydrogen is direct
It is discharged into atmosphere and causes security risk.
3, the hydride hydrogen-storing method that the present invention uses is to improve the safety of hydrogen storage with solid-state approach hydrogen storage
Property, alloy itself is nontoxic, and in air, burning or explosion phenomenon will not occur for even powder exposure, using hydrogen storage
It is reliable that alloy recycles hydric safe；In addition, hydrogen bearing alloy generally has very high cycle life, thousands of times of charge and discharge hydrogen repeatedly are held
Amount still will not decay, therefore whole system is reliable and stable；Heat treatment process hydrogen recovery efficiency is close to 100%；With system
The increase of service life can significantly save hydrogen use cost.Single heat treatment process save the cost of the present invention is about 150 yuan,
Under thousands of service life, production 200-300 times is recoverable system cost, has very high economic benefit.
Detailed description of the invention
Fig. 1 is hydrogen retrieval system principle of the present invention and structural schematic diagram；
Wherein, 1- hydrogen cylinder, 2- one-level pressure relief valve, 3- gas cylinder valve, 4- hydrogen supply device valve, 5- hydrogen supply device, 6- hydrogen supply device
Pressure gauge, 7- second depressurized valve, 8- reset valve, 9- hydrogen output stream meter, 10- furnace body pressure gauge, 11- atmosphere furnace, 12- exhaust valve
Door, 13- exhaust check valve, 14- hydrogen retrieval valve, 15- hydrogen retrieval flowmeter, 16- counterbalance valve, 17- hydrogen retrieval check valve, 18-
Hydrogen storage device, 19- oil bath, 20- hydrogen storage device pressure gauge, 21- hydrogen reflux check valve, the first threeway of 22-, the second threeway of 23-, 24-
Third threeway, the 4th threeway of 25-, the 5th threeway of 26-, the 6th threeway of 27-, the 7th threeway (28) of 28-.
Fig. 2 is that high platform presses P-C-T curve of the hydrogen bearing alloy at 30 DEG C in embodiment.
Fig. 3 is that low platform presses P-C-T curve of the hydrogen bearing alloy at 30 DEG C in embodiment.
Fig. 4 is that low platform presses P-C-T curve of the hydrogen bearing alloy at 180 DEG C in embodiment.
Specific embodiment
Below with reference to embodiment, the present invention is further described in detail.
The hydrogen retrieval system of metal hydride of the present invention is as shown in Figure 1, include hydrogen cylinder (1), one-level pressure relief valve
(2), gas cylinder valve (3), hydrogen supply device valve (4), hydrogen supply device (5), hydrogen supply device pressure gauge (6), second depressurized valve (7), reset valve
(8), hydrogen output stream meter (9), furnace body pressure gauge (10), drain tap (12), exhaust check valve (13), hydrogen retrieval valve
(14), hydrogen retrieval flowmeter (15), counterbalance valve (16), hydrogen retrieval check valve (17), hydrogen storage device (18), oil bath (19), hydrogen storage
Device pressure gauge (20), hydrogen reflux check valve (21), the first threeway (22), third threeway (24), the 5th threeway (26), the 6th threeway
(27)。
The hydrogen cylinder (1) is connected by one-level pressure relief valve (2), gas cylinder valve (3) with one end of third threeway (24)；The
The other end of three threeways (24) is connected by hydrogen supply device valve (4) with hydrogen supply device (5), and second level is passed through at third threeway (24) third end
Pressure reducing valve (7), reset valve (8), hydrogen output stream meter (9) are connected with the air inlet of atmosphere furnace (11)；The outlet of atmosphere furnace (11)
Mouth is connected with one end of the 5th threeway (26), and the other end of the 5th threeway (26) passes through drain tap (12) and exhaust check valve
(13) it accesses in outside atmosphere, hydrogen retrieval flowmeter (15), counterbalance valve (16), hydrogen are successively passed through in the third end of the 5th threeway (26)
Recycling check valve (17) is connect with hydrogen storage device (18)；Hydrogen storage device (18) setting, can be by adding in oil bath in oil bath (19)
Hot device heating；Hydrogen storage device (18) is also connected by hydrogen reflux check valve (21) with hydrogen supply device (5).
The hydrogen supply device (5) is composed in parallel by n hydrogen container, n=1-20, and hydrogen container is provided with high platform pressure hydrogen storage and closes
Bronze, the high voltage platform hydrogen storing alloy powder chemical composition are La1-xCexNi5.2-y-zMnyAlz, wherein x=0.4-0.6, y=
0.2-0.5, z=0.1-0.3 (atomic ratio), preferably La0.5Ce0.5Ni4.7Mn0.3Al0.2；The hydrogen storage device (18) is by m hydrogen storage
Tank composes in parallel, m=1-20, and hydrogen container is provided with low platform pressure hydrogen storing alloy powder, the low-voltage plateau hydrogen bearing alloy dusting
Group becomes La1-uCeuNi5-v-wMnvAlw, wherein u=0.05-0.2, v=0.3-0.7, w=0.3-0.7 (atomic ratio), preferably
La0.9Ce0.1Ni4.1Mn0.5Al0.4.The high platform pressure hydrogen bearing alloy and low platform pressure hydrogen bearing alloy are well known materials, such as logical
The vacuum smelting method for crossing " hydrogen storage material " (beard dragon, Chemical Industry Press, 2002) statement is prepared, and uses gas
Stream mill is broken for 50-200 mesh powder.
High pressure gas in the hydrogen cylinder (1) passes through one-level pressure relief valve (2) by pressure reduction to 1-3MPa, by gas cylinder
Valve (3) accesses gas circuit by third threeway (24)；Hydrogen cylinder (1) temporarily can provide hydrogen source gas for system, while can be
Hydrogen supply device (5) hydrogen make-up.
The hydrogen supply device (5) uses at room temperature, accesses gas circuit by the first threeway (22)；Alloyed powder theory gross mass
By in actual use throughput and duration of ventilation determine, be specifically calculated as follows:
Wherein W1It is gas flow (L/min) for required alloy gross mass (kg), Q, t is duration of ventilation (min), ω1For height
Platform presses the effective hydrogen storage capability of hydrogen bearing alloy (wt.%)；For the high platform in hydrogen supply device (5) presses hydrogen bearing alloy, effectively
Hydrogen storage capability ω1Alloy corresponding hydrogen content under 1MPa hydrogen power is corresponding under 0.15MPa hydrogen power under the conditions of being 30 DEG C
Hydrogen content between difference, can be obtained by the P-C-T curve of alloy at such a temperature.
The hydrogen supply device pressure gauge (6) is used to show the Hydrogen Vapor Pressure in hydrogen supply device (5), by the second threeway (23) access gas
Road；Hydrogen in hydrogen supply device (5) can enter second depressurized valve (7) by hydrogen supply device valve (4), and gas pressure is made to be reduced to 0.1-
0.2MPa, reset valve (8) can be with accuracy controlling hydrogen flowing quantities；Gas enters atmosphere furnace (11) through hydrogen output stream meter (9), furnace body
Pressure gauge (10) accesses gas circuit by the 4th threeway (25), can indicate the intracorporal gas pressure of furnace；By switching gas cylinder valve (3)
Unlatching with hydrogen supply device valve (4) can choose atmosphere furnace by hydrogen cylinder (1) or hydrogen supply device (5) hydrogen supply；When hydrogen supply device (5) interior gas
When body surplus deficiency, can open gas cylinder valve (3) and hydrogen supply device valve (4) simultaneously with hydrogen cylinder (1) is in hydrogen supply device (5)
Hydrogen bearing alloy is flushed with hydrogen.
The drain tap (12) is by opening exhaust valve in the 5th threeway (26) and exhaust check valve (13) access atmosphere
After door (12) and closing hydrogen retrieval valve (14), hydrogen is discharged into air, and exhaust check valve (13) can prevent air inversion；Hydrogen storage device
(18) gas circuit is accessed by the 6th threeway (27), when drain tap (12) are closed and hydrogen retrieval valve (14) is opened, in atmosphere furnace
The hydrogen of outflow is flowed into hydrogen storage device (18) by hydrogen retrieval flowmeter (15), counterbalance valve (16) and hydrogen retrieval check valve (17),
It is stored in a manner of solid metal hydride after being absorbed by low platform pressure hydrogen bearing alloy；Described counterbalance valve (16) cracking pressure should be omited
Higher than atmospheric pressure (such as 0.1-0.12MPa), when furnace inner gas pressure is higher than back pressure valve opening pressure, hydrogen can pass through back pressure
Valve (16) and hydrogen retrieval check valve (17) flow into hydrogen storage device (18)；The gas when furnace inner gas pressure is lower than back pressure valve opening pressure
Body cannot flow through counterbalance valve, make to form negative pressure in atmosphere furnace (11) after hydrogen storage device (18) can be prevented to absorb hydrogen.
The hydrogen storage device pressure gauge (20) accesses gas circuit by the 7th threeway (28), can indicate the hydrogen in hydrogen storage device (18)
Pressure；Hydrogen storage device (18) can be heated by oil bath (19), and the rate of heat addition is 1-5 DEG C/min, heating temperature range 50-250
℃；The hydrogen sucting platform pressure range of low platform pressure hydrogen bearing alloy at room temperature in the hydrogen storage device (18) is 0.01-
0.1MPa；Low platform pressure hydrogen bearing alloy in the hydrogen storage device (18) also needs to meet the hydrogen desorption plateau pressure at 50-250 DEG C
Range is 1-5MPa, can be inversely flushed with hydrogen into hydrogen supply device (5) after realizing heating hydrogen storage device (18) with this；In the hydrogen storage device (18)
Low platform pressure hydrogen storing alloy powder theory gross mass is equally determined by throughput in actual use and duration of ventilation, is specifically pressed
Formula calculates:
Wherein W2Hydrogen bearing alloy gross mass (kg) is pressed for required low platform, Q is gas flow (L/min), and t is duration of ventilation
(min), ω2The effective hydrogen storage capability of hydrogen bearing alloy (wt.%) is pressed for low platform；Hydrogen storage is pressed for the low platform in hydrogen storage device (18)
For alloy, effective hydrogen storage capability ω2Corresponding hydrogen content and alloy heat hydrogen release under 0.1MPa hydrogen power when for 30 DEG C of conditions
Afterwards in the difference under 1MPa hydrogen power between corresponding hydrogen content, can be obtained by P-C-T curve of the alloy under above-mentioned different temperatures
?.Since duration of ventilation is identical with gas flow, quality needed for high platform presses hydrogen bearing alloy and low platform pressure hydrogen bearing alloy is full
Foot formula:
The P-C-T curve of the high platform pressure and low platform pressure hydrogen bearing alloy at different temperatures can be surveyed by Sievert's
It tries equipment to obtain, such as the PCT Pro-2000 gas absorption measuring instrument of French SETARAM company, Suzuki commercial office can be used
Hydrogen storage material PCT tester, Beijing Yi Youkai Science and Technology Ltd. the equipment such as AGAS material adsorbed gas performance evaluation instrument
Test.
Embodiment 1
The present invention selects round ambient anneal furnace as objective for implementation, and furnace chamber diameter is 0.2m, and furnace chamber length is 2m, annealing
Temperature is 950 DEG C, and heating rate is about 20 DEG C/min, soaking time 5h, and heat preservation terminates rear furnace body cooled to room temperature.
Two kinds of hydrogen bearing alloys with different platform pressure are contained in the embodiment of the present invention, wherein high platform pressure hydrogen storage is closed
Golden chemical composition is La0.5Ce0.5Ni4.7Mn0.3Al0.2(atomic ratio), low platform pressure hydrogen bearing alloy chemical composition are
La0.9Ce0.1Ni4.1Mn0.5Al0.4(atomic ratio).The alloy of above two heterogeneity is prepared using vacuum smelting method first,
It then is alloy powder that average grain diameter is 100 microns by above-mentioned alloy breaks down with airflow milling.It is tested with Sievert's equipment
The suction hydrogen and hydrogen release P-C-T curve of two kinds of alloys at different temperatures, as a result as shown in attached drawing 2, attached drawing 3 and attached drawing 4.High platform
Pressing hydrogen desorption plateau pressure of the hydrogen bearing alloy at 30 DEG C is about 0.5MPa, it is ensured that hydrogen storage device has certain output pressure；This
Outside, the hydrogen sucting platform pressure of high platform pressure hydrogen bearing alloy is about 0.7MPa, is in a reasonable range, can make hydrogen storage device
(18) it is easier to reach the suction hydrogen pressure of hydrogen supply device (5) interior alloy after heating, realizes that hydrogen is turned from hydrogen storage device (18) into hydrogen supply device (5)
It moves.By attached drawing 3 it can be seen that hydrogen sucting platform pressure of the low platform pressure hydrogen bearing alloy at 30 DEG C is about 0.04MPa, it is higher than this pressure
Alloy can inhale rapidly hydrogen when power；When balancing pressure and reaching 0.1MPa, hydrogen-sucking amount is up to 1wt.% or more.It is low flat at 180 DEG C
It is about 1.4MPa that platform, which presses the hydrogen desorption plateau pressure of hydrogen bearing alloy, presses the suction hydrogen pressure of hydrogen bearing alloy at room temperature higher than high platform,
Therefore the alloy in hydrogen storage device (18) be saturated after suction hydrogen at room temperature be again heated to 180 DEG C can the alloy into hydrogen supply device (5) fill
Hydrogen.2 it can calculate the high platform pressure hydrogen bearing alloy (La in hydrogen supply device (5) with reference to the accompanying drawings0.5Ce0.5Ni4.7Mn0.3Al0.2) effectively
Hydrogen storage capability ω1For 0.94wt.%；Equally, 3 the low platform pressure in hydrogen storage device (18) can be calculated with attached drawing 4 with reference to the accompanying drawings
Hydrogen bearing alloy (La0.9Ce0.1Ni4.1Mn0.5Al0.4) effectively hydrogen storage capability ω2For 0.78wt.%.The present embodiment designs gas flow
For 5L/min, duration of ventilation 20h, then Theoretical Mass needed for can be calculated the high platform pressure hydrogen bearing alloy in hydrogen supply device (5)
For 57kg, Theoretical Mass needed for the low platform pressure hydrogen bearing alloy in hydrogen storage device (18) is 68kg.Hydrogen supply device (5) in the present embodiment
Actual use amount with alloy in hydrogen storage device (18) is respectively 60kg and 70kg, slightly above Theoretical Mass.
Hydrogen supply device (5) in the present embodiment is composed in parallel by the high-pressure cylinder of 6 2L, and inside is filled with the high platform of 60kg
Press hydrogen storing alloy powder；Hydrogen storage device (18) is composed in parallel by the high-pressure cylinder of 7 2L, and inside is filled with the low platform pressure of 70kg
Hydrogen storing alloy powder.Hydrogen storage device is before use, be both needed to by 1-2 complete suction hydrogen and hydrogen release circulation, to guarantee that alloy is sufficiently lived
Change, reaches normal using effect.Hydrogen supply device is placed in room temperature environment, be should be at saturation before use and is inhaled hydrogen state；Hydrogen storage device is set
In in the thermostatical oil bath (19) of 50L, it should be heated before use and empty the hydrogen of absorption.Oil bath (19) has automatic temperature-controlled function
Can, heating power 5kW, heat-conducting medium selects DOW CORNING PMX-200 type dimethicone.
Gas circuit is connected according to attached piping diagram shown in FIG. 1, wherein connecting pipe is 6mm stainless steel pressure piping, hydrogen cylinder
It (1) is 40L high pressure gas cylinder, rated pressure 15MPa；Gas cylinder valve (3), hydrogen supply device valve (4), drain tap (12), hydrogen return
Receiving valve (14) is two pass ball valves；One-level pressure relief valve (2) output pressure is set as 2.5MPa, second depressurized valve (7) output pressure
Power is set as 0.15MPa；Hydrogen output stream meter (9) and hydrogen retrieval flowmeter (15) are hydrogen Special rotor flowmeter, range
For 0-10L/min；Counterbalance valve (16) cracking pressure is set as 0.11MPa；Hydrogen supply device pressure gauge (6) and hydrogen storage device pressure gauge (20)
Range is 0-6MPa, and furnace body pressure gauge (10) range is -0.1-0.25MPa.
The hydrogen retrieval of the metal hydride systematically application method, comprising the following steps:
A) fire door is closed after being packed into workpiece to be processed in atmosphere furnace (11), keeps hydrogen supply device valve (4) and hydrogen retrieval valve
Door (14) is closed, and hydrogen cylinder (1) valve is opened, and opens gas cylinder valve (3) and drain tap (12), and adjusting reset valve (8) makes hydrogen
Gas enters in furnace, gas flow 5L/min, and furnace air is discharged in ventilation 15min；
B) gas cylinder valve (3) and drain tap (12) are closed, while opening hydrogen supply device valve (4) and hydrogen retrieval valve
(14), system turns by hydrogen supply device (5) hydrogen supply；Simultaneously adjust annealing furnace temperature, make annealing furnace with the heating rate of 10 DEG C/min from
Room temperature is started to warm up to 950 DEG C, is closed annealing furnace heating system after keeping the temperature 10h, is made furnace body natural cooling, in furnace body cooling procedure
Continue to keep hydrogen gas stream；Hydrogen absorbs storage by the hydrogen bearing alloy in hydrogen storage device (18) after atmosphere furnace (11)；Hydrogen supply device
(5) the effective working pressure range of high platform pressure hydrogen bearing alloy at room temperature in is 0.15-1MPa, and hydrogen storage device (18) is interior
Low platform pressure hydrogen bearing alloy suction hydrogen working pressure range at room temperature be 0.01-0.1MPa.
If c) temporarily extending annealing time or increasing hydrogen flowing quantity, the hydrogen pressure in hydrogen supply device (5) can when being lower than 0.15MPa
It selects to continue by switching gas cylinder valve (3) and hydrogen supply device valve (4) with hydrogen cylinder hydrogen supply；Equally, if in hydrogen storage device (18)
Pressure close to 0.1MPa when show in hydrogen storage device (18) low platform pressure hydrogen bearing alloy inhale hydrogen and have reached theoretical hydrogen storage capability, can
Subsequent hydrogen is discharged in outdoor air by switching drain tap (12) and hydrogen retrieval valve (14)；D) heat treatment finishes
Afterwards, gas cylinder valve (3), hydrogen supply device valve (4), drain tap (12), hydrogen retrieval valve (14) and reset valve (8), control are closed
Liquefaction bath (19) is started to warm up with the heating rate of 3 DEG C/min, and the gas pressure in heating process in hydrogen storage device (18) is gradually
Rise；When the gas pressure in hydrogen storage device (18) reaches the gas pressure in hydrogen supply device (5) under room temperature, flow back check valve
(21) it automatically turns on, the hydrogen in hydrogen storage device (18) is stored after check valve (21) by flow back by the alloy absorption in hydrogen supply device (5)；
E) continue to heat hydrogen storage device (18), when gas pressure reaches 1MPa, oil bath (19) stops heating, and current
At a temperature of keep the temperature 30min, so that the pressure in hydrogen storage device (18) and hydrogen supply device (5) is reached balance, recycling in hydrogen storage device (18) at this time
Hydrogen have been transferred in hydrogen supply device (5)；Be then turned off oil bath (19) heating device, to oil bath (19) and hydrogen storage device (8) from
It is so cooled to room temperature, can proceed with heat treatment process next time.
In above-described embodiment, the heating-up time is about 1.5h, and soaking time 10h, temperature fall time is about 4h, then when total ventilation
Between about 15.5h, hydrogen flowing quantity 5L/min, then single heat treatment process save hydrogen 4650L (about 15MPa pressure 40L hold
The 78% of product standard steel cylinder).After heat treatment, oil bath heating process is about 1h, and the electric energy of consumption is about 5kwh.If single bottle
High-purity hydrogen cost is 200 yuan, and the 5kwh cost of electric energy is about 5 yuan, then single heat treatment process save the cost is about 150 yuan, raw
Produce i.e. 200-300 recoverable system cost.
It should be noted that the present embodiment only remarks additionally to the present invention, more so as to those skilled in the art staff
Understand that the content of present invention, hydrogen retrieval technical solution provided by the invention are equally applicable to hydrogen as protection gas or reaction gas well
Vacuum atmosphere oven and all kinds of reactors etc..
Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of hydrogen retrieval system based on metal hydride, it is characterized in that the system includes hydrogen cylinder, one-level pressure relief valve, gas cylinder
Valve, hydrogen supply device valve, hydrogen supply device, hydrogen supply device pressure gauge, second depressurized valve, reset valve, hydrogen output stream meter, furnace body pressure
Table, exhaust check valve, hydrogen retrieval valve, hydrogen retrieval flowmeter, counterbalance valve, hydrogen retrieval check valve, hydrogen storage device, adds drain tap
Thermal, hydrogen storage device pressure gauge, hydrogen reflux check valve, the first threeway, third threeway, the 5th threeway, the 6th threeway；
The hydrogen cylinder is connected by one-level pressure relief valve, gas cylinder valve with one end of third threeway；The other end of third threeway passes through
It crosses hydrogen supply device valve to be connected with hydrogen supply device, second depressurized valve, reset valve, hydrogen output stream meter and gas are passed through in third threeway third end
The air inlet of atmosphere furnace is connected；The gas outlet of atmosphere furnace is connected with one end of the 5th threeway, and the other end of the 5th threeway is by exhaust
In valve and exhaust check valve access outside atmosphere, hydrogen retrieval flowmeter, counterbalance valve, hydrogen are successively passed through in the third end of the 5th threeway
Recycling check valve is connect with hydrogen storage device；Hydrogen storage device is placed in heating device；Hydrogen storage device also passes through hydrogen reflux check valve and hydrogen supply device
It is connected.
2. the hydrogen retrieval system as belonging to claim 1 based on metal hydride, it is characterized in that the hydrogen supply device is stored up by n
Hydrogen tank composes in parallel, n=1-20, and hydrogen container is provided with high platform pressure hydrogen storing alloy powder, the high voltage platform hydrogen storing alloy powder
Chemical composition is La1-xCexNi5.2-y-zMnyAlz, wherein x=0.4-0.6, y=0.2-0.5, z=0.1-0.3 (atomic ratio)；
The hydrogen storage device is composed in parallel by m hydrogen container, m=1-20, and hydrogen container is provided with low platform pressure hydrogen storing alloy powder, institute
The low-voltage plateau hydrogen storing alloy powder chemical composition stated is La1-uCeuNi5-v-wMnvAlw, wherein u=0.05-0.2, v=0.3-0.7,
W=0.3-0.7 (atomic ratio).
3. the hydrogen retrieval system as belonging to claim 1 based on metal hydride, it is characterized in that in the heating device
Heat medium is water, conduction oil or heating wire.
4. the hydrogen retrieval system as belonging to claim 1 based on metal hydride, it is characterized in that the high voltage platform hydrogen storage
The preferred La of alloyed powder chemical composition0.5Ce0.5Ni4.7Mn0.3Al0.2；The low-voltage plateau hydrogen storing alloy powder chemical composition is preferred
La0.9Ce0.1Ni4.1Mn0.5Al0.4。
5. a kind of hydrogen retrieval method based on metal hydride, it is characterized in that the method includes the steps of:
A) it is packed into the fire door for closing atmosphere furnace after workpiece to be processed in atmosphere furnace, hydrogen supply device valve and hydrogen retrieval valve is kept to close
It closes, opens hydrogen bottle valve, open gas cylinder valve and drain tap, adjusting reset valve enters hydrogen in furnace, and gas flow is
Furnace air is discharged in 3-20L/min, ventilation 10-30min；
B) gas cylinder valve and drain tap are closed, while opening hydrogen supply device valve and hydrogen retrieval valve, system turns to be supplied by hydrogen supply device
Hydrogen, hydrogen absorb storage by the hydrogen bearing alloy in hydrogen storage device after atmosphere furnace；High platform pressure hydrogen bearing alloy in hydrogen supply device exists
Effective working pressure range under room temperature is 0.15-1MPa, and the low platform pressure hydrogen bearing alloy in hydrogen storage device is in room temperature condition
Under suction hydrogen working pressure range be 0.01-0.1MPa；Heat treatment operation needed for then being carried out to atmosphere furnace；
C) when atmosphere heat treatment time and gas flow have been more than hydrogen bearing alloy weight configuration index, the amount of required hydrogen is greater than
High platform presses the hydrogen storage capability of hydrogen bearing alloy in hydrogen supply device, when the hydrogen pressure in hydrogen supply device is lower than 0.15MPa, passes through and switches gas cylinder
Valve and hydrogen supply device valve select to continue with hydrogen cylinder hydrogen supply；Equally, show when the pressure in hydrogen storage device reaches 0.1MPa
In hydrogen storage device low platform pressure hydrogen bearing alloy inhale hydrogen have reached hydrogen storage capability, by switching drain tap and hydrogen retrieval valve by
Subsequent hydrogen is discharged in outdoor air；
D) after being heat-treated, gas cylinder valve, hydrogen supply device valve, drain tap, hydrogen retrieval valve and reset valve, control control are closed
Hydrogen storage device heating system is started to warm up with the heating rate of 1-5 DEG C/min, and heating temperature range is 50-250 DEG C, in heating process
Gas pressure in hydrogen storage device is gradually increasing；When the gas pressure in hydrogen storage device reaches the gas pressure in hydrogen supply device under room temperature
When power, reflux check valve is automatically turned on, and the hydrogen in hydrogen storage device absorbs storage by the alloy in hydrogen supply device after the check valve that flows back；
E) continue heating hydrogen storage device to keep the temperature 10-30min when gas pressure reaches 1MPa in hydrogen storage device under Current Temperatures, make
Pressure in hydrogen storage device and hydrogen supply device is equal, and the hydrogen recycled in hydrogen storage device at this time has been transferred in hydrogen supply device；It is then turned off heating
Installation's power source continues heat treatment process next time to hydrogen storage device cooled to room temperature.
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| US6593017B1 (en) * | 2002-01-30 | 2003-07-15 | Energy Conversion Devices, Inc. | High capacity calcium lithium based hydrogen storage material and method of making the same |
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