CN1022097C - Zirconium base alloy for purifying hydrogen - Google Patents
Zirconium base alloy for purifying hydrogen Download PDFInfo
- Publication number
- CN1022097C CN1022097C CN 89103775 CN89103775A CN1022097C CN 1022097 C CN1022097 C CN 1022097C CN 89103775 CN89103775 CN 89103775 CN 89103775 A CN89103775 A CN 89103775A CN 1022097 C CN1022097 C CN 1022097C
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- China
- Prior art keywords
- hydrogen
- purifying
- zirconium
- purification
- alloy
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- 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.)
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- C—CHEMISTRY; METALLURGY
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention puts forward one material for purifying hydrogen, which is alloy powder particles containing zirconium-auminum-hafnium, zirconium-auminum-titanium and zirconium-nickel-mischmetal. The material has the performance of no absorption or little absorption for hydrogen but absorption for foreign gases in the hydrogen, and thus, the material can be used for purifying the hydrogen. The present invention has the advantages of low material cost and good effects on purifying the hydrogen and continuously purifies the hydrogen under high flow rate and high pressure. After purification for a long time, purification efficiency does not obviously descend. After single-stage purification, the hydrogen purity of industrially pure hydrogen can reach 99.999%.
Description
The present invention relates to remove the functional materials of composition such as foreign gas in the hydrogen.
High-purity hydrogen is semiconductor technology, high pure metal industry, chemical analysis, reaches widely used important source material in other high pure raw material production, occupy extremely important status in The modern industry.But the hydrogen that the production that ins all sorts of ways at present makes generally all contains impurity such as aerobic, nitrogen, carbon monoxide, water, reach the practical hydrogen of industry and also should hydrogen be carried out purifying according to different purposes.Hydrogen purification method commonly used has absorption process, absorption method, low temperature processing and penetrant method etc.They adopt different materials and device to realize the purifying of hydrogen respectively.Absorption process is that the feature of utilizing hydrogen storage material such as ferrotianium, titanium Mn series alloy or lanthanum nickel system alloy to have suction hydrogen and dehydrogenation realizes purifying hydrogen, earlier hydrogen is solid-solubilized in and forms all kinds of hydride in the alloy, hydride is decomposed discharge hydrogen, this storage hydrogen, dehydrogenation are the purge processes of being interrupted, therefore can not continuous purification, the flow of purified gases is also little.Penetrant method mainly is to utilize palladium or palladium alloy membrane to guarantee that the perviousness to the simple selection in the raw hydrogen under the temperature that is held in 300-500 ℃ realizes purifying hydrogen.Utilize this material can obtain high-purity hydrogen more than 99.999%.But its shortcoming is: (1) material price costliness, and the poor durability of (2) material membrane, the work of palladium film long term high temperature is easily poisoned, purification is reduced, (3) hydrogen pressure can not be excessive, otherwise palladium film sealing of tube part easily cracks, and this has just limited the flow of purifying hydrogen.
The objective of the invention is to propose the material that a kind of hydrogen purification is used, hydrogen is not inhaled or seldom inhaled to this material, but ability with gases such as absorbing various foreign gases in the hydrogen such as oxygen, nitrogen, carbon monoxide, carbonic acid gas, aqueous vapor, methane, thereby to the hydrogen by filling this material powder sealed vessel can continuous uninterrupted, big flow carry out purifying, and material cost low more than palladium or palladium alloy membrane.
The material that the hydrogen purification that the present invention proposes is used is to be the alloy powder of base with the zirconium.It comprises a kind of interpolation element in zirconium, aluminium and titanium and the hafnium.Wherein the content of aluminium is 10-25(weight %), the content of hafnium is 0.01-10(weight %), the content of titanium is 5-10(weight %), the zirconium surplus.Another kind of material comprises zirconium, nickel and mishmetal, and wherein the content of nickel is 15-25(weight %), the content of mishmetal is 2-8(weight %), the zirconium surplus.
The production technique of the Zirconium base alloy for purifying hydrogen that the present invention proposes can be used the general technology of called optical imaging in the metal manufacture field, promptly press the composition weighing and burden earlier, become alloy pig with the vacuum arc fumace heat fused, be ground into 8-300 purpose powder particle then, the powder of making is through activation treatment more than 700 ℃, has the performance of not inhaling or seldom inhaling hydrogen under 300 ℃ the working temperature and can purifying hydrogen being higher than.
Therefore the Zirconium base alloy for purifying hydrogen that the present invention proposes can be used as the purifying hydrogen material owing to have the performance of not inhaling or seldom inhaling hydrogen.The price of material is far below palladium or palladium alloy membrane.When purifying hydrogen, hydrogen flowing quantity is up to 500 liters/hour, and hydrogen pressure is 6 kgfs up to every square centimeter, still has fabulous purification, can realize continuous purification, and not obvious reduction purification in long-time, continuous purification after 1000 hours purification effect still be 99%.With purity is that technical pure hydrogen purity behind the single-stage purifying of 99.9% can reach 99.999%.Material of the present invention also can be used for rare gas elementes such as purifying argon gas, helium.
Further specify embodiments of the present invention and effect with the following example.
Example one, use zirconium sponge, hafnium sponge and high refined aluminium to be raw material, according to zirconium 83, hafnium 0.03, aluminium 16(weight %) the ratio weighing and burden, be pressed into electrode, heat fused becomes alloy pig in vacuum arc fumace, uses crusher that alloy pig is broken for 100 purpose powder particles then.When needing purifying hydrogen, alloy powder is contained in the sealed vessel of band hydrogen gangway, activation treatment is 3 hours under hydrogen atmosphere, 800 ℃ of temperature.Alloy powder after the activated processing can absorb the foreign gas in the hydrogen effectively under 500 ℃ working temperature.With purity be 99.9% technical pure hydrogen behind the single-stage purifying, oxygen level is less than 0.5PPM in the hydrogen, dew point is less than-70 ℃, purification efficiency is 99.68%.Reach the effect of palladium film purifying hydrogen, hydrogen flowing quantity is per hour 500 liters, and pressure is every square centimeter 6 kgf, and continuous purification is after 1000 hours, and purification efficiency still reaches more than 99%.
Example two makes use-case one identical raw material and manufacturing process, makes powder particle according to the prescription batching that table 1 is listed.The purifying hydrogen ability of this class material is basic identical with example one.Dew point behind the purifying is listed in the table 1.
Table 1
Alloy powder composition (weight %) dew point
Zirconium hafnium aluminium ℃
83 1 16 ≤-72
83 0.5 15.3 ≤-72
84 0.1 15.9 ≤-74
90 0.02 10 ≤-70
75 0.01 25 ≤-70
81 3 16 ≤-70
81 3 16 ≤-70
Example three, use zirconium sponge, titanium sponge and high refined aluminium to be raw material, according to the listed proportion ingredient of table 2, make powder particle by example one identical technology, after 900 ℃ of 3 hours activation treatment, under 500 ℃ of working temperatures, be that-40 ℃ the purification effect and the example one of plant hydrogen is basic identical to dew point, the dew point of hydrogen behind the purifying is listed in the table 2.The cost of this class alloy powder is lower.
Table 2
Alloy powder composition (weight %) dew point
Zirconium titanium aluminium ℃
84 6 10 ≤-70
84 4 12 ≤-72
75 5 20 ≤-70
80 6 14 ≤-70
70 5 25 ≤-70
84 10 6 ≤-70
Example four, with zirconium sponge, electrolytic nickel and mishmetal is raw material, and the composition of mishmetal (weight %) is lanthanum La 52, cerium Ce 4, praseodymium Pa 10, neodymium Nd 33 presses listed proportion ingredient in the table 3, adopts example one identical technology to make powder particle, after 900 ℃ of 3 hours activation treatment, under 750 ℃ of working temperatures, be that-40 ℃ the purification effect and the example one of plant hydrogen is basic identical to dew point, the dew point of hydrogen behind the purifying is listed in the table 3.
Table 3
Alloy powder composition (weight %) dew point
Zirconium nickel mishmetal ℃
83 15 2 ≤-70
76 20 4 ≤-73
72 22 6 ≤-73
70 22 8 ≤-70
Claims (3)
1, a kind of purifying hydrogen zirconium base alloy, it is characterized by: this alloy contains aluminium and hafnium, and wherein the content of aluminium is 10-25 (weight %), and the content of hafnium is 0.01-10 (weight %), and zirconium is a surplus.
2, a kind of purifying hydrogen zirconium base alloy, it is characterized by: this alloy contains aluminium and titanium, wherein the content of aluminium is 10-25(weight %), the content of titanium is 5-10(weight %), zirconium is a surplus.
3, a kind of purifying hydrogen zirconium base alloy, it is characterized by: this alloy contains nickel and mishmetal, wherein the content of nickel is 15-25(weight %), the content of mishmetal is 2-8(weight %), zirconium is a surplus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103775 CN1022097C (en) | 1989-06-16 | 1989-06-16 | Zirconium base alloy for purifying hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103775 CN1022097C (en) | 1989-06-16 | 1989-06-16 | Zirconium base alloy for purifying hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1048199A CN1048199A (en) | 1991-01-02 |
| CN1022097C true CN1022097C (en) | 1993-09-15 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89103775 Expired - Fee Related CN1022097C (en) | 1989-06-16 | 1989-06-16 | Zirconium base alloy for purifying hydrogen |
Country Status (1)
| Country | Link |
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| CN (1) | CN1022097C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4363633B2 (en) * | 2004-02-17 | 2009-11-11 | 株式会社アルバック | Double phase alloy for hydrogen separation / purification and production method thereof, metal membrane for hydrogen separation / purification and production method thereof |
| CN108147365A (en) * | 2016-12-04 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of Hydrogen Separation and the method for purifying |
-
1989
- 1989-06-16 CN CN 89103775 patent/CN1022097C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1048199A (en) | 1991-01-02 |
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| CF01 | Termination of patent right due to non-payment of annual fee |