TW201332631A - 製備鈀-銀合金氣體分離薄膜系統的方法 - Google Patents
製備鈀-銀合金氣體分離薄膜系統的方法 Download PDFInfo
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- TW201332631A TW201332631A TW101148823A TW101148823A TW201332631A TW 201332631 A TW201332631 A TW 201332631A TW 101148823 A TW101148823 A TW 101148823A TW 101148823 A TW101148823 A TW 101148823A TW 201332631 A TW201332631 A TW 201332631A
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- Prior art keywords
- palladium
- silver
- layer
- deposited
- microns
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000000926 separation method Methods 0.000 title claims abstract description 44
- 239000012528 membrane Substances 0.000 title claims abstract description 26
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910001316 Ag alloy Inorganic materials 0.000 title claims abstract description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 212
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 105
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000004332 silver Substances 0.000 claims abstract description 97
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- 238000006243 chemical reaction Methods 0.000 description 7
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Classifications
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- 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
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0053—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0055—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment
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- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C—CHEMISTRY; METALLURGY
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- 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
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
- C01B3/503—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion characterised by the membrane
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
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- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1651—Two or more layers only obtained by electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
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Abstract
本發明係關於一種製備鈀-銀合金氣體分離薄膜系統之方法,其中藉由非化學活化方法來活化鈀層或銀層之表面,該非化學活化方法涉及打磨出受控的表面粗糙度及磨蝕圖案,從而允許在鈀層上鍍覆或沉積銀之上覆層,在銀層上鍍覆或沉積銀之上覆層,或在銀層上鍍覆或沉積鈀之上覆層。該等鈀及銀層較佳係支撐在業已施加金屬間擴散障壁之多孔金屬支撐體上。
Description
本發明係關於一種製備鈀-銀合金氣體分離薄膜系統之方法,該氣體分離薄膜系統本身,及其用途。
複合氣體分離模組通常係用以自氣體混合物選擇性地分離一種特定氣體。此等複合氣體分離模組可由各種材料組成,包括,例如聚合物及金屬複合材料。雖然此等複合氣體分離模組可在低溫處理條件下提供氣體分離之有效及具成本效益的選擇,但其通常不適於在高溫及高壓氣體分離處理下使用。
先前技術中揭示若干種氣體分離模組,其意欲用於高溫氣體分離應用中,且具有由安裝在多孔基板表面之選擇性氣體滲透金屬薄膜組成之結構。例如,美國專利公開案2004/0237780及2009/0120287揭示用於選擇性分離氣體之氣體分離系統。二者皆教示,氣體分離系統之製造係首先藉由無電鍍覆沉積氣體選擇性金屬,其通常為將鈀無電鍍覆至多孔基板上,接著打磨所得經塗佈之基板,及此後,沉積第二層氣體選擇性金屬,其通常亦為將鈀沉積於該經塗佈拋光的多孔基板上。在US 2004/0237780中,採用打磨或拋光經塗佈之基板之中間步驟以自該經塗佈之基板表面移除不利形態。在US 2009/0120287中,採用中間打磨步驟之目的在於移除首先所沉積之材料之絕大部分,以提供較薄緻密氣體選擇性薄膜。此等公開案並未解決與試圖
將銀層沉積於鈀層上相關之問題。
銀黏聚之問題係眾所周知。「The Inhibition of Silver Agglomeration by Gold Activation in Silver Electroless Plating」,Cha等人,Journal of the Electrochemcial Society(2005),C388-C391,將銀黏聚描述為獲得薄銀膜之阻礙。將金層用作基板之活化材料,此後將銀膜無電沉積於經金活化之基板上。銀具有不同於鈀之晶體結構,且若試圖將銀鍍覆於鈀上,則銀將覆蓋於本身上,並在鈀表面形成島狀物。
克服銀黏聚問題之另一途徑係在沉積銀前對待鍍覆之表面進行化學活化。US 7,175,694中揭示化學活化之一種如此方法,其中經氧化的不鏽鋼管之表面係藉由將該管浸沒於SnCl2及PdCl2之水浴中而活化,接著相繼施加鈀及銀層。此種活化方法消耗大量水,並產生大量需在排放前處理之廢水,且同樣遺留需移除之錫殘餘物及氯離子。
鈀表面活化之另一方法採用乙酸鈀之氯仿溶液,並涉及蒸發、乾燥及分解乙酸鹽,接著還原為鈀金屬晶種。
由於化學活化方法(諸如上文所述之方法)涉及多個步驟,故其有昂貴且耗費時間之傾向,此外還產生需處理之廢物。
US 2011/0232821中揭示一種用於使金屬表面活化之非化學方法。然而,所揭示之方法採用不同於本發明方法中所採用之表面粗糙度及形態。
因此,此項技術中需一種製備鈀-銀合金氣體分離薄膜
系統之有效且具成本效益之方法,其中可將銀均勻地沉積於鈀層上,而無化學活化之需求或包括作為活化材料之金層之需求。
本發明提供一種使鈀表面活化,以利於施加銀之上覆層及/或鈀之額外層,而無需昂貴且費時之化學活化之廉價且高效的方法。
本發明部分係基於可藉由以下步驟將銀施加至鈀表面,而無對費時化學活化技術之需求,或者包括金層之需求之發現:利用研磨介質,藉由打磨表面使鈀層表面活化,以達到如下文所述之某種表面粗糙度及磨蝕圖案;不藉助化學活化,將包括銀之上覆層沉積於經活化之鈀層上(其係鍍覆於鈀層上),及;對該鈀層及銀上覆層進行退火,以提供鈀-銀合金氣體分離薄膜系統。本發明方法可用於將銀鍍覆於鈀層上,將銀鍍覆於銀層上,或將鈀鍍覆於銀層上。
雖然拋光或打磨鈀表面係此項技術中已知,但進行此種拋光或打磨之目的通常在於產生較光滑鈀表面,化學活化後可在其上沉積鈀之後續層。在本發明方法中進行打磨步驟之主要目的在於使表面活化,例如藉由刮劃該表面,或於該表面上施加表面圖案及受控的表面粗糙度,此將允許不藉助化學活化進行額外鍍覆。因此,如描述本發明方法所用之術語「打磨」或「拋光」係指將一種研磨介質施加於金屬薄膜表面,以使該金屬薄膜表面活化,進而利於額
外鍍覆,而無需進行化學活化。
本發明亦提供一種鈀-銀合金氣體分離薄膜系統,其包括:多孔支撐體,其上支撐一個業已經藉由利用研磨介質活化至某種表面粗糙度之鈀層,其中在該經活化的鈀層上覆蓋以包括銀之上覆層,此係經鍍覆於該鈀層上,並對該等所合併的鈀及銀層進行退火,以形成鈀-銀合金氣體分離薄膜系統。在一較佳實施例中,多孔支撐體係經金屬間擴散障壁塗佈,其上沉積有鈀及/或銀層。
尤其可將本鈀-銀合金氣體分離薄膜系統用於在於高溫及高壓條件下自含氫氣流分離氫氣之製程中。
本發明係關於一種製造具有至少一層鈀及至少一層銀沉積於其上之氣體分離薄膜系統之具經濟優勢的方法。本發明亦係關於由此所製造之氣體分離薄膜系統,及其於分離氣體之用途。
本發明方法之一重要特徵在於打磨步驟,其中鈀層表面係藉由打磨或研磨該表面以施加適宜磨蝕圖案及受控表面粗糙度而活化。已發現,若鈀表面係如下文所述活化,則可在該鈀表面塗佈銀之均勻層或塗層,而不存在對昂貴且費時的化學活化之需求或包括作為活化材料之金層之需求,惟可將一或多層金層塗佈至鈀-銀合金薄膜,以改良其抗硫性。
按照本發明,為在相對光滑的鈀表面(將其定義為平均表面粗糙度(Sa)低於0.8微米之鈀表面)塗佈均勻銀上覆
層,藉由打磨使該鈀表面活化,以達到超過0.8微米上至2.5微米之平均表面粗糙度(Sa),及適宜磨蝕圖案。較佳地,將平均表面粗糙度(Sa)控制在0.85微米至1.5微米之範圍內,更佳在0.9微米至1.2微米之範圍內。
適宜磨蝕圖案可呈設計圖案(lay pattern)之形式,其係鈀表面上之重複壓痕。表面精製設計圖案之實例包括垂直狀、水平狀、輻射狀、交叉網格狀、環狀、正弦狀、卵形、橢圓形、線圈形、花生形及其他圖案。美國公開申請案第2011-0232821號中更詳細地論述適宜及較佳設計圖案及其中一些在鈀表面上壓印或施加此等設計圖案之方法及方式,該案以引用的方式併入本文中。就按照本方法之表面活化而言,較佳為交叉網格磨蝕圖案。
平均表面粗糙度或算數平均高度(Sa)為衡量表面之粗糙度之已知量度,且可輕易利用光學表面輪廓儀確定。可使用任何市售光學表面輪廓儀。此種市售光學表面輪廓儀之一實例為ST400 3D表面輪廓儀,其係由Nonovea推廣及銷售。
適於在打磨步驟中使用以產生所需表面粗糙度之磨料可選自任何類型之磨料,諸如,黏合磨料、砂紙及鬆散磨料,包括懸浮於液體中之磨料顆粒或含於糊劑中之磨料。研磨顆粒之尺寸應使其發揮產生適宜磨蝕圖案及將表面粗糙度控制在所定義範圍內之功能。已發現,平均粒徑為1至10微米之研磨介質可產生適宜表面粗糙度。然而,可使用平均粒徑高於或低於此範圍之其他研磨介質,只要其可
產生大於0.8微米上至2.5微米之最終平均表面粗糙度(Sa)即可。
磨料顆粒之組成並不嚴苛,且磨料顆粒可選自天然磨料,諸如例如金剛石、金剛砂、剛玉粉及矽石,或選自人造磨料,諸如例如碳化矽、氧化鋁(熔融、燒結、溶膠-凝膠燒結)、碳化硼及立方氮化硼。
藉由打磨將鈀表面活化至所需表面粗糙度及磨蝕圖案後,可藉由任何已知方式將一或多層銀沉積於該鈀表面上,該等方式包括例如無電鍍覆、熱沉積、化學氣相沉積、電鍍、噴霧沉積、濺鍍塗佈、電子束蒸鍍、離子束蒸鍍及噴霧熱解。較佳沉積方法為無電鍍覆。
銀可經分層(即沉積為多層)或沉積於一層中。亦可將銀沉積於金屬間擴散障壁上,並用以將該金屬間擴散障壁固定在多孔支撐體上,接著進行額外銀鍍覆步驟。在本發明之另一實施例中,可將銀層夾在鈀層間。較佳係最後鍍覆鈀層,也就是在最終銀層之後。
所沉積銀之量可構成全部鈀層之1 wt%至35 wt%。較佳地,銀將構成全部鈀層之5 wt%至30 wt%,更佳全部鈀層之10 wt%至25 wt%。
可將上述銀之百分比適用於一或多個鍍覆操作中。通常,銀上覆層之厚度將小於10微米,較佳地,小於8微米,及最佳地,小於5微米。上覆層厚度之下限為約0.01微米。因此,銀上覆層厚度可在0.01微米與10微米間之範圍內,較佳地,在0.1微米與5微米之間,及最佳地,在1
微米與2微米之間。
合併之鈀及銀層之總厚度應小於10微米,較佳小於8微米,最佳小於6微米。
在本發明之一較佳實施例中,鈀-銀合金氣體分離薄膜系統係支撐在經金屬間擴散障壁塗佈之多孔基板上。在此實施例中,將金屬間擴散障壁施加至多孔基板;將一或多層鈀或鈀合金沉積於該金屬間擴散障壁上;藉由利用一種研磨介質打磨使鈀層表面活化,以產生所需磨蝕圖案,並將表面粗糙度控制在所界定之範圍內;接著不藉助化學活化,藉由使該經活化的鈀層與含銀鹽(諸如硝酸銀)之溶液接觸,在該經打磨活化的鈀層上沉積一或多層銀。該等銀層及鈀層經熱處理(即退火),以得到鈀-銀合金氣體分離薄膜系統。
在本發明之另一實施例中,首先將銀層沉積於金屬間擴散障壁上。接著藉由打磨使銀層表面活化,且接著將一或多層鈀沉積於該銀層上,並對該等經合併之層實施退火。
可在本發明方法之各種實施例中採用之多孔支撐體包括任何適於作為金屬間擴散障壁及鈀及/或鈀-銀合金之層之支撐體之多孔金屬材料。多孔支撐體可呈任何形狀或幾何形狀;限制條件為其具有能將金屬間擴散障壁及鈀、鈀合金及銀之層施加至其上或沉積於其上之表面。此等形狀可包括具有一起界定薄片厚度之下表面及上表面之多孔金屬材料之平坦或曲線薄片,或者此等形狀可為管狀,諸如例如具有一起界定壁厚之內表面及外表面之矩形、方形及環
形管狀,且該管狀之內表面界定管狀管道。
多孔金屬材料可選自熟習此項技術者所知之任何材料,包括(但不限於)不鏽鋼(諸如例如301、304、305、316、317及321系列不鏽鋼)、HASTELLOY®合金(例如,HASTELLOY® B-2、C-4、C-22、C-276、G-30、X及其他)及INCONEL®合金(例如,INCONEL®合金600、625、690及718)。因此,多孔金屬材料可包括一種可滲透氫之合金,且其包括鐵及鉻。多孔金屬材料可進一步包括一種選自由下列組成之群之額外合金金屬:鎳、錳、鉬及其任何組合。
一種適合用作多孔金屬材料之尤其適宜的合金可包括含量為上至該合金總重之約70重量%之範圍之鎳及含量為該合金總重之10至30重量%之範圍之鉻。另一種可用作多孔金屬材料之適宜金屬包括範圍於30至70重量%之鎳、範圍於12至35重量%之鉻及範圍於5至30重量%之鉬,且該等重量%係基於合金之總重。英高鎳(Inconel)合金係優於其他合金。
多孔金屬基板之厚度(例如如上所述之壁厚或薄片厚度)、孔隙率及孔之孔徑分佈係為提供具有所需特性之本發明氣體分離薄膜系統所選擇的多孔支撐體之特性,且同樣亦係製造本發明氣體分離薄膜系統所需。應瞭解,隨著多孔支撐體之厚度增加,當將其用於氫分離應用時,氫通量將傾向於降低。諸如壓力、溫度及流體流組成之操作條件亦可影響氫通量。但是,在任何情況下,宜使用厚度薄
得合理之多孔支撐體,以提供高氣體通量。下文所涵蓋之典型應用之多孔基板厚度可在約0.1 mm至約25 mm之範圍,但是,較佳地,厚度係在1 mm至15 mm之範圍,及更佳地,2 mm至12.5 mm,及最佳地,2 mm至10 mm。
多孔金屬基板之孔隙率可在0.01至約1之範圍。將術語孔隙率定義為多孔金屬基板材料之非實體體積對總體積(即非實體加實體)之比例。較典型孔隙率係於0.05至0.8之範圍,甚至0.1至0.6。
多孔金屬基板之孔之孔徑分佈可隨多孔金屬基板材料之孔之中值孔徑而變化,通常係在約0.1微米至約50微米之範圍。更典型地,多孔金屬基板材料之孔之中值孔徑係於0.1微米至25微米之範圍,及最典型地,0.1微米至7微米。
如上所述,本發明之經改良方法亦包括將金屬間擴散障壁施加至多孔基板表面,接著於其上形成鈀、銀或鈀合金之層。適宜金屬間擴散障壁包括選自無機氧化物、耐火金屬及貴金屬蛋殼催化劑組成之群之材料之顆粒。此等顆粒之尺寸應為可使其等(或至少部分顆粒)符合(至少部分符合)用以支撐鈀-銀薄膜之多孔基板之某些孔之尺寸範圍。因此,此等顆粒通常應具有小於約50微米(μm)之最大尺寸。
顆粒之粒徑(即顆粒之最大尺寸)通常亦將取決於本發明方法中所用多孔基板之孔之孔徑分佈。通常,無機氧化物、耐火金屬或貴金屬蛋殼催化劑顆粒之中值粒徑將係於0.1微米至50微米之範圍。更具體言之,中值粒徑係於0.1
微米至15微米之範圍。該等顆粒之中值粒徑較佳係於0.2微米至3微米之範圍。
可能適宜用作金屬間擴散障壁顆粒層之無機氧化物之實例包括氧化鋁、矽石、氧化鋯、經安定之氧化鋯(諸如經氧化釔或氧化鈰安定之氧化鋯)、二氧化鈦、氧化鈰、矽、碳化物、氧化鉻、陶瓷材料及沸石。耐火金屬可包括鎢、鉭、錸、鋨、銥、鈮、釕、鉿、鋯、釩、鉻及鉬。就可適宜用作施加至多孔基板表面之金屬間擴散障壁顆粒層之貴金屬蛋殼催化劑顆粒而言,美國專利案7,744,675中更為詳細地定義並描述貴金屬蛋殼催化劑顆粒,該案之全文以引用的方式併入本文中。用於本發明方法之較佳金屬間擴散障壁為貴金屬蛋殼催化劑,其包括經氧化釔安定之氧化鋯,特定言之經6至8 wt%氧化釔安定之氧化鋯。在一些情況中,同樣亦發現,添加氧化鈰可增加穩定性。
施加至多孔基板表面以提供經塗佈的基板之金屬間擴散障壁顆粒層應覆蓋該多孔基板之孔,並提供層厚度大於0.01微米,及通常於0.01微米至25微米之範圍之層。金屬間擴散障壁之層厚度較佳係於0.1微米至20微米之範圍,及最佳地,2微米至3微米。
將金屬間擴散障壁施加至多孔基板後,可利用熟習此項技術者所知之任何適宜方式或方法將一或多層氣體選擇性材料(諸如鈀或銀)沉積於經塗佈之多孔基板上,該等方式或方法係諸如例如無電鍍覆、熱沉積、化學氣相沉積、電鍍、噴霧沉積、濺鍍塗佈、電子束蒸鍍、離子束蒸鍍及噴
霧熱解。將鈀及/或銀沉積於經塗佈之多孔基板上之較佳沉積方法為無電鍍覆。
如本文所用之術語氣體選擇性材料為一種當其係呈緻密薄膜之形式時,可選擇性滲透氣體之材料,且因此,此種材料之緻密薄層將發揮作用,以選擇性允許所選擇氣體穿過同時阻礙其他氣體穿過。本文所用之較佳氣體選擇性金屬為鈀及銀,以及其合金。銀亦可與其他金屬之鈀合金一起使用。
多孔支撐體上所支撐之鈀薄膜層之典型薄膜厚度可在1微米至50微米之範圍,但對於許多氣體分離應用而言,薄膜厚度於此範圍之上限值之可能太厚,而無法提供允許所需氣體分離之合理氣體通量。而且,各種先前技術製造方法亦通常提供無法接受之過厚之氣體選擇性材料之薄膜層之氣體分離薄膜系統,以致於其提供不可接受之氣體分離能力。一般而言,大於20微米之薄膜厚度係太厚,而無法提供自氣流之可接受的氫分離,且,甚至大於15微米之薄膜厚度亦不宜。
本文所述本發明方法之優勢之一在於,其可一致性地製造具有在多孔支撐體上所支撐之鈀層上均勻分佈的銀層之氣體分離薄膜系統。特定言之,可將緻密鈀-銀合金薄膜一致地製成10微米或更薄。通常,由本發明方法所製造之緻密鈀-銀合金薄膜具有範圍於0.001微米與10微米間之厚度,較佳地,0.01微米與8微米之間,及最佳地0.1微米與6微米之間。
如上所述,一般而言,當試圖將一層銀沉積於尚未活化之鈀層上時,則銀在鈀表面係沉積為島狀物之形式,而非均勻分佈的層體。此需在最後銀層上沉積數個額外鈀層,方能得到緻密氣密薄膜。本方法(採用非化學表面活化)可克服此問題,並可形成極薄但高效的鈀-銀氣體分離薄膜。
可使用熟習此項技術者所知之任何適宜方式或方法將銀上覆層沉積於鈀薄膜層上,該等方式或方法包括例如,無電鍍覆、熱沉積、化學氣相沉積、電鍍、噴霧沉積、濺鍍塗佈、電子束蒸鍍、離子束蒸鍍及噴霧熱解。用於沉積此銀上覆層之較佳沉積方法為無電鍍覆。
對鈀層或經合併以形成合金之鈀-銀層進行退火或熱處理可適宜地在400℃與800℃之間,較佳500℃與550℃之間之溫度下完成。上述層之退火可在氫氣氛或/及惰性氣體(諸如氮氣、氬氣或氦氣)中進行。在一較佳實施例中,退火係在100%氫氣氣氛或包含氫氣與3wt%至97 wt%選自氮氣、氬氣及氦氣組成之群之惰性氣體之混合物氣氛中完成。
沉積鈀層並退火後,接著打磨鈀表面,以產生於上述範圍內之平均表面粗糙度(Sa),即大於0.8微米至2.5微米,較佳在0.85微米與1.5微米之間,及更佳在0.9與1.2微米之間。已發現,雖然經塗佈之多孔基板上之鈀表面通常係以相對光滑為宜,也就是在所控制表面粗糙度範圍之內,但重要的是,表面不宜過於光滑。若鈀層表面係經高度拋
光,則無法將銀均勻地鍍覆於該表面上。
可將本發明氣體分離薄膜用於自氣體混合物選擇性分離一種選定氣體。特別可將氣體分離薄膜用於自含氫氣流分離氫氣,尤其係在高溫應用中。可使用本發明氣體分離薄膜之高溫應用之一實例為,在烴(諸如甲烷)之蒸汽重組中產生一氧化碳及氫氣,接著使所產生之一氧化碳與水以所謂的水煤氣轉化反應來反應,以產生二氧化碳及氫氣。此等催化反應為平衡型反應,而本發明氣體分離薄膜可用於同時分離所產生之氫氣,同時進行反應,以加強利於氫氣產生之平衡條件。同時進行反應所處之反應條件可包括於400℃至600℃範圍內之反應溫度及於1至30巴範圍內之反應壓力。
如上所述,可將本發明氣體分離薄膜用於各種涉及自含其他氣體(例如彼等選自由二氧化碳、水、甲烷或其混合物組成之群之氣體)之氣流中分離氫氣之應用。在此等應用中,溫度條件可係於上至600℃之範圍內,例如,於100℃至600℃之範圍內,而壓力條件可係於上至60巴之範圍內,例如,於1至60巴之範圍內。
下列實例係為進一步說明本發明而提供,然而,但並不應將其等視為限制本發明範圍。
此實例說明利用本發明方法製造含鈀及銀之氣體分離薄膜系統,該方法包括將一或多層銀沉積於一或多層鈀上,該(等)鈀係沉積於業已經金屬間擴散障壁塗佈之多孔基板
上。
將含鈀及經氧化釔安定之氧化鋯之貴金屬蛋殼催化劑之漿液沉積於1" OD×15"之英高鎳(Inconel)多孔金屬管表面上,以形成金屬間擴散障壁,其具有2-3微米之厚度,並係在5-8" Hg下藉由鍍覆5分鐘而附接。此後,藉由使含水、氫氧化銨、四胺基二氯化鈀(II)、EDTA二鈉及肼之鈀鍍覆浴溶液在經塗佈之多孔管表面上循環,將第一鈀膜沉積於經金屬間擴散障壁塗佈之多孔管上,直至得到厚度為1-2微米之第一鈀層。清洗、乾燥該鈀層並對其實施退火。接著利用5微米砂紙打磨(即交叉網格)經退火之鈀層表面,以提供介於0.85微米與2.5微米之間之平均表面粗糙度(Sa)。此後,利用含651 ml 28-30%氫氧化銨溶液/公升、4.86 g硝酸銀(AgNO3)/公升、0.54 g四胺基二氯化鈀(II)(Pd(NH3)4Cl2)、33.6 g乙二胺四乙酸二鈉鹽(Na2EDTA.2H2O)/公升、2.9 ml 1M肼溶液及足以製備總體積為1公升之去離子(DI)水之溶液,在具有經退火、經打磨的鈀表面層之經塗佈的多孔管之經打磨的鈀表面上鍍覆第一銀膜,直至沉積第一銀層。此外,使複合薄膜每15分鐘旋轉¼圈。溶液溫度為50℃,而鍍覆時間為120分鐘。重複鍍覆、清洗、乾燥、退火及拋光步驟,以產生額外銀或鈀層,直至薄膜係氣密。所採用退火溫度為約500-550℃。
本文將具有經退火、經打磨之表面之經銀或鈀塗佈之多孔管稱為「複合薄膜」。
使Mott corp之6英寸多孔Inconel 625支撐體塗佈經氧化釔安定之氧化鋯金屬間擴散障壁,並藉由在50℃下,在5-7英寸Hg下牽引鈀鍍覆液穿過該支撐體而附接。清洗並乾燥此含金屬間擴散障壁之多孔管,接著利用第一鍍覆步驟對其進行鍍覆。以7個鍍覆步驟製備鈀及銀薄膜。該等金屬係以下列順序鍍覆:
1)鈀
2)銀
3)鈀
4)銀
5)鈀
6)鈀
7)鈀
藉由使含水、氫氧化銨、四胺基二氯化鈀(II)、EDTA二鈉及肼之鈀鍍覆浴溶液在經塗佈之多孔管表面上流動進行鈀鍍覆步驟,直至得到厚度為1-2微米之第一鈀層。清洗、乾燥該鈀層並對其進行退火。接著利用砂紙打磨(即交叉網格)經退火之鈀層表面,以使鈀層之表面粗糙度增加至提供0.85微米與2.5微米之間之平均表面粗糙度(Sa)。此後,利用含氫氧化銨溶液、硝酸銀(AgNO3)、四胺基二氯化鈀(II)(Pd(NH3)4Cl2)及乙二胺四乙酸二鈉鹽(Na2EDTA.2H2O)以及1M肼溶液之銀鍍覆浴溶液,在具有經退火、經打磨的鈀表面層之經塗佈的多孔管之經打磨的
鈀表面上鍍覆第一銀層膜,直至沉積第一銀層。此外,使複合薄膜每15分鐘旋轉¼圈。具有經銀塗佈之鈀層之經塗布之多孔管經清洗、乾燥、退火,並經砂紙打磨(即交叉網格),以提供0.85微米與2.5微米之間之平均表面粗糙度(Sa)。以上文所給定之順序重複鍍覆操作。
藉由XRF(x-射線螢光)監測薄膜之組成,並藉由光學輪廓儀得到表面粗糙度Sa。下表顯示各種操作之數值。最終密封鈀/銀薄膜包含22 wt.%銀。
雖然利用硝酸銀溶液之銀之無電鍍覆通常係藉由使鍍覆液流動進行,但已發現,當硝酸銀採用上實例1中所用鍍覆液所採用之濃度時,來自銀鍍覆液之沉積物之擴散並未受到控制。因此,無需使銀鍍覆液流動,也就是說在相對靜止條件下,在無電鍍覆槽中可有效完成銀鍍覆。
雖然參考其較佳實施例已描述本發明,但熟習此項技術者應瞭解,可對其形式及細節作各種修改而不脫離下列申請專利範圍中所列出之本發明範圍。
Claims (15)
- 一種製備鈀-銀合金氣體分離薄膜系統之方法,其中該方法包括:提供多孔性支撐體,於其上支撐包括鈀之層;藉由使用一種研磨介質打磨該鈀層以施加磨蝕圖案及超過0.8微米上至2.5微米之平均表面粗糙度(Sa)而使該鈀層表面活化;不藉助化學活化,將包括銀之上覆層沉積於該經活化的鈀層表面上,該包括銀之上覆層係鍍覆於該經活化的鈀層表面上,及使該鈀層及銀上覆層在400℃與800℃間之溫度下退火。
- 如請求項1之方法,其中在沉積該銀上覆層之前,將該鈀層打磨至於0.85微米至1.5微米範圍內之平均表面粗糙度(Sa)。
- 如請求項1或請求項2之方法,其中將金屬間擴散障壁施加於該多孔基板,並置於該多孔基板與該鈀層之間。
- 如請求項1至請求項3中任一項之方法,其中所沉積銀之量係介於全部鈀層之1 wt%至35 wt%之間。
- 如請求項1至請求項4中任一項之方法,其中該鈀層係利用粒徑為1至10微米之研磨介質進行打磨。
- 如請求項1至請求項5中任一項之方法,其中沉積於該經活化的鈀層上之該銀上覆層具有介於0.01微米與10微米間之厚度。
- 如請求項1至請求項6中任一項之方法,其中在藉由打磨至超過0.8微米至2.5微米之表面粗糙度(Sa)使該銀上覆層活化後,將另一鈀層沉積於該銀上覆層上。
- 如請求項1至請求項7中任一項之方法,其中在鍍覆該銀上覆層之前,將該鈀層打磨至於0.9微米至1.2微米範圍內之平均表面粗糙度(Sa)。
- 如請求項1至請求項8中任一項之方法,其中該鈀-銀合金薄膜具有0.001微米至10微米之厚度。
- 如請求項1至請求項9中任一項之方法,其中在沉積該鈀層之前,將一層銀沉積於該金屬間擴散障壁上。
- 如請求項1至請求項10中任一項之方法,其中在將鈀層沉積於該銀層上之前,藉由打磨至介於0.85微米與1.5微米間之平均表面粗糙度(Sa)來使沉積於該金屬間擴散障壁上之該銀層活化。
- 如請求項1至請求項11中任一項之方法,其中沉積於該經活化的鈀層上之該銀上覆層具有介於1微米與2微米間之厚度。
- 如請求項1至請求項12中任一項之方法,其中該銀上覆層係在不使鍍覆液循環的情況下藉由無電鍍覆來沉積。
- 一種藉由如請求項1至13之方法中之任一者所製備之鈀-銀合金氣體分離薄膜系統。
- 一種自含氫氣體混合物分離氫氣之方法,其係藉由使該氣體混合物穿過藉由如請求項1至14之方法中之任一者所製備之鈀-銀合金氣體分離薄膜系統。
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US20140251131A1 (en) * | 2013-03-07 | 2014-09-11 | James Douglas Way | Palladium-alloyed membranes and methods of making and using the same |
WO2015157414A1 (en) * | 2014-04-10 | 2015-10-15 | Shell Oil Company | A method of making a supported gas separation membrane |
US20150292090A1 (en) * | 2014-04-10 | 2015-10-15 | Shell Oil Company | Method of making a supported gas separation membrane |
US9987612B1 (en) | 2017-04-13 | 2018-06-05 | Caterpillar Inc. | Reactor assembly |
JP2024023015A (ja) * | 2022-08-08 | 2024-02-21 | トヨタ自動車株式会社 | 水素分離フィルター |
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US6152987A (en) * | 1997-12-15 | 2000-11-28 | Worcester Polytechnic Institute | Hydrogen gas-extraction module and method of fabrication |
AU2004224370C1 (en) * | 2003-03-21 | 2008-03-13 | Worcester Polytechnic Institute | Composite gas separations modules having intermediate metal layers |
JP2006520687A (ja) | 2003-03-21 | 2006-09-14 | ウスター ポリテクニック インスティチュート | 複合ガス分離モジュールを製造する方法 |
US7959711B2 (en) * | 2006-11-08 | 2011-06-14 | Shell Oil Company | Gas separation membrane system and method of making thereof using nanoscale metal material |
US7744675B2 (en) | 2006-11-08 | 2010-06-29 | Shell Oil Company | Gas separation membrane comprising a substrate with a layer of coated inorganic oxide particles and an overlayer of a gas-selective material, and its manufacture and use |
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US8048199B2 (en) * | 2007-02-20 | 2011-11-01 | Shell Oil Company | Method of making a leak stable gas separation membrane system |
JP5882295B2 (ja) * | 2010-03-26 | 2016-03-09 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | 担持ガス分離膜を形成する方法および装置 |
US8721773B2 (en) * | 2011-10-26 | 2014-05-13 | Shell Oil Company | Method for preparing a palladium-gold alloy gas separation membrane system |
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- 2012-12-17 CA CA2858597A patent/CA2858597A1/en not_active Abandoned
- 2012-12-17 EP EP12809961.1A patent/EP2794079A1/en not_active Ceased
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CA2858597A1 (en) | 2013-06-27 |
WO2013096184A1 (en) | 2013-06-27 |
KR20140108644A (ko) | 2014-09-12 |
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US20130152785A1 (en) | 2013-06-20 |
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