CN1094378A - 从氢气流中分离气态杂质的改进方法 - Google Patents
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000012535 impurity Substances 0.000 title claims abstract description 25
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 43
- 239000000956 alloy Substances 0.000 claims description 43
- 239000011572 manganese Substances 0.000 claims description 20
- 239000010936 titanium Substances 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 14
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910004688 Ti-V Inorganic materials 0.000 claims description 6
- 229910010968 Ti—V Inorganic materials 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004891 communication Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 150000002816 nickel compounds Chemical class 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 229910004337 Ti-Ni Inorganic materials 0.000 claims description 3
- 229910011209 Ti—Ni Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052713 technetium Inorganic materials 0.000 claims description 3
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 8
- 125000004429 atom Chemical group 0.000 description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910003126 Zr–Ni Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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Abstract
从含易分离杂质如COX和难分离杂质如主要为
氮气和甲烷的氢气流中分离杂质的方法包括：
A.先于5—50℃下将该气流与含镍和/或Ni化
合物的材料接触，其中镍总量的至少1wt％以还原态
存在，
B.来自(A)的仍含难分离N2和CH4的气流在
更高温度下与不蒸发吸气材料接触。
Description
本发明涉及从氢气流中分离气态杂质的改进方法，其中没有残余微量甲烷并且不会形成任何新的甲烷，尤其宜于长期制造含不足50，优选不足20ppb（即109份中20份（体积））甲烷的纯氢）。
半导体工业一直在开发线性密度更高的集成电路，因此要求制造工艺中所用材料纯度要高，由于氢为该工艺所用气体之一，所以必须保证其杂质含量应尽可能低，市售氢气中主要气态杂质为湿汽（水蒸汽），氧，一氧化碳（CO），二氧化碳（CO2）及其混合物（COx）以及氮气和甲烷，后两种（N2，尤其是CH4）特别难分离。
长期以来，氢气提纯方法之一为氢气选择性扩散经过钯或钯合金，但扩散速度是随Pd隔板相对两侧之间压降而提高的，而且从Pd提纯氢气的经济角度看操作温度很高，另外因氢气杂质被Pd隔板阻隔，所以必须设置清除设备或探测器，US3368329说明了这类设备之一，而另一种扩散膜提纯氢的办法见于US3534531。
虽然这种扩散隔板很有效，但仍有不少缺点，若隔板很薄以保证达到提纯氢气的高产量，则会出现机械失效，随后就会有不纯氢气漏入提纯气中，而由于隔板两侧压降高，所以问题就更严重，而若隔板厚度增加以避免机械失效，则必须用过高的温度才能保证提纯气的高产出。在氢存在下用高温是极危险的，因为一旦温度过高就可能存在爆炸性氢-氧（或空气）混合物，并且增加隔板厚度就会用更大量昂贵的钯。
因此，本发明目的之一是提出提纯氢气的改进方法，该新方法没有现有技术上述一或多方面的缺点。
本发明另一目的是提出不用向钯或其合金扩散即可提纯氢气的改进方法。
本发明再一目的是提出不出现高压差的氢气提纯改进方法。
本发明又一目的是提出不存在任何甲烷并且不会形成任何新甲烷的长期制造高纯度氢气的改进方法。
本发明上述及其它优点详见于以下所述及附图。
广义地讲，本发明涉及从氢气流中分离气态杂质的改进方法，其中氢气流含第一类易分离杂质，如COx，及第二类难分离杂质，主要包括氮气和甲烷，该方法基本上包括以下步骤：
A.该气流先于5-50℃与一层或多层含镍和/或镍化合物及必要时的载体的粒料床接触，其中镍总量的至少1wt%（优选5%）以还原（元素）态存在，接触到所说易分离杂质基本上完全分离为止;
B.来自步骤A，基本上没有所说易分离杂质，但仍含所说难分离氮气和甲烷的气流在更高温度下与一层或多层不蒸发吸气材料床接触。
所说氢气流压力宜为1-20巴，步骤（B）温度宜为400-600℃，优选500-600℃。
氢气流空一定般0.5-50标准cm3/分钟/g吸气材料，不需要的甲烷量一般最多5ppm（5000ppb）。
本发明两步方法中第一步（A）所用元素镍和镍化合物（如氧化物）宜用优选由有效表面积等于或高于100m2/g（优选100-200m2/g）的硅质岩，钛-硅质岩，干凝胶（EP-A-537851）或二氧化硅（US4713224）构成的载体载负并且含镍床层前后（优选前面）可设基本上由天然或合成分子筛如天然或合成沸石，硅质岩或钛-硅质岩组成的第二吸收床。
本发明所用吸气材料宜为吸气合金，选自：
a）Ti-Ni或Zr-Ni合金，优选为含50-80wt%钛或锆（其余为镍）的合金，其中最多50wt%的锝可由铁和/或锰和/或镍和/或铼代替，
b）高锰Ti-V合金（下称HM合金，US4457891），
c）低锰Ti-V合金（下称LM合金）。
该HM合金组成如下（wt%）：
Ti：25-30.9%
V：10-42%
Mn：27.1-65.1%，
其中存在2-2.2个其它原子/钛原子。
该HM合金中优选最多约40%钒原子可由铁原子代替并且最多10%钒原子可由铝原子代替，但其中不多于40%的钒原子可由所说铁和铝原子总量代替。
而且该HM合金必要时还可进行以下组成变化：
ⅰ）最多约20%Ti原子可由Ca，Y，La，混合稀土或其混合物代替，
ⅱ）最多0.2个Cr原子（/Ti原子）可代替相应数量的锰和/或钒原子，
ⅲ）合金中可存在最多0.1个Ni原子和/或0.05个Cu原子（/Ti原子），其中优选不多于约0.1个Ni和Cu原子可代替相应数量的锰和/或钒原子。
所说LM合金组成如下（wt%）：
Ti：25-65%
V：10-52%
其中最多40wt%钒可由铁代替且最多20wt%钛可由锰代替。
吸气材料可以松散粉状形式应用，其平均粒径1-500μm，优选1-250μm，更优选1-128μm，但该粉可烧结成型，而且又可简单加热或加热并用第二种粉进行烧结以获得令人满意的孔隙率（如GB专利No.2077487），成型体平均尺寸一般等于几个mm（0.5-5mm）。
与氢气流接触的含吸附杂质的合金的装置表面应以均匀平滑的方式充分抛光以尽可能减少污染，该表面要求的光滑度可表示为氢接触的内壁面粗糙度，按本发明优选方案该粗糙度必须等于或低于0.50，优选低于0.25μm，即中心线平均高度（Ra），虽然该值并不关键，但建议用其作为安全可靠的条件。
图1示出了从含杂质氢气流中分离杂质的提纯设备100，其中设有管104，104′与预提纯室106，106′流体相通的气体入口102，阀108，108′可交替开关以使含杂质气流经过第一或第二预提纯室106，106′，室中设基于带载体镍的粒料床110，其中该床在相对低温下分出易分离杂质（COx等），而且室中可另外含天然或合成分子筛111以更好地分离二氧化碳或另外设置单独的分子筛，所说室还可将湿汽分离而达到微量水平，但不分离氮气和甲烷。
因此可得仅含基本上由氮气和甲烷构成的第二类杂质的部分提纯氢气，离开预提纯室106，106′后进入保持更高温度的最终提纯室112，该室经管114，114′与室106，106′流体相通，可用阀116，116′控制部分提纯气从第一预提纯室106，106′之一出来的流量，其中两室之一中再生镍，而另一室正常工作，在该最终提纯室112中部分提纯氢气与不蒸发吸气材料床118接触。
以下实施例详述本发明，其中除另有说明而外，所有份数和百分比均以体积计，但这些实施例仅仅示意性说明本发明，并不能理解为以任何形式限制本发明构思和保护范围。
实施例1
含5ppm（体积）甲烷（5000ppb）以及微量氮气和COx的氢气流室温（低于40℃）和4巴压力下以100标准cm3/分钟的流速流经含两层吸收材料床的第一预提纯室（106），所说床层上游离有分子筛（合成沸石）床（111），下游有含约20g物料的另一床（110），该物料含58wt%镍（主要为氧化镍形式），其载体为表面积稍高于100m2/g的二氧化硅载体（Engelhard Company以“Ni0104T”商名销售），其中至少5wt%所说镍为还原态。
在该预提纯室出口不可能回收任何微量COx，该气流再流经第二（最终）室，其中放有40g不挥发Ti2Ni吸气合金，为松散粉状，平均粒径1-150μm，组成为62wt%Ti和38wt%Ni，试验中该吸气合金温度一直保持550℃。
在该第二室出口测定剩余CH4浓度，其中用VALCO气相色谱仪和对甲烷灵敏度为5ppb的亚稳态氦离子化探测仪操作。
开始时新鲜吸气合金的确完全吸附新有甲烷并且在该第二室出口设探测到任何微量剩余甲烷，然后吸气合金开始达到饱和并在剩余甲烷浓度达50ppb时终止试验，计算出这段时间内已吸收的甲烷总量超过1.36乇×l/g，表Ⅰ中将该值计为“吸收能力”。
实施例2和3
重复例1，其中用另两种不同的本发明吸气合金代替上述吸气合金，其中两种合金具体组成如下（wt%）：
例2：
56.7%Ti，30.2%V，6.6%Fe，6.5%Mn（LM合金），
例3：
30.1%Ti，14.4%V，10.5%Fe，44.9%Mn（HM合金）。
数据和结果列于表1。
例 吸收甲烷的材料 Mn(%) 吸收能力
(乇×l/h)
1 Ti2Ni 0 >1.36
2 LM合金 6.5 >0.96
3 HM合金 44.9 >1.22
Claims (15)
1、从氢气流中分离气态杂质的改进方法，其中氢气流含第一类易分离杂质，如COx，及第二类难分离杂质，主要包括氮气和甲烷，该方法基本上包括以下步骤：
A.该气流先于5-50℃与一层或多层含镍和/或镍化合物的粒料床接触，其中镍总量的至少1wt%(优选5%)以还原态存在，接触到所说易分离杂质基本上完全分离为止；
B.来自步骤A，基本上没有所说易分离杂质，但仍含所说难分离氮气和甲烷的气流在更高温度下与一层或多层不蒸发吸气材料层接触。
2、权利要求1的方法，其中该气流压力为1-20巴并且步骤B温度为400-600℃，优选500-600℃。
3、权利要求1的方法，其中所说镍和/或镍化合物用基本上由有效表面积等于或大于100m2/g（优选100-200m2/g）的硅质岩，钛-硅质岩，干凝胶或二氧化硅组成的载体载负。
4、权利要求1的方法，其中含镍床层前后（优选前面）可设由一层或多层天然或合成的分子筛如天然或合成沸石，硅质岩或钛-硅质岩组成的第二吸收床。
5、权利要求1的方法，其中所说吸气材料含于有均匀并平滑抛光内壁面的壳体内，该内壁粗糙度以中心线平均高度（Ra）计为等于或低于0.50，优选低于0.25μm。
6、权利要求1的方法，其中氢气空速0.5-50标准cm3/分钟/g吸气材料且难分离甲烷量最多5ppm。
7、权利要求1的方法，其中该吸气材料为平均尺寸1-500，优选1-250μm的松散粉状。
8、权利要求1的方法，其中该吸气材料为成型体，尤其为粒状，其平均尺寸优选0.5-5mm。
9、权利要求1的方法，其中吸气材料选自：
a）Ti-Ni合金，优选为含50-80wt%钛或锆（其余为镍）的合金，其中最多50wt%的镍可由铁和/或锰和/或锝和/或铼代替，
b）高锰Ti-V合金（HM合金），
c）低锰Ti-V（LM合金）。
10、权利要求9的方法，其中该HM合金组成如下（wt%）：
Ti：25-30.9%
V：10-42%
Mn：27.1-65.1%，
其中存在2-2.2个其它原子/钛原子。
11、权利要求10的方法，其中该HM合金中优选最多约40%钒原子可由铁原子代替并且最多10%钒原子可由铝原子代替，但其中不多于40%的钒原子可由所说铁和铝原子总量代替。
12、权利要求11的方法，其中该HM合金必要时还可进行以下组成变化：
ⅰ）最多约20%Ti原子可由Ca，Y，La混合稀土或其混合物代替，
ⅱ）最多0.2个Cr原子（/Ti原子）可代替相应数量的锰和/或钒原子，
ⅲ）合金中可存在最多0.1个Ni原子和/或0.05个Cu原子（/Ti原子），其中优选不多于约0.1个Ni和Cu原子可代替相应数量的锰和/或钒原子。
13、权利要求9的方法，其中该LM合金组成如下（wt%）：
Ti：25-65%
V：10-52%
其中最多40wt%钒可由铁代替且最多20wt%钛可由锰代替。
14、从氢气流中分离气态杂质设备，其中氢气流含第一类易分离杂质，如COx，及第二类难分离杂质，主要包括氮气和甲烷，该设备包括：
经管104，104′与预提纯室106，106′流体相通的气体入口102以及阀108，108′，这两个阀可交替开关以使含杂质氢气经过第一或第二预提纯室106，106′，室中设有基于带载体镍的粒料床110，而且该室中必要时还可含天然或合金分子筛材料第二床（111），
B.经管114，114′与预提纯室106，106′流体相通的最终提纯室112以及阀116，116′，这两个阀可控制从预提纯室106，106′之一出来的部分提纯氢气流量，其中两室之一再生镍，而另一室正常工作，并且该最终提纯室112含不蒸发吸气材料床118。
15、权利要求14的设备，其中所说吸气材料选自：
a）Ti-Ni合金，优选为含50-80wt%钛或锆（其余为镍）的合金，其中最多50wt%的镍可由铁和/或锰和/或锝和/或铼代替，
b）高锰Ti-V合金（HM合金），
c）低锰Ti-V合金（LM合金）。
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| ITMI930851A IT1270876B (it) | 1993-04-29 | 1993-04-29 | Processo perfezionato per la rimozione di impurezze gassose da una corrente di idrogeno |
| ITMI93A000851 | 1993-05-29 |
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| EP (1) | EP0696257B1 (zh) |
| JP (1) | JP3094235B2 (zh) |
| KR (1) | KR0180946B1 (zh) |
| CN (1) | CN1032055C (zh) |
| CA (1) | CA2137791A1 (zh) |
| DE (1) | DE69314670T2 (zh) |
| IT (1) | IT1270876B (zh) |
| RU (1) | RU2123971C1 (zh) |
| WO (1) | WO1994025395A1 (zh) |
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| CN104245090A (zh) * | 2012-02-10 | 2014-12-24 | 恩特格林斯公司 | 气体纯化器 |
| CN112301264A (zh) * | 2020-10-16 | 2021-02-02 | 北京赛博泰科科技有限公司 | 一种非蒸散型低温激活吸气合金及其制备方法 |
| CN115786768A (zh) * | 2022-11-17 | 2023-03-14 | 北京锦正茂科技有限公司 | 一种超低温真空杜瓦结构的气体吸附材料及其制备方法 |
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| IT1270875B (it) * | 1993-04-29 | 1997-05-13 | Getters Spa | Procedimento di purificazione dell'idrogeno e purificatore relativo |
| US6436352B1 (en) | 1993-04-29 | 2002-08-20 | Saes Getter, S.P.A. | Hydrogen purification |
| IT1269978B (it) * | 1994-07-01 | 1997-04-16 | Getters Spa | Metodo per la creazione ed il mantenimento di un'atmosfera controllata in un dispositivo ad emissione di campo tramite l'uso di un materiale getter |
| IT1277458B1 (it) * | 1995-08-07 | 1997-11-10 | Getters Spa | Processo per la rimozione di ossigeno da ammoniaca a temperatura ambiente |
| US6776970B1 (en) | 1995-08-07 | 2004-08-17 | Giorgio Vergani | Getter materials for deoxygenating ammonia/oxygen gas mixtures at low temperature |
| WO1997014648A1 (en) * | 1995-10-20 | 1997-04-24 | Ultrapure Systems, Inc. | Hydrogen purification using metal hydride getter material |
| US6325972B1 (en) * | 1998-12-30 | 2001-12-04 | Ethicon, Inc. | Apparatus and process for concentrating a liquid sterilant and sterilizing articles therewith |
| US5955044A (en) * | 1997-09-30 | 1999-09-21 | Johnson Matthey Inc. | Method and apparatus for making ultra-pure hydrogen |
| US6641625B1 (en) | 1999-05-03 | 2003-11-04 | Nuvera Fuel Cells, Inc. | Integrated hydrocarbon reforming system and controls |
| EP1072351A1 (en) * | 1999-07-08 | 2001-01-31 | Pierre Diserens | Method for laser cutting |
| US6521192B1 (en) | 1999-08-06 | 2003-02-18 | Saes Pure Gas, Inc. | Rejuvenable ambient temperature purifier |
| KR100379625B1 (ko) * | 2000-08-05 | 2003-04-10 | 주식회사 세종소재 | 수소 정제용 게터 |
| ITMI20010018A1 (it) * | 2001-01-08 | 2002-07-08 | Getters Spa | Metodo per la misura della concentrazione di impurezze in elio mediante spettroscopia di mobilita' ionica |
| US7507384B2 (en) * | 2002-06-13 | 2009-03-24 | Nuvera Fuel Cells, Inc. | Preferential oxidation reactor temperature regulation |
| US6931711B2 (en) * | 2002-09-03 | 2005-08-23 | Honeywell International Inc. | Methods and apparatus for removing gases from enclosures |
| KR100825080B1 (ko) * | 2008-02-26 | 2008-04-25 | 하양호 | 충전물의 비중이 일정한 게터 |
| US20100037655A1 (en) * | 2008-08-13 | 2010-02-18 | Air Liquide Process And Construction Inc. | Hydrogen Recovery From A Mixture Of Hydrogen and Hydrocarbons At Low Pressure And Of Low Hydrogen Content |
| RU2415075C1 (ru) * | 2009-08-27 | 2011-03-27 | Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) | Способ глубокой очистки водорода |
| ITMI20120676A1 (it) * | 2012-04-24 | 2013-10-25 | Getters Spa | Metodo e dispositivo rigenerabile di purificazione a temperatura ambiente per monossido di diazoto |
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-
1993
- 1993-04-24 RU RU95106479A patent/RU2123971C1/ru active
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- 1993-05-24 WO PCT/IT1993/000053 patent/WO1994025395A1/en active IP Right Grant
- 1993-05-24 EP EP93914924A patent/EP0696257B1/en not_active Expired - Lifetime
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- 1993-05-31 CN CN93106486A patent/CN1032055C/zh not_active Expired - Lifetime
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245090A (zh) * | 2012-02-10 | 2014-12-24 | 恩特格林斯公司 | 气体纯化器 |
| US9694319B2 (en) | 2012-02-10 | 2017-07-04 | Entegris, Inc. | Gas purifier |
| CN108097036A (zh) * | 2012-02-10 | 2018-06-01 | 恩特格里斯公司 | 气体纯化器 |
| US10245554B2 (en) | 2012-02-10 | 2019-04-02 | Entegris, Inc. | Gas purifier |
| CN112301264A (zh) * | 2020-10-16 | 2021-02-02 | 北京赛博泰科科技有限公司 | 一种非蒸散型低温激活吸气合金及其制备方法 |
| CN115786768A (zh) * | 2022-11-17 | 2023-03-14 | 北京锦正茂科技有限公司 | 一种超低温真空杜瓦结构的气体吸附材料及其制备方法 |
| CN115786768B (zh) * | 2022-11-17 | 2024-01-12 | 北京锦正茂科技有限公司 | 一种超低温真空杜瓦结构的气体吸附材料及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2137791A1 (en) | 1994-11-10 |
| KR0180946B1 (ko) | 1999-03-20 |
| CN1032055C (zh) | 1996-06-19 |
| KR950704185A (ko) | 1995-11-17 |
| EP0696257B1 (en) | 1997-10-15 |
| JPH08508968A (ja) | 1996-09-24 |
| ITMI930851A0 (it) | 1993-04-29 |
| WO1994025395A1 (en) | 1994-11-10 |
| US5492682A (en) | 1996-02-20 |
| EP0696257A1 (en) | 1996-02-14 |
| IT1270876B (it) | 1997-05-13 |
| RU95106479A (ru) | 1997-01-10 |
| RU2123971C1 (ru) | 1998-12-27 |
| JP3094235B2 (ja) | 2000-10-03 |
| DE69314670T2 (de) | 1998-02-12 |
| DE69314670D1 (de) | 1997-11-20 |
| ITMI930851A1 (it) | 1994-10-29 |
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