CN1390625A - Method and equipment using hydrogen bearing alloy slurry for continuously absorbing and releasing hydrogen gas - Google Patents
Method and equipment using hydrogen bearing alloy slurry for continuously absorbing and releasing hydrogen gas Download PDFInfo
- Publication number
- CN1390625A CN1390625A CN 01120906 CN01120906A CN1390625A CN 1390625 A CN1390625 A CN 1390625A CN 01120906 CN01120906 CN 01120906 CN 01120906 A CN01120906 A CN 01120906A CN 1390625 A CN1390625 A CN 1390625A
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- Prior art keywords
- tower
- hydrogen
- absorption
- slurry
- gas
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 88
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 88
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002002 slurry Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000001996 bearing alloy Substances 0.000 title claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 title claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 36
- 239000007789 gas Substances 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 238000003795 desorption Methods 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 3
- MECMQNITHCOSAF-UHFFFAOYSA-N manganese titanium Chemical compound [Ti].[Mn] MECMQNITHCOSAF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 229910052987 metal hydride Inorganic materials 0.000 description 5
- 150000004681 metal hydrides Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Gas Separation By Absorption (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
An equipment for continuously absorbing and releasing hydrogen by hydrogen-bearing alloy slurry is composed of absorption tower, two flash towers, deabsorption tower, slurry tank and slurry pump. Its method features that under the drive of slurry pump, the slurry which is the mixture of hydrogen bearing alloy and organic solvent and the hydrogen contained gas flow through said 4 towers in opposite direction while is contacted with each other for continuously absorbing and releaving hydrogen. Its advantages are less investment and high productivity.
Description
The present invention relates to utilize metal hydride to absorb and the method and the device of releasing hydrogen gas.
So far, the method with metal hydride separation, recover hydrogen has two kinds:
A kind of method be react with hydrogen-containing gas with the solid hydrogen-storing alloy material separate, recover hydrogen, Gu adopt the device of this method that various gas-reaction beds are arranged, one section in four towers and two sections metal hydride hydrogen device for continuously recycling of four towers of for example having Japanese Patent JP55-56001 to propose are used for from the hydrogen manufacturing of stone refinery gas tail gas; Tail gas hydrogen recovery unit (L.J.Kaplan speeds to put with the ammonia that MPD technology company develops jointly in U.S.'s air products and chemical company, Chem.Eng., 89,1982, p34 and J.J.SheridanIIIet al., J.Less-CommonMetals, 89,1083, p447) and a kind of method and device that utilizes synthesis ammonia plant emptying gas mixture to make High Purity Hydrogen of providing of Chinese invention patent ZL92108324.6.Owing to the solid hydrogen-storing metallic substance is the cracked powder that is after hydrogenation first, and volumetric expansion constantly takes place and causes the efflorescence sustainable development in hydrogen storing alloy powder in inhaling the hydrogen process repeatedly, and line clogging in the device, powder are piled up in container until bursting container; On the other hand, (suitable with glass, sand) can not effectively discharge reaction heat when inhaling hydrogen because the metal hydride powder poor thermal conductivity, can not import enough heats effectively when putting hydrogen, therefore can't bring into play the due efficient of device.In addition, Gu all these class gas-reactive systems are periodical operation, form production system by a plurality of metal hydrides, the some of them bed is in inhales the hydrogen operation, other beds (it is saturated to have inhaled hydrogen) then are in puts the hydrogen operation, so reaches near continuous operation by switching.Obviously, this system has equipment complexity, inefficient shortcoming.
Another kind method is with the fluidised method separation of hydrogen storage metal, recover hydrogen, as R.D.Holstvoogdet al., and Z.fur Phxs.Chemie Neue Folge, 164,1989, p1429 provides and has used LaNi
5Form storage hydrogen slurries with silicone oil, the device that utilization is made up of absorption tower, desorption tower and the slush pump absorption hydrogen of working continuously, valve tray column is selected on its absorption tower for use, desorption tower is one and has the thermal compressor that pulsation is stirred, owing to use valve tray column as the absorption tower, annex is too much on the plate, deposits so stagnate onboard when being easy to make solid particulate in the hydrogen bearing alloy slurry to flow, and desorption tower must need the certain energy input in addition.Te Kaiping 6-174196 provides another kind of and has absorbed hydrogen with the hydrogen storage metal fluidization, and its storage hydrogen slurries are by LaNi
5Form with silicone oil or n-undecane, adopt the device batch operation of forming by reactor (be used for hydrogen simultaneously and absorb and take off suctions), heat exchanger and the slush pump of belt stirrer to inhale and put hydrogen, want the successive suction and put hydrogen and then need multiple arrangement to carry out the switching of complexity.
In view of above-mentioned, the objective of the invention is to propose a kind of method that can conveniently realize with hydrogen bearing alloy slurry continuous absorption and releasing hydrogen gas.
Another object of the present invention is to design a kind of simple in structure, reduced investment, fluidised form good fluidity, device that efficient is high for the method for implementing above-mentioned proposition.
The method of utilizing hydrogen bearing alloy slurry continuous absorption and releasing hydrogen gas of the present invention, it is characterized in that hydrogen storage alloy and organic solvent blended slurries are driven with slush pump, pass through the absorption tower successively, first flashing tower, second flashing tower, desorption tower four-column process flow contact with the hydrogen-containing gas of countercurrent flow, at room temperature carry out continuous absorption and releasing hydrogen gas.
Said hydrogen storage alloy can be the binary or the multicomponent alloy of mishmetal-nickel system, also can be the binary or the multicomponent alloy of ferrotianium system or titanium manganese system, above-mentioned these alloys are at room temperature inhaled the equilibrium pressure≤1.5MPa of hydrogen, and the equilibrium pressure of putting hydrogen is 0.1～1.4MPa.Generally, so that to adopt granularity be 50～400 purpose hydrogen storing alloy powders for well.Organic solvent can be to clean kerosene or diesel oil or silicone oil.Hydrogen-containing gas comprises various industrial tail gas hydrogen, hydrogeneous gas mixture or industrial general hydrogen.
Usually, making the content of hydrogen storage alloy is 10～70% of slurries gross weight.
For implement device that the inventive method designs comprise successively with pipeline be linked to be path absorption tower, first flashing tower, second flashing tower, desorption tower, slurry tank and slush pump, above each tower, be provided with the slurry feed mouth, the below of each tower is provided with the slurries discharge port, the top of each tower is provided with blow-off valve respectively, on the connecting tube between tower and the tower, be respectively equipped with reducing valve, inlet mouth is arranged below the absorption tower.
During work, hydrogeneous source of the gas enters the absorption tower from below, absorption tower inlet mouth, contact with organic solvent blended slurries with the hydrogen storage alloy of countercurrent flow, hydrogen is absorbed by hydrogen bearing alloy slurry and discharges tail gas, and the slurries behind the suction hydrogen flow through two flashing towers successively, remove impurity gas wherein, flow into release hydrogen in the desorption tower at last, so finish a process of inhaling hydrogen and putting hydrogen, when hydrogeneous source of the gas constantly enters, and slurries return absorption tower and source of the gas by slush pump and form reverse circulation and can reach the purpose that hydrogen is put in continuous suction.
Below in conjunction with accompanying drawing apparatus of the present invention are further described.
Accompanying drawing is the formation synoptic diagram of apparatus of the present invention.
With reference to accompanying drawing, the inventive system comprises successively with pipeline be linked to be path absorption tower 1, first flashing tower 2, second flashing tower 3, desorption tower 4, slurry tank 5 and slush pump 6, above each tower, establish the slurry feed mouth, in the legend, the discharge port of slurries is located at the bottom of each tower, top at each tower is provided with blow-off valve K5, K6, K7, K8 respectively, on the connecting tube between tower and the tower, be respectively equipped with reducing valve K2, K3, K4, the inlet mouth of useful reducing valve K1 control below the absorption tower.
When hydrogeneous source of the gas through reducing valve K1 enter absorption tower 1 from bottom to top with the hydrogen bearing alloy slurry counter current contact of being sent into the absorption tower by slush pump 6, hydrogen is just absorbed by the hydrogen storage alloy in the slurries, unabsorbed tail gas is discharged through blow-off valve K5 from cat head, the slurries of inhaling behind the hydrogen then enter first flashing tower 2 through reducing valve K2 at the bottom of the Tata and flow from top to bottom from absorbing, the impurity gas that mixes in slurries discharges through blow-off valve K6 from cat head, slurries are discharged at the bottom of the tower and are entered second flashing tower 3 through reducing valve K3 and flow from top to bottom, and discharge impurity gas from the cat head blow-off valve once more, slurries are discharged at the bottom of the tower and are entered desorption tower 4 through reducing valve K4 and flow from top to bottom, hydrogen is constantly by discharging in the slurries and drawing from the desorption tower top simultaneously, the hydrogen bearing alloy slurry that discharges behind the hydrogen then goes out to slurry tank 5 from tower bottom flow, is driven by mashing pump 6 reentering in the absorption tower circulation and inhale hydrogen.
Here, the macroporous plate tower is adopted on the absorption tower, can make hydrogen bearing alloy slurry be difficult for resulting in blockage in flow process, and sieve-tray tower is cheap, and the manufacturing maintenance is easy, and operating restraint is stablized greatly, and tray efficiency is higher.Desorption tower also adopts the wide aperture sieve-tray tower, and sieve plate and slurries collide and it is shunted again, has played the effect of stirring, and has so both helped dehydrogenation, has saved extra power input again, is beneficial to save energy.Flashing tower just flows through for the slurries step-down, owing to there is no other annexes in the tower, its structure is also comparatively simple.
With prior art relatively, the present invention has following advantage:
1) because the adding of organic solvent, avoid in fixed bed incident blocking pipe, damaged phenomenon such as container, the good thermal conductivity of organic solvent in addition, the heat that discharges when making absorption hydrogen again can in time be discharged, and guarantees that it inhales carrying out smoothly of hydrogen;
2) absorption tower and desorption tower adopt the macroporous plate tower, be difficult for taking place the column plate slurry and stop up, and cost is low, reduced investment, easy to maintenance;
3) with kerosene, diesel oil etc. as organic solvent, not only cheap, conveniently be easy to get, and good fluidity, mass-and heat-transfer performance height;
4) slurries continuous flow in four towers is constantly carried out the absorption of hydrogen and is taken off suction, Gu compare with gas-rhythmic reaction bed, the utilization ratio of its hydrogen storage alloy improves 10～25 times.
Embodiment 1:
Adopt device shown in the drawings, utilize synthesis ammonia plant refining gas mixture to be the raw material separating hydrogen gas, hydrogen content is 70vol% in the gas mixture, and all the other are N
2, Ar and CH
4Impurity gas.Hydrogen storage alloy adopts MlNi
4.7Al
0.3, make the slurries that alloy content is 16% (weight) with cleaning kerosene.Slurries are the gas mixture counter current contact of 0.77m/s with empty tower gas velocity with 2.0MPa pressure in the absorption tower, flow through first flashing tower (pressure is reduced to 1.3MPa), second flashing tower (pressure is reduced to 0.6MPa) successively and in desorption tower (pressure is 0.1MPa), discharge hydrogen after absorbing hydrogen, hydrogen purity is 95～99%, and the hydrogen rate of recovery is 70～80%.
Embodiment 2:
Adopt device shown in the drawings, utilize industrial general hydrogen to separate for raw material, purity 〉=98%, all the other are O
2, N
2, Ar, CH
4And H
2O impurity gas.Hydrogen storage alloy adopts MlNi
47Al
0.3, make the slurries that alloy content is 32% (weight) with cleaning kerosene.Slurries are the general hydrogen counter current contact of 1.2m/s with empty tower gas velocity with 2.0MPa pressure in the absorption tower, flow through first flashing tower (pressure is 1.8MPa), second flashing tower (pressure is 1.0MPa) successively behind the absorption hydrogen, in desorption tower (pressure is 0.1MPa), discharge hydrogen, hydrogen purity is 99.9～99.99%, and the hydrogen rate of recovery is 85～95%.
Claims (6)
1. utilize the method for hydrogen bearing alloy slurry continuous absorption and releasing hydrogen gas, it is characterized in that hydrogen storage alloy and organic solvent blended slurries are driven with slush pump, pass through the absorption tower successively, first flashing tower, second flashing tower, desorption tower four-column process flow contact with the hydrogen-containing gas of countercurrent flow, at room temperature carry out continuous absorption and releasing hydrogen gas.
2. by the described method of utilizing hydrogen bearing alloy slurry continuous absorption and releasing hydrogen gas of claim 1, it is characterized in that said hydrogen storage alloy is the binary or the multicomponent alloy of mishmetal-nickel system, or the binary or the multicomponent alloy of ferrotianium system or titanium manganese system, above-mentioned these alloys are at room temperature inhaled the equilibrium pressure≤1.5MPa of hydrogen, and the equilibrium pressure of putting hydrogen is 0.1～1.4MPa.
3. by the described method of utilizing hydrogen bearing alloy slurry continuous absorption and releasing hydrogen gas of claim 1, it is characterized in that said organic solvent is to clean kerosene or diesel oil or silicone oil.
4. by the described method of utilizing hydrogen bearing alloy slurry continuous absorption and releasing hydrogen gas of claim 1, the content that it is characterized in that hydrogen storage alloy is 10～70% of slurries gross weight.
5. device that is used to implement the described method of claim 1, it is characterized in that it comprise successively with pipeline be linked to be path absorption tower [1], first flashing tower [2], second flashing tower [3], desorption tower [4], slurry tank [5] and slush pump [6], above each tower, be provided with the slurry feed mouth, the below of each tower is provided with the slurries discharge port, the top of each tower is provided with blow-off valve [K5], [K6], [K7], [K8] respectively, on the connecting tube between tower and the tower, be respectively equipped with reducing valve [K2], [K3], [K4], inlet mouth is arranged below the absorption tower.
6. by the described device of claim 5, it is characterized in that said absorption tower [1] and desorption tower [4] adopt the macroporous plate tower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01120906 CN1242833C (en) | 2001-06-08 | 2001-06-08 | Method and equipment using hydrogen bearing alloy slurry for continuously absorbing and releasing hydrogen gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01120906 CN1242833C (en) | 2001-06-08 | 2001-06-08 | Method and equipment using hydrogen bearing alloy slurry for continuously absorbing and releasing hydrogen gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1390625A true CN1390625A (en) | 2003-01-15 |
| CN1242833C CN1242833C (en) | 2006-02-22 |
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ID=4664334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01120906 Expired - Fee Related CN1242833C (en) | 2001-06-08 | 2001-06-08 | Method and equipment using hydrogen bearing alloy slurry for continuously absorbing and releasing hydrogen gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1242833C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761040A (en) * | 2014-03-20 | 2015-07-08 | 叶小剑 | Portable preparation method and device of hydrogen ion water prepared at any time |
| CN109236400A (en) * | 2018-10-20 | 2019-01-18 | 上海柯来浦能源科技有限公司 | A kind of hydrogen nitrogen mixed working fluid electricity generation system |
-
2001
- 2001-06-08 CN CN 01120906 patent/CN1242833C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761040A (en) * | 2014-03-20 | 2015-07-08 | 叶小剑 | Portable preparation method and device of hydrogen ion water prepared at any time |
| CN104761040B (en) * | 2014-03-20 | 2017-01-04 | 叶小剑 | Portable preparation method and device of hydrogen ion water prepared at any time |
| CN109236400A (en) * | 2018-10-20 | 2019-01-18 | 上海柯来浦能源科技有限公司 | A kind of hydrogen nitrogen mixed working fluid electricity generation system |
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| Publication number | Publication date |
|---|---|
| CN1242833C (en) | 2006-02-22 |
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Granted publication date: 20060222 Termination date: 20100608 |