TWI554469B - A hydrogen purifying apparatus and a hydrogen purifying system using the same - Google Patents
A hydrogen purifying apparatus and a hydrogen purifying system using the same Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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本發明涉及一種利用了鈀合金薄膜的氫氣選 擇透過性的氫純化裝置及使用其的氫純化系統,更具體而言,本發明涉及一種可對導入於槽室的一次側空間的含雜質的原料氫進行高效加熱的氫純化裝置及使用其的氫純化系統。 The invention relates to a hydrogen selection using a palladium alloy film A selective hydrogen purification apparatus and a hydrogen purification system using the same, and more particularly, the present invention relates to a hydrogen purification apparatus capable of efficiently heating an impurity-containing raw material hydrogen introduced into a primary side space of a cell chamber, and using the same Hydrogen purification system.
一直以來,在半導體製造工程中,大量使用高純度的氫氣作為環境氣體。關於這樣的氫氣,因半導體的積合度的提高而要求雜質的濃度為極低的濃度(ppb程度以下)。 High-purity hydrogen gas has been used in large quantities as an ambient gas in semiconductor manufacturing engineering. With regard to such hydrogen gas, the concentration of the impurity is required to be an extremely low concentration (below the ppb level) due to an increase in the degree of integration of the semiconductor.
另一方面,作為工業大量製造高純度氫的方法,人們公知的方法如下:以深冷吸附法、變壓法等,將從甲醇、二甲醚、天然氣、液化石油氣等以水蒸氣重組反應(steam reforming reaction)而得到的重組氣體分離為氫與氫以外的氣體,從而得到氫。 On the other hand, as a method for industrially producing high-purity hydrogen in large quantities, a known method is as follows: a rehydration reaction of methanol, dimethyl ether, natural gas, liquefied petroleum gas, or the like is carried out by a cryogenic adsorption method, a pressure swing method, or the like ( The reformed gas obtained by the steam reforming reaction is separated into a gas other than hydrogen and hydrogen to obtain hydrogen.
深冷吸附法為如下純化方法:將含氫氣體流通於吸附筒以除去氫以外的雜質,該吸附筒中填充了將液化氮作為冷卻劑而被極低溫化後的吸附材料。變壓法為如下純化方法:使含氫氣體依次流通於複數個吸附筒 The cryogenic adsorption method is a purification method in which a hydrogen-containing gas is circulated to an adsorption tube to remove impurities other than hydrogen, and the adsorption tube is filled with an adsorption material that is extremely low temperature by using liquefied nitrogen as a coolant. The pressure transformation method is a purification method in which a hydrogen-containing gas is sequentially circulated to a plurality of adsorption cartridges.
,並且重複進行升壓、雜質的吸附、雜質的脫附以及吸附材料的再生的各個操作,從而去除氫以外的雜質。在上述那樣的重組氣體中,除了氫以外,還含有一氧化碳、二氧化碳、甲烷、氮、水等,在深冷吸附法、變壓法中,很難使這些雜質達到極低的濃度(ppb程度以下)而去除。 And each operation of boosting, adsorption of impurities, desorption of impurities, and regeneration of adsorbed material is repeated, thereby removing impurities other than hydrogen. In addition to hydrogen, the above-mentioned reformed gas contains carbon monoxide, carbon dioxide, methane, nitrogen, water, etc., and in the cryogenic adsorption method and the pressure transformation method, it is difficult to achieve extremely low concentrations of these impurities (below ppb). ) and removed.
對此,作為以比較少量的方式得到極高純度 的氫氣的方法,人們公知的方法如下:將含雜質的原料氫供給至由鈀合金的薄膜構成的氫分離膜,利用氫氣的選擇透過性而僅使氫透過而取出。用於這樣的氫純化的裝置為如下氫純化裝置,其在含雜質的原料氫的導入口、純氫的取出口以及在該導入口和該取出口之間的氣體流路中具有鈀合金的薄膜,例如專利文獻1~3所示,為具有如下結構的氫純化裝置,其中,一端被封住的複數根鈀合金細管(氫分離膜)在其另一端的開口部以管板支承,被收納於槽室(cell)內,藉由該鈀合金細管和管板,槽室內被分隔為一次側空間(含雜質的原料氫的供給側空間)和二次側空間(純氫的取出側空間)這兩個空間。 In this regard, as a relatively small amount of way to obtain extremely high purity As a method of hydrogen gas, a known method is as follows: a hydrogen-containing raw material hydrogen is supplied to a hydrogen separation membrane made of a thin film of a palladium alloy, and only hydrogen is permeated and taken out by selective permeability of hydrogen gas. The apparatus for purifying such hydrogen is a hydrogen purifying apparatus having a palladium alloy in the inlet of the impurity-containing raw material hydrogen, the outlet of pure hydrogen, and the gas flow path between the inlet and the outlet. The film is a hydrogen purification device having a structure in which a plurality of palladium alloy thin tubes (hydrogen separation membrane) sealed at one end are supported by a tube sheet at the opening of the other end, as shown in Patent Documents 1 to 3. The inside of the tank is partitioned into a primary side space (supply side space of the raw material hydrogen containing impurities) and a secondary side space (the extraction side space of pure hydrogen) by the palladium alloy thin tube and the tube sheet. ) These two spaces.
[專利文獻1]日本特開昭62-128903號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 62-128903
[專利文獻2]日本特開平1-145302號公報 [Patent Document 2] Japanese Patent Laid-Open No. 1-145302
[專利文獻3]日本特開平1-145303號公報 [Patent Document 3] Japanese Patent Laid-Open No. 1-145303
利用鈀合金的氫分離膜的氫純化方法與深冷吸附法、變壓法相比,具有每單位時間之純氫取出量少的缺點,但是除了上述那樣能得到高純度的氫氣以外,具有能使裝置小型化、簡化的長處。但是使含雜質的原料氫接觸於鈀合金細管而透過該細管時,有需要充分地加熱該細管和原料氫,除了用於將槽室的內部加熱的加熱器以外,需要用於預先加熱原料氫的加熱器等的設備。 The hydrogen purification method using a hydrogen separation membrane of a palladium alloy has a disadvantage that the amount of pure hydrogen taken out per unit time is small as compared with the cryogenic adsorption method and the pressure transformation method. However, in addition to the above-described high purity hydrogen gas, it is possible to The device is miniaturized and simplified. However, when the hydrogen containing the impurity-containing raw material is passed through the thin tube of the palladium alloy and is passed through the thin tube, it is necessary to sufficiently heat the thin tube and the raw material hydrogen, and in addition to the heater for heating the inside of the chamber, it is necessary to preheat the raw material hydrogen. Equipment such as heaters.
在利用了鈀合金薄膜的氫分離膜的氫純化中,為了增加每單位時間的純氫的取出量,例如,如果進行氫純化裝置的大型化,則具有用於預先加熱原料氫的加熱器等的設備也為大型的問題,另外,增加氫純化裝置的話,則具有配管等設備增多而變得複雜,削弱小型化、簡化的長處的問題。因此,本發明想要解決的問題為提供一種氫純化裝置、以及使用複數個該氫純化裝置的氫純化系統,該氫純化裝置可對導入於槽室的一次側空間的含雜質的原料氫進行高效加熱。 In the hydrogen purification of the hydrogen separation membrane using the palladium alloy thin film, in order to increase the amount of pure hydrogen extracted per unit time, for example, when the hydrogen purification apparatus is increased in size, a heater for preheating the raw material hydrogen or the like is provided. In addition, when the hydrogen purification device is added, the number of devices such as piping increases and becomes complicated, and the problem of miniaturization and simplification is weakened. Therefore, the problem to be solved by the present invention is to provide a hydrogen purification apparatus and a hydrogen purification system using a plurality of the hydrogen purification apparatuses, which can perform impurity-containing raw material hydrogen introduced into the primary side space of the chamber. Efficient heating.
本發明人等為了解決上述問題而進行了深入研究,結果發現如下成果,進而達成了本發明的氫純化裝置,即,如果在上述那樣的氫純化裝置中,將槽室(cell)的一次側空間的形狀設定為細長的形狀,並且將含雜質的原料氫的導入配管以通過該槽室的細長的側壁與用於將槽室內加熱的加熱器之間的間隙的方式設置,則用該加熱器的熱量充分地加熱流通於該導入配管內部的原料 氫,即使氫純化裝置為大型的情況下,或使用許多個氫純化裝置的情況下,仍能夠將裝置維持於小型且簡化的形態。 The present inventors have conducted intensive studies to solve the above problems, and as a result, have found the following results, and have achieved the hydrogen purification apparatus of the present invention, that is, in the above-described hydrogen purification apparatus, the primary side of the cell The shape of the space is set to an elongated shape, and the introduction pipe of the raw material hydrogen containing impurities is disposed in such a manner as to pass through a gap between the elongated side wall of the chamber and a heater for heating the chamber, and the heating is used. The heat of the device sufficiently heats the raw material flowing inside the introduction pipe Hydrogen can maintain the device in a small and simplified form even when the hydrogen purification device is large or when a plurality of hydrogen purification devices are used.
即,本發明為一種氫純化裝置,其係具有藉 由一端被封住的複數根鈀合金細管和在細管的開口端部中支撐該細管的管板,將在外周具有加熱部的槽室的內部分隔為一次側空間和二次側空間,其中,將含雜質的原料氫從一次側空間導入,使其透過鈀合金細管而從二次側空間取出純氫,該氫純化裝置之特徵在於,鈀合金細管的長度為管板的直徑的15倍以上,含雜質的原料氫的導入配管以通過槽室的側壁與加熱器之間的間隙的方式而設置。 That is, the present invention is a hydrogen purification device, which has a a plurality of palladium alloy thin tubes sealed at one end and a tube sheet supporting the thin tube in the open end of the thin tube, and the inside of the chamber having the heating portion on the outer circumference is partitioned into a primary side space and a secondary side space, wherein The raw material hydrogen containing impurities is introduced from the primary side space, and is passed through a palladium alloy thin tube to extract pure hydrogen from the secondary side space. The hydrogen purification apparatus is characterized in that the length of the palladium alloy thin tube is 15 times or more the diameter of the tube sheet. The introduction piping of the raw material hydrogen containing impurities is provided in such a manner as to pass through a gap between the side wall of the chamber and the heater.
另外,本發明為一種氫純化系統,其特徵在於,並列設置複數個上述氫純化裝置,將複數個該氫純化裝置的各個原料氫的導入配管連接於外部的一根原料氫供給配管,將複數個該氫純化裝置的各個純氫取出配管連接於外部的一根純氫回收配管。 Moreover, the present invention is a hydrogen purification system in which a plurality of the above-described hydrogen purification apparatuses are arranged in parallel, and a plurality of raw material hydrogen introduction pipes of the plurality of hydrogen purification apparatuses are connected to one external raw material hydrogen supply pipe, and the plural Each of the pure hydrogen extraction pipes of the hydrogen purification device is connected to an external pure hydrogen recovery pipe.
在本發明的氫純化裝置中,將槽室的一次側空間設定為細長的形狀,含雜質的原料氫的導入配管以通過該槽室的細長的側壁與用於將槽室內加熱的加熱器之間的方式構成。即,在本發明中,為藉用於將槽室內加熱的加熱器而充分加熱原料氫的導入配管的結構,故能夠縮小或不需要用於預先加熱原料氫的加熱器等設備。特別是在氫純化裝置為大型的場合、氫純化裝置為複 數個的場合,能在能夠謀求裝置的小型化、簡化的方面發揮效果。 In the hydrogen purification apparatus of the present invention, the primary side space of the tank chamber is set to an elongated shape, and the introduction piping of the raw material hydrogen containing impurities is passed through the elongated side wall of the chamber and the heater for heating the chamber. The way between the two. In other words, in the present invention, the introduction piping for sufficiently heating the raw material hydrogen by the heater for heating the inside of the tank can reduce or eliminate equipment such as a heater for heating the raw material hydrogen in advance. Especially in the case where the hydrogen purification device is large, the hydrogen purification device is complex In a few cases, it is possible to achieve an effect in miniaturization and simplification of the device.
1‧‧‧鈀合金細管 1‧‧‧Palladium alloy thin tube
2‧‧‧管板 2‧‧‧ tube plate
3‧‧‧加熱器 3‧‧‧heater
4‧‧‧槽室 4‧‧‧Slot room
4’‧‧‧槽室的一次側空間 4'‧‧‧ one-side space of the trough
4”‧‧‧槽室的二次側空間 4"‧‧‧Second side space of the chamber
5‧‧‧原料氫的導入配管 5‧‧‧Introduction of raw material hydrogen
6‧‧‧槽室的側壁 6‧‧‧ Side wall of the chamber
7‧‧‧開口端部 7‧‧‧Open end
8‧‧‧閉口端部 8‧‧‧Closed end
9‧‧‧原料氫供給口 9‧‧‧ Raw material hydrogen supply port
10‧‧‧含雜質氣體取出口 10‧‧‧Extracted gas containing impurities
11‧‧‧純氫取出口 11‧‧‧ Pure hydrogen is exported
12‧‧‧導熱介質 12‧‧‧ Thermal medium
13‧‧‧發熱線 13‧‧‧heating line
14‧‧‧原料氫供給配管 14‧‧‧ Raw material hydrogen supply piping
15‧‧‧含雜質的氣體回收配管 15‧‧‧Gas recovery piping containing impurities
16‧‧‧純氫取出配管 16‧‧‧Pure hydrogen extraction piping
17‧‧‧純氫回收配管 17‧‧‧Pure hydrogen recovery piping
圖1表示本發明的氫純化裝置的一個例子的結構圖。 Fig. 1 is a view showing the configuration of an example of a hydrogen purifying apparatus of the present invention.
圖2表示本發明的圖1以外的氫純化裝置的一個例子的結構圖。 Fig. 2 is a view showing the configuration of an example of a hydrogen purifying apparatus other than Fig. 1 of the present invention.
圖3(1)表示在圖1的氫純化裝置的管板位置的剖面的一個例子的結構圖。圖3(2)表示在圖1的氫純化裝置的鈀合金細管位置的剖面的一個例子的結構圖。 Fig. 3 (1) is a structural view showing an example of a cross section at the position of the tube sheet of the hydrogen purification apparatus of Fig. 1. Fig. 3 (2) is a structural view showing an example of a cross section of the palladium alloy capillary tube position of the hydrogen purification device of Fig. 1.
圖4表示本發明的氫純化系統的例子的結構圖。 Fig. 4 is a view showing the configuration of an example of the hydrogen purification system of the present invention.
本發明適用於如下述方式的氫純化裝置,其中,藉由一端被封住的鈀合金細管和支撐該細管的開口端部的管板將槽室的內部分隔為一次側空間和二次側空間,將含雜質的氫從一次側空間導入,使其透過鈀合金細管而從二次側空間取出純氫。另外,作為適用於本發明的原料氫,可列舉出:將從甲醇、二甲醚、天然氣、液化石油氣等利用水蒸氣重組反應得到的重組氣體;利用深冷吸附法、變壓法預備純化該重組氣體而得到的高純度氫。利用該方法得到的氫通常貯藏於氣體鋼瓶、貯藏槽等貯藏裝置。根據本發明得到的極高純度的純化氫例如用於半導體製造工程中的環境氣體(載氣)。 The present invention is applicable to a hydrogen purifying apparatus in which the inside of the tank chamber is partitioned into a primary side space and a secondary side space by a palladium alloy thin tube sealed at one end and a tube sheet supporting the open end of the thin tube Hydrogen containing impurities is introduced from the primary side space, and is passed through a palladium alloy capillary tube to take out pure hydrogen from the secondary side space. Further, examples of the raw material hydrogen to be used in the present invention include a reformed gas obtained by recombination reaction of methanol, dimethyl ether, natural gas, and liquefied petroleum gas by steam; and preliminary purification by a cryogenic adsorption method or a pressure swing method. High purity hydrogen obtained by the reformed gas. The hydrogen obtained by this method is usually stored in a storage device such as a gas cylinder or a storage tank. The extremely high purity purified hydrogen obtained according to the present invention is used, for example, as an ambient gas (carrier gas) in semiconductor manufacturing engineering.
以下,基於圖1~圖4對本發明的氫純化裝置 和使用其的氫純化系統進行詳細說明,但本發明並不限於此。另外,圖1、圖2為顯示本發明的氫純化裝置的一個例子的結構圖,圖3(1)為表示在圖1的氫純化裝置的管板位置的剖面的一個例子的結構圖,圖3(2)為表示在圖1的鈀合金細管位置的剖面的一個例子的結構圖,圖4為表示本發明的氫純化系統的一個例子的結構圖。 Hereinafter, the hydrogen purification device of the present invention will be described based on FIGS. 1 to 4 . The hydrogen purification system using the same will be described in detail, but the present invention is not limited thereto. 1 and 2 are structural views showing an example of a hydrogen purifying apparatus of the present invention, and FIG. 3 (1) is a structural view showing an example of a cross section at the tube sheet position of the hydrogen purifying apparatus of FIG. 3(2) is a structural view showing an example of a cross section at the position of the palladium alloy capillary tube of Fig. 1, and Fig. 4 is a configuration diagram showing an example of the hydrogen purification system of the present invention.
本發明的氫純化裝置如圖1、圖2所示,其係 具有藉由一端被封住的複數根鈀合金細管1和在細管的開口端部中支撐該細管的管板2,將在外周具有加熱器3的槽室4的內部分隔為一次側空間4’和二次側空間4”,將含雜質的原料氫從一次側空間4’的原料氫供給口9導入,使其透過鈀合金細管而從二次側空間4”的純氫取出口11取出純氫,該氫純化裝置特徵在於,鈀合金細管1的長度為管板2的直徑的15倍以上,如圖1~圖3所示,含雜質的原料氫的導入配管5以通過槽室4的側壁6與加熱器3之間的間隙的方式而設置。 The hydrogen purification device of the present invention is shown in Fig. 1 and Fig. 2, There is a plurality of palladium alloy thin tubes 1 sealed at one end and a tube sheet 2 supporting the thin tubes in the open end of the thin tubes, and the inside of the chamber 4 having the heater 3 on the outer circumference is partitioned into the primary side space 4' And the secondary side space 4", the raw material hydrogen containing impurities is introduced from the raw material hydrogen supply port 9 of the primary space 4', and is passed through the palladium alloy thin tube to take out the pure hydrogen from the secondary side space 4". Hydrogen, the hydrogen purification apparatus is characterized in that the length of the palladium alloy thin tube 1 is 15 times or more the diameter of the tube sheet 2, and as shown in FIGS. 1 to 3, the introduction piping 5 of the raw material hydrogen containing impurities passes through the tank chamber 4. The gap between the side wall 6 and the heater 3 is provided.
以下,對本發明的氫純化裝置的各個組成部 進行詳細說明。 Hereinafter, each component of the hydrogen purification device of the present invention Detailed instructions are given.
本發明的氫純化裝置的槽室的形態如圖1、2 所示,正面的外形呈U字形、ㄈ字形或與其類似的形狀,在剖面為圓形的容器的開口部上設置具有純氫取出口的蓋。在本發明的氫純化裝置中,流通原料氫的導入配管5的內部的原料氫藉由加熱器3充分加熱直到到達原料氫供給口9,以該方式將槽室4(特別是4’側)設定為細長形狀(以管板的直徑變小的方式)。另外,加熱器3橫跨設置於 槽室的側壁中的至少鈀合金細管所設置部分的側壁的外周整體上。由此,在本發明中,較佳為將鈀合金細管1的長度設定為遠長於管板2的直徑,通常為管板直徑的15倍以上,較佳為20倍以上。另外,槽室4的二次側空間4”側在裝置小型化的方面較佳為較小,故槽室的管板的上游側的空間的體積相對地比槽室的管板的下游側的空間的體積大,通常為槽室的管板的下游側的空間的體積的10倍以上,較佳為15倍以上,更佳為20倍以上。但是,上述體積為不考慮上述鈀合金細管的存在的情況。 The shape of the tank chamber of the hydrogen purification device of the present invention is shown in Figs. As shown in the figure, the front surface has a U-shape, a U-shape or a shape similar thereto, and a cover having a pure hydrogen take-out port is provided on the opening of the container having a circular cross section. In the hydrogen purification apparatus of the present invention, the raw material hydrogen flowing inside the introduction pipe 5 through which the raw material hydrogen flows is sufficiently heated by the heater 3 until reaching the raw material hydrogen supply port 9, and the groove chamber 4 (especially the 4' side) is disposed in this manner. It is set to an elongated shape (in such a manner that the diameter of the tube sheet becomes smaller). In addition, the heater 3 is disposed across At least the outer periphery of the side wall of the portion where the palladium alloy thin tube is disposed in the side wall of the tank chamber is entirely. Therefore, in the present invention, it is preferable to set the length of the palladium alloy thin tube 1 to be much longer than the diameter of the tube sheet 2, and is usually 15 times or more, preferably 20 times or more the diameter of the tube sheet. Further, the secondary side space 4" side of the tank chamber 4 is preferably small in terms of miniaturization of the apparatus, so that the volume of the space on the upstream side of the tube sheet of the tank chamber is relatively larger than the downstream side of the tube sheet of the tank chamber. The volume of the space is large, and is usually 10 times or more, preferably 15 times or more, more preferably 20 times or more, the volume of the space on the downstream side of the tube sheet of the chamber. However, the above volume is not considered in the above-mentioned palladium alloy thin tube. The situation exists.
在本發明的氫純化裝置中,含雜質的原料氫 的導入配管5如前述那樣,以通過槽室4的側壁6與加熱器3之間的間隙的方式而設定,但如圖3所示,較佳為在原料氫的導入配管5與槽室的側壁6與加熱器3之間的間隙中填充導熱水泥(cement)等固體的導熱介質12,將源自加熱器3的熱量高效地傳遞給原料氫的導入配管5。以隔著導熱介質而通過槽室的側壁與加熱器之間的間隙的方式設定的原料氫的導入配管(具有圖3那樣的結構的原料氫的導入配管)的長度通常為槽室4的側壁6的長度的50%以上,較佳為80%以上,更佳為90%以上。另外,上述槽室4的側壁6的長度為圖1、圖2中的槽室4的側壁6的直線部分的長度。 In the hydrogen purification device of the present invention, the impurity-containing raw material hydrogen As described above, the introduction pipe 5 is set so as to pass through the gap between the side wall 6 of the tank chamber 4 and the heater 3. However, as shown in Fig. 3, the introduction pipe 5 and the groove chamber of the raw material hydrogen are preferably used. The gap between the side wall 6 and the heater 3 is filled with a solid heat transfer medium 12 such as a cement, and the heat derived from the heater 3 is efficiently transmitted to the introduction pipe 5 of the raw material hydrogen. The length of the raw material hydrogen introduction pipe (the introduction pipe of the raw material hydrogen having the structure shown in FIG. 3) which is set to pass through the gap between the side wall of the tank chamber and the heater via the heat transfer medium is usually the side wall of the tank chamber 4 The length of 6 is 50% or more, preferably 80% or more, more preferably 90% or more. Further, the length of the side wall 6 of the above-described tank chamber 4 is the length of the straight portion of the side wall 6 of the tank chamber 4 in Figs. 1 and 2 .
另外,在本發明的氫純化裝置中,原料氫的 導入配管5通常以與鈀合金細管平行的方式設置,但也可設置為螺旋狀。在以與鈀合金細管平行的方式設置的場合,通過槽室的側壁與加熱器之間的間隙的結構的原料 氫的導入配管的長度通常為30cm以上,較佳為40cm以上。另外,原料氫的導入配管5的內徑通常為6mm以下。如果導入配管5的內徑超過6mm,則流通導入配管5的內部的原料氫將有可能無法充分加熱。 In addition, in the hydrogen purification device of the present invention, the raw material hydrogen The introduction pipe 5 is usually provided in parallel with the palladium alloy thin tube, but may be provided in a spiral shape. In the case where it is disposed in parallel with the palladium alloy thin tube, the material of the structure passing through the gap between the side wall of the chamber and the heater The length of the hydrogen introduction pipe is usually 30 cm or more, preferably 40 cm or more. Moreover, the inner diameter of the raw material hydrogen introduction pipe 5 is usually 6 mm or less. When the inner diameter of the introduction pipe 5 exceeds 6 mm, the raw material hydrogen flowing into the inside of the introduction pipe 5 may not be sufficiently heated.
本發明的氫純化裝置中使用的鈀合金細管1如圖1所示,由在管板2側的一端具有開口端部7,在相反側的一端具有閉口端部8的管構成。鈀合金細管1如上述那樣,其長度為管板的直徑的15倍以上,具體為20~200cm。另外,外徑通常為1.0~5.0mm,厚度通常為30~100μm。另外,鈀合金細管1相對於一個鈀合金膜單元而言使用3~100根。它們的配置沒有特別限制,相鄰的鈀合金細管之間的間隔通常設定為1.0~2.5mm。 As shown in Fig. 1, the palladium alloy capillary tube 1 used in the hydrogen purification apparatus of the present invention comprises a tube having an open end portion 7 at one end on the tube sheet 2 side and a closed end portion 8 at one end on the opposite side. As described above, the palladium alloy thin tube 1 has a length of 15 times or more, specifically 20 to 200 cm, of the diameter of the tube sheet. Further, the outer diameter is usually 1.0 to 5.0 mm, and the thickness is usually 30 to 100 μm. Further, the palladium alloy thin tube 1 is used in an amount of 3 to 100 with respect to one palladium alloy film unit. Their configuration is not particularly limited, and the interval between adjacent palladium alloy thin tubes is usually set to 1.0 to 2.5 mm.
作為上述鈀合金細管1的結構成分,可示例出 以鈀和銅為主成分的合金、以鈀和銀為主成分的合金、以鈀和銀和金為主成分的合金。使用這些合金的場合,較佳為鈀50~70wt%和銅30~50wt%的合金、鈀60~90wt%和銀10~40wt%的合金、鈀60~80wt%和銀10~37wt%和金3~10wt%的合金。鈀合金也可含有其他金屬,但上述金屬通常為95wt%以上,較佳為99wt%以上。 As a structural component of the above-mentioned palladium alloy thin tube 1, it can be exemplified An alloy mainly composed of palladium and copper, an alloy mainly composed of palladium and silver, and an alloy mainly composed of palladium, silver and gold. When these alloys are used, an alloy of palladium 50 to 70 wt% and copper 30 to 50 wt%, an alloy of palladium 60 to 90 wt% and silver 10 to 40 wt%, palladium 60 to 80 wt%, and silver 10 to 37 wt% and gold 3 are preferable. ~10wt% alloy. The palladium alloy may also contain other metals, but the above metal is usually 95% by weight or more, preferably 99% by weight or more.
本發明中使用的管板2通常為厚度3~30mm的 圓盤。另外,管板2的直徑為鈀合金細管的長度的1/15以下,較佳為1/20以下,並且根據鈀合金細管1的直徑、根數等而不同,通常為10~40mm。在管板2中,如圖3(1)所示,在安裝鈀合金細管1的位置上預先設置使其插入的通孔。鈀合金細管1向管板2的支撐以焊接來進行。此時, 為了確保透過氫分離膜的純氫的流路空間,可根據需要將螺旋狀的彈簧插入到鈀合金細管1的內部。另外,管板2較佳為鎳製。 The tube sheet 2 used in the present invention is usually 3 to 30 mm in thickness. disc. In addition, the diameter of the tube sheet 2 is 1/15 or less, preferably 1/20 or less, and is different from the diameter and the number of the palladium alloy thin tubes 1, and is usually 10 to 40 mm. In the tube sheet 2, as shown in Fig. 3 (1), a through hole through which the palladium alloy thin tube 1 is attached is inserted in advance. The support of the palladium alloy thin tube 1 to the tube sheet 2 is performed by welding. at this time, In order to secure a flow path space of pure hydrogen permeating through the hydrogen separation membrane, a spiral spring may be inserted into the inside of the palladium alloy thin tube 1 as needed. Further, the tube sheet 2 is preferably made of nickel.
關於本發明中使用的加熱器3,如果能以規定 的溫度高效地加熱槽室4的內部的鈀合金細管1和原料氫、以及流通於原料氫的導入配管5的內部之原料氫的話,則沒有特別限制,例如,如圖1、2所示,可將發熱線13呈螺旋狀捲繞於槽室4的側壁6的外周、使用導熱性能優異的導熱水泥等的導熱介質12而覆蓋發熱線13,並且固定槽室4的側壁6的加熱器。加熱器3較佳為以至少覆蓋槽室在管板上游側的側壁整體而加熱的方式設定。 Regarding the heater 3 used in the present invention, if it can be specified The temperature of the palladium alloy thin tube 1 and the raw material hydrogen in the inside of the tank chamber 4 and the raw material hydrogen flowing inside the introduction pipe 5 of the raw material hydrogen are efficiently heated, for example, as shown in FIGS. The heating wire 13 can be wound around the outer circumference of the side wall 6 of the chamber 4 in a spiral shape, and the heating wire 13 can be covered with the heat transfer medium 12 such as heat conductive cement having excellent heat conductivity, and the heater of the side wall 6 of the chamber 4 can be fixed. The heater 3 is preferably set so as to cover at least the entire side wall of the tank chamber on the upstream side of the tube sheet.
在本發明的氫純化裝置中,為了回收不透過 鈀合金細管1的氣體,在槽室的一次側空間設置含雜質氣體取出口10。原料氫供給口9和含雜質氣體取出口10的位置如果在管板2的上游側位置的話,則沒有特別限制,以它們彼此遠離的方式設定較佳。例如,如圖1所示,將原料氫供給口9設置於遠離於管板2的位置的場合,含雜質氣體取出口10設置於靠近管板2的位置,如圖2所示,將原料氫供給口9設置於靠近管板2的位置的場合,含雜質氣體取出口10設置於遠離於管板2的位置。另外,為了回收透過鈀合金細管1的氫,在槽室的二次側空間設置純氫取出口11,並進一步設置用於回收到達純氫取出口11的純氫的純氫取出配管16。 In the hydrogen purification device of the present invention, in order to recover The gas of the palladium alloy thin tube 1 is provided with an impurity-containing gas take-out port 10 in the primary side space of the chamber. The position of the raw material hydrogen supply port 9 and the impurity-containing gas take-out port 10 is not particularly limited as long as it is located on the upstream side of the tube sheet 2, and is preferably set so as to be distant from each other. For example, as shown in FIG. 1, when the raw material hydrogen supply port 9 is disposed at a position away from the tube sheet 2, the impurity-containing gas take-out port 10 is disposed at a position close to the tube sheet 2, as shown in FIG. When the supply port 9 is provided at a position close to the tube sheet 2, the impurity-containing gas take-out port 10 is provided at a position away from the tube sheet 2. In addition, in order to collect hydrogen which has passed through the palladium alloy capillary tube 1, a pure hydrogen take-out port 11 is provided in the secondary side space of the cell chamber, and a pure hydrogen take-out pipe 16 for recovering pure hydrogen reaching the pure hydrogen take-out port 11 is further provided.
接著,對本發明的氫純化系統進行說明。 Next, the hydrogen purification system of the present invention will be described.
本發明的氫純化系統為如下氫純化系統:如圖4所示 那樣並列設置複數個上述氫純化裝置,將複數個該氫純化裝置的各個原料氫的導入配管5連接於外部的一根原料氫供給配管14,將複數個該氫純化裝置的各個純氫取出配管16連接於外部的一個純氫回收配管17。另外,在本發明的氫純化系統中,以從複數個氫純化裝置的含雜質氣體取出口10回收的含雜質的氫回收於外部的含雜質的氣體回收配管15的方式連接配管。 The hydrogen purification system of the present invention is the following hydrogen purification system: as shown in FIG. In the same manner, a plurality of the above-described hydrogen purification devices are arranged in parallel, and a plurality of raw material hydrogen introduction pipes 5 of the hydrogen purification device are connected to one external raw material hydrogen supply pipe 14 to take out a plurality of pure hydrogen extraction pipes of the hydrogen purification device. 16 is a pure hydrogen recovery pipe 17 connected to the outside. In the hydrogen purification system of the present invention, the impurity-containing gas recovered from the impurity-containing gas take-out port 10 of the plurality of hydrogen purification devices is connected to the external impurity-containing gas recovery pipe 15 so as to be connected to the pipe.
根據本發明進行氫純化時,將一個本發明的 氫純化裝置或圖4所示那樣設置的複數個本發明的氫純化裝置連接於外部的各個配管後,利用加熱器3對原料氫的導入配管5的內部和槽室4的內部進行加熱,並且藉由從原料氫供給配管供給原料氫來進行氫的純化。氫純化時的鈀合金細管1的溫度通常為250~500℃,較佳為300~450℃。原料氫與加熱後的鈀合金細管1接觸,只有氫透過鈀合金細管1,經由純氫取出口11、純氫取出配管16、純氫回收配管17而被回收。 When performing hydrogen purification according to the present invention, a method of the present invention The hydrogen purifying apparatus or the plurality of hydrogen purifying apparatuses of the present invention, which are provided as shown in FIG. 4, are connected to the respective external pipes, and then the inside of the raw material hydrogen introduction pipe 5 and the inside of the tank chamber 4 are heated by the heater 3, and Purification of hydrogen is carried out by supplying raw material hydrogen from a raw material hydrogen supply pipe. The temperature of the palladium alloy thin tube 1 at the time of hydrogen purification is usually 250 to 500 ° C, preferably 300 to 450 ° C. The raw material hydrogen is brought into contact with the heated palladium alloy thin tube 1 , and only hydrogen is transmitted through the palladium alloy thin tube 1 , and is recovered through the pure hydrogen take-out port 11 , the pure hydrogen take-out pipe 16 , and the pure hydrogen recovery pipe 17 .
接著,藉由實施例具體說明本發明,但本發明不侷限於此。 Next, the invention will be specifically described by way of examples, but the invention is not limited thereto.
在直徑20mm、厚度5mm的圓盤狀的鎳製管板2中,在複數個同心圓上焊接19根由鈀、銀和金作為主成分之合金構成的鈀合金細管1(外徑1.8mm、厚度70μm、長度600mm)。接著,在如圖1所示的位置上,在具有原料氫 供給口9、含雜質氣體取出口10和純氫取出口11的內徑20mm、長度700mm的SUS316L製的槽室4中收納上述管板2和鈀合金細管1。另外,槽室的管板2的上游側的空間的體積大約為槽室的管板2的下游側的空間的體積的35倍。 In a disk-shaped nickel tube sheet 2 having a diameter of 20 mm and a thickness of 5 mm, a palladium alloy thin tube 1 composed of an alloy of palladium, silver and gold as a main component was welded to a plurality of concentric circles (outer diameter 1.8 mm, thickness) 70 μm, length 600 mm). Next, at the position shown in Figure 1, there is a raw material hydrogen The tube plate 2 and the palladium alloy thin tube 1 are housed in the tank chamber 4 made of SUS316L having an inner diameter of 20 mm and a length of 700 mm, which are the supply port 9, the impurity-containing gas take-out port 10, and the pure hydrogen take-out port 11. Further, the volume of the space on the upstream side of the tube sheet 2 of the tank chamber is approximately 35 times the volume of the space on the downstream side of the tube sheet 2 of the tank chamber.
將具有內徑4.3mm長度800mm的直線配管部 的SUS316L製的原料氫的導入配管5以該直線配管部與槽室的側壁6接觸的方式設置,並且使其連接於槽室4的原料氫供給口9。另外,將電熱線13以螺旋狀捲繞於槽室的側壁6的外周以及導入配管5的直線配管部的外周,以構成如圖3所示那樣的結構的方式用導熱水泥充滿它們的間隙,從而製作出如圖1所示之形態的氫純化裝置。另外,以隔著導熱水泥而通過槽室的側壁6與加熱器3之間的間隙的方式設定的原料氫的導入配管5的長度為槽室的側壁6的長度的95%。並且,連接純氫取出配管16等。 A linear piping unit having an inner diameter of 4.3 mm and a length of 800 mm The raw material hydrogen introduction pipe 5 made of SUS316L is provided so that the linear pipe portion comes into contact with the side wall 6 of the tank chamber, and is connected to the raw material hydrogen supply port 9 of the tank chamber 4. In addition, the heating wire 13 is spirally wound around the outer circumference of the side wall 6 of the tank chamber and the outer circumference of the straight piping portion of the introduction pipe 5, and the gap is filled with the heat transfer cement so as to constitute a structure as shown in FIG. Thus, a hydrogen purifying apparatus having the form shown in Fig. 1 was produced. Moreover, the length of the raw material hydrogen introduction pipe 5 set so as to pass through the gap between the side wall 6 of the tank chamber and the heater 3 via the heat conductive cement is 95% of the length of the side wall 6 of the tank chamber. Further, the pure hydrogen extraction pipe 16 and the like are connected.
將氫純化裝置的槽室的一次側空間4’的內部的溫度升溫至600℃並導入氫,進行10個小時的加熱處理。接著,降低氫純化裝置的槽室的一次側空間4’的內部的溫度至420℃,一邊以槽室的一次側空間4’與槽室的二次側空間4”之壓差為1.0Mpa的方式進行控制,一邊從原料氫的導入配管5導入總計大約含有400ppm雜質(氮、氧、二氧化碳等)的原料氫,從而進行氫的純化。此時,原料氫供給口9的原料氫的溫度約為400℃。進行1個小時處理後的結果,從純氫取出配管得到了900L的純氫。 The temperature inside the primary side space 4' of the cell chamber of the hydrogen purification apparatus was raised to 600 °C, and hydrogen was introduced thereto, followed by heat treatment for 10 hours. Next, the temperature inside the primary side space 4' of the tank chamber of the hydrogen purification apparatus is lowered to 420 ° C, and the pressure difference between the primary side space 4' of the tank chamber and the secondary side space 4" of the tank chamber is 1.0 MPa. By controlling the method, hydrogen is purified by introducing a raw material hydrogen containing approximately 400 ppm of impurities (nitrogen, oxygen, carbon dioxide, etc.) from the raw material hydrogen introduction pipe 5. At this time, the temperature of the raw material hydrogen of the raw material hydrogen supply port 9 is about At 400 ° C. After 1 hour of treatment, 900 L of pure hydrogen was obtained by taking out the piping from pure hydrogen.
在實施例1的氫純化裝置的製作中,除了使用交換了原料氫供給口9與含雜質氣體的取出口10的位置的槽室以外,與實施例1同樣地製作了如圖2所示的形態的氫純化裝置。另外,以隔著導熱水泥而通過槽室4的側壁6與加熱器3之間的間隙的方式設定的原料氫的導入配管5的長度為槽室4的側壁6的長度的85%。 In the production of the hydrogen purification apparatus of the first embodiment, a tank chamber in which the raw material hydrogen supply port 9 and the outlet port 10 containing the impurity gas were exchanged was used, and a sample as shown in FIG. 2 was produced in the same manner as in the first embodiment. Form hydrogen purification unit. Moreover, the length of the raw material hydrogen introduction pipe 5 set so as to pass through the gap between the side wall 6 of the tank chamber 4 and the heater 3 via the heat transfer cement is 85% of the length of the side wall 6 of the tank chamber 4.
除了使用上述氫純化裝置以外,與實施例1同樣地進行了氫純化試驗。其結果為:原料氫供給口9的原料氫的溫度約為390℃。另外,經過1個小時的處理,從純氫取出配管得到了900L的純氫。 A hydrogen purification test was carried out in the same manner as in Example 1 except that the above hydrogen purification apparatus was used. As a result, the temperature of the raw material hydrogen of the raw material hydrogen supply port 9 was about 390 °C. Further, after one hour of treatment, 900 L of pure hydrogen was obtained by taking out the piping from pure hydrogen.
製作三個與實施例1相同的氫純化裝置,並且並列設置複數個氫純化裝置。將這些氫純化裝置的各個原料氫的導入配管5連接於外部的一根原料氫供給配管14,將這些氫純化裝置的各個純氫取出配管16連接於外部的一根純氫回收配管17,並且,隔著中途的配管將含雜質氣體的取出口10與外部的一根含雜質氣體的回收配管15連接,如圖4那樣製作了氫純化系統。 Three hydrogen purification apparatuses identical to those of Example 1 were produced, and a plurality of hydrogen purification apparatuses were arranged in parallel. The raw material hydrogen supply pipe 5 of the hydrogen purification device is connected to the external raw material hydrogen supply pipe 14 , and the pure hydrogen extraction pipe 16 of the hydrogen purification device is connected to one of the external pure hydrogen recovery pipes 17 , and The outlet port 10 containing the impurity gas was connected to the external recovery pipe 15 containing the impurity gas via a pipe in the middle, and a hydrogen purification system was produced as shown in FIG.
將每個氫純化裝置的槽室的一次側空間4’的內部的溫度升溫至600℃並導入氫,進行10個小時的加熱處理。接著,降低每個氫純化裝置的槽室的一次側空間4’的內部的溫度至420℃,一邊以槽室的一次側空間4’與槽室的二次側空間4”的壓差為1.0Mpa的方式進行控制,一邊從 原料氫供給配管14導入總計大約含有400ppm雜質(氮、氧、二氧化碳等)的原料氫,從而進行氫的純化。進行1個小時處理後的結果,從純氫回收配管17得到了總計2600L的純氫。 The temperature inside the primary side space 4' of the tank chamber of each hydrogen purification apparatus was raised to 600 °C, and hydrogen was introduced thereto, followed by heat treatment for 10 hours. Next, the temperature inside the primary side space 4' of the cell chamber of each hydrogen purification device is lowered to 420 ° C, and the pressure difference between the primary side space 4' of the cell chamber and the secondary side space 4" of the cell chamber is 1.0. Mpa way to control, while from The raw material hydrogen supply pipe 14 introduces a total of hydrogen which contains approximately 400 ppm of impurities (nitrogen, oxygen, carbon dioxide, etc.) to purify the hydrogen. As a result of the treatment for one hour, a total of 2,600 L of pure hydrogen was obtained from the pure hydrogen recovery pipe 17.
如上所述,本發明的氫純化裝置以及氫純化系統如實施例所示,能夠不需要設置用於預先加熱原料氫的加熱器。因此,能夠謀求裝置以及系統的小型化和簡化。 As described above, the hydrogen purifying apparatus and the hydrogen purifying system of the present invention can provide a heater for preheating the raw material hydrogen as shown in the embodiment. Therefore, it is possible to reduce the size and simplification of the device and the system.
1‧‧‧鈀合金細管 1‧‧‧Palladium alloy thin tube
2‧‧‧管板 2‧‧‧ tube plate
3‧‧‧加熱器 3‧‧‧heater
4‧‧‧槽室 4‧‧‧Slot room
4’‧‧‧槽室的一次側空間 4'‧‧‧ one-side space of the trough
4”‧‧‧槽室的二次側空間 4"‧‧‧Second side space of the chamber
5‧‧‧原料氫的導入配管 5‧‧‧Introduction of raw material hydrogen
6‧‧‧槽室的側壁 6‧‧‧ Side wall of the chamber
7‧‧‧開口端部 7‧‧‧Open end
8‧‧‧閉口端部 8‧‧‧Closed end
9‧‧‧原料氫供給口 9‧‧‧ Raw material hydrogen supply port
10‧‧‧含雜質氣體取出口 10‧‧‧Extracted gas containing impurities
11‧‧‧純氫取出口 11‧‧‧ Pure hydrogen is exported
13‧‧‧發熱線 13‧‧‧heating line
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