TW204305B - - Google Patents

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Publication number
TW204305B
TW204305B TW081103266A TW81103266A TW204305B TW 204305 B TW204305 B TW 204305B TW 081103266 A TW081103266 A TW 081103266A TW 81103266 A TW81103266 A TW 81103266A TW 204305 B TW204305 B TW 204305B
Authority
TW
Taiwan
Prior art keywords
catalyst
gas
catalyst particles
nozzle
reactor
Prior art date
Application number
TW081103266A
Other languages
English (en)
Original Assignee
Standard Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Standard Company filed Critical Standard Company
Application granted granted Critical
Publication of TW204305B publication Critical patent/TW204305B/zh

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1818Feeding of the fluidising gas
    • B01J8/1827Feeding of the fluidising gas the fluidising gas being a reactant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00Regeneration or reactivation of catalysts, in general
    • B01J38/04Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12Treating with free oxygen-containing gas
    • B01J38/30Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005Separating solid material from the gas/liquid stream
    • B01J8/0055Separating solid material from the gas/liquid stream using cyclones
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/38Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • B01J8/384Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only
    • B01J8/386Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it being subject to a circulatory movement only internally, i.e. the particles rotate within the vessel
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00654Controlling the process by measures relating to the particulate material
    • B01J2208/00681Agglomeration
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/515Specific contaminant removal
    • Y10S502/518Carbonaceous contaminant

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Catalysts (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)

Description

0430b A 6 Π 6 經濟部屮央桴準而Μ工消"合作社印製 五、發明説明() 本發明偽有朗一種加強流體化床催化劑性質的方法 ,其偽在催化劑表面上因污染物或其他物理或化學變化而 失去活性或流醱化性質。更明確地説,本發明係有關於一 種在使用中磨掉催化劑的表面以除去催化劑表面的k薄層 使得新鮮的催化劑得以暴露出來的方法。此外,本發明是 有關一種使催化粒子去黏聚的方法。 在一個流體床催化反應器中,經過撤細分割的固態催 化粒子典型上與蒸氣的反竈媒介接觸。這些催化粒子由一 處理氣賭之上升氣流抬起且攪動以使其看起來是懸浮在氣 流中而似一沸騰掖龌,所以叫做「流醱床」。 最廣為人知也是最早應用流體床反應器技術是油的催 化裂解製造汽油及其它輕烴類。其它的用途包括殘餘物之 煉焦;煤焦氣化;苯或丁烷催化氣化成順丁烯二酸醉;丙 烯之氨氣化成丙烯丨S :以及氮化氫氣化成氣。 本發明著重在使用於流體床反應器的催化劑。經過使 用及一段時間後,因催化劑表面被污染物或反鼴生成的副 産物堵塞,或因催化劑的表面進行一種物理或化學的變化 而成一種較不具催化性的形式,流體床催化劑會失掉活性 。此外,當污染物或一種物理或化學的變化發生在催化劑 的表面時,有些催化劑變成“黏性”而小流體床粒子開始 凝聚成較大粒子。凝聚的粒子導致催化表面積的減少,因 此影《到流體床催化劑的總體性質。更甚者,凝聚的粒子 阻礙了催化劑床的自然循琛及流體化。 上述問題的代表性的解決方法是在流體床反窸器中更 (請先閲誚背而之注意事項#蜞窍本頁) 裝· 訂_ 線_ 本紙尺度逍用中國81家楳準仰5)甲4規格(210父297公;《:> -3- 81. 4. 10,000¾ (II) 經濟部屮央#準局ex工消赀合作杜印3i Λ (5 _I5J_ 五、發明説明() 換全部或部分的催化劃。這方法花费很大,不僅在於催化 劑成本.且因鼷掉流腰床反應器以進行催化薄交換;時造成 的生産損失的成本也是很大。 在此所敘述的發明的目的是提供一可解決因凝聚、污 染物或催化劑表面上的物理或化學變化所帶來的問題及延 長催化劑的壽命的方法。 已發現一種使流髏床催化劑去凝聚及因催化劑表面上 之污染作用或物理或化學變化而失去活性或流$化性質的 流體床催化劑再暴露其表面的方法。此方法^^在操作 ' & 的流體床反匾器内部實行,但也可随意地在反籯絮外被實 行,用一種連鑛或非連鑛的方式。 在一個較好的實施例中,此方法包含了在一流體床反 應器設置至少一噴嘴,經其可自反應器外部之源將氣e供 應至此反應器中。此噴嘴是設置在反應器内部使得噴嘴没 於催化床中以使逸出管口的氣體立即與催化劑接觸。從噴 嘴出來的氣體之逃脱速度為足以接觸流體化的流體床催化 劑粒子並且在谙些催化劑粒子中産生許多的碰撞。催化劑 粒子多重碰撞之衝擊力磨掉了催化劑表面,因此移去了催 化劑表面上任何的污染物或較不具催化性的物質而暴s出 新鮮的催化劑。 圖示為一簡化的流體床反應器横截面圖.説明本發明 的實施例。 流體床反應器是任何可發生氣一固或液一固接觸過程 之反應瓶。在反應瓶中.微細分割的固態粒子床(即流體 (請先間誚背而之注意事項冉場寫本頁) 裝· 本紙尺度边用中S國家標準(CNS)T4規格(210x297公;《:) —4 — 81. 4. 10,000¾ (|[) Λ 6 Π6 eft 1305 五、發明説明() (請先W1讀背而之注意事項-?!-填窍本頁) 床催化劑)藉利用處理之氣體或掖體流抬起且分開。流鱧 床反窸器可以是各種形狀及大小。典型的反應器是在反應 器底部設置一雄檷,其可容許處理之進料通過時支撑催化 劑床。本敘述的其餘部分著重在本發明的氣-固相接觸製 法的實施上。但是.此«所述的方法也同樣可應用在掖一 '固相接觭製程。 在氣一固相接觸製程中,處理産物氣體在反應器頂端 逸出。因産物氣雔通常撝帶催化劑粒子,將産物氣體流經 一分離器以移去催化劑粒子,而這些粒子經由一浸漬座回 到催化劑床上。此分離器可以是任何固體回收裝置,如抽 氣過濾器。 流體床催化劑為細撖分割的固體粒子,視其應用之不 同在大小、重量、形狀及組成不間。具觀來看,流觼床催 化劑常類似一種粉末,但是也可能為小珠狀。典型的流體 床催化粒子大小從10至200撤米不等。 經濟部屮央標準灼β工消赀合作社印¾ 在某些醮用上,流腥床催化劑的效果會因催化劑表面 上污染物的形成或物理或化學變化而降低。這種狀況會導 致催化劑活性的降低或造成催化劑變成《黏性”,因此使 催化粒子易凝聚,而失掉了流動性及/或催化活性。 在本發明的實際操作上,流體床反應器的内部設置了 一個或更多噴嘴.而一高速流動的氣體會經由此噴嘴送至 催化劑床。在本發明的實際操作的過程中,催化劑是保持 在流體化狀態(即被流體化),而這是導因於處理氣體或 其它氣體的上升氣流將催化劑粒子抬升、擾亂、及懸浮於 本紙尺度遑用中a S家標毕(CNS> Y4規格(210x297公龙) -5- 81. 4. 10,000張⑻ δ 五、發明説明() 上升氣鼸中。氣髏流的力量造成許多流體化催化》粒子間 的碰撞,而埴些碰撞的衝量會磨掉催化劑的表面Μ移去表 面上的任何汚染物,因而顯露出新鮮的催化劑。此外.催 化劑粒子碰撞造成的衝擊力將會去凝聚(即斷開)任何凝 聚的催化劑粒子。本發明也可在備有任何可使高速氣體流 與流髏化催化剤粒子接觸的裝備(如噴_或氣體分布鐵柵 或單或多孔金颶板)的任何反應器内操作。 本發明在裝備有多於一値噴嘴的流體床反應器内操作 較受偏好。此«所用的噴嘴可以是任何形狀或大小.做任 何形式的噴射。此电.廒可以簡如一開口管子或一端有燭心 或窳縮器用來加速或導引氣體逸出的短試管。管口的大小 -------- 對本發明的實際操作並不重要。管口小到直徑只有0.016 英吋的曾被使用過(在氣醱分布鐵栅中含有三個直徑0,016 英吋的鑲嵌的洞)。典型的管口大小是直徑0.0625英吋到 0.25英吋。更典型的管口大小是直徑介於0.125英吋到 ...........··'·. 經濟部屮央標準而A工消"合作社印^ (請先閲讀背而之注意事項再蜞寫本頁) 0,1875英吋。管口直徑為9/64”及5/32”者較受偏好。氣體 之逃脱速度必須足以驅使催化劑粒子産生許多力量足以磨 去催化剤表面的碰撞。通常較硬的催化劑需要較大的逃脱 速度。可以用大到轚速的逃脱速度。管口及氣體流速大小 之測定是為了決定所要使用的氣體的速度。受偏好的氣體 速度是介於200至1200fps。而氣體速度600到llOOfps更受 偏好。較合宜地,造樣的氣體速度使得氣體一催化劑的“ 接觸區域”伸展到噴嘴前數英吋而進入催化劑床。此噴嘴 可被導向以提供一値與流體化處理氣體成同流、反流或交 本紙張尺度边用中B國家標準(CNS) Ή規格(210X297公;¢) 一 6- 81. 4. 10,000張(f[) 05 Λ 6 Η 6 經洧部屮央標準而员工消伢合作杜印製 五、發明説明() 叉流向的高速氣饅流。而較合宜的是將此管嘴導向提供一 值舆流體化處理氣腥同流向的高速度氣體流。 噴嘴可放置於催化Μ床的任何地方,在此噴射的氣髖 將可接觸到流體化催化劑粒子。例如,噴嘴可放在反應器 壁之内或反慝器中間。為了使本發明的效果達到最大,噴 嘴鼴位於反窸器内部,此處催化劑的循環最好。這樣增大 了與氣匾接觸的催化劑總量。因此,噴嘴較適宜位於與浸 潰座開口相鄰或在其附近(浸潰座開口即催化劑從分離器 回到反應器的入口點)。應小心以確保自噴嘴逸出的氣醱 不會驅使催化劑進入反_器的任何内部組成,因為催化劑 與反應器組成間的碰撞將更可能摧毀催化劑,而重覆的碰 撞將損壊反窸器組成。 此高速氣體可以是任何氣鳢或液醱蒸氣,該氣體對反 應過程是羥鈍或是有助益的。典型地,此氣體是從反醮器 外部之源供應到噴嘴。當流體床反應器被用於一氧化反應 時,氣體通常是用空氣。但是,活性較差的氣體如氮氣或 反醢進料氣體也可使用。在本發明的實際操作中(卽生産 中),商用刻度的反應器以及氣體總産量的增加可被忽略 〇 將摧化劑去凝聚及再暴霉其表面的過程可以斷鑛地或 連續地被操作,其決定於催化劑與噴嘴特色之需要如噴嘴 數目、噴嘴位置及維開噴喊的氣體逃脱速度。 從催化朗表面上磨掉的污染或催化性較差的物質通常 随著反醮器的廢料移走,然後經由適當的分離方法(如抽 (請先間讀背而之注意事項再塥裒木頁) 裝- 線· 本紙尺度边用中國Β家標準(CNS) Ή規格(210x297公:《:) —Π — 81. 4. 10,000張⑻ 經濟部屮央榀準杓β工消赀合作社印製 --- 五、發明説明() 氣裝置、過濾器等)將其與反應産物分開。本發明的操作 .的一餡重要闢鍵在於控制氣體流速及噴嘴的放置使得再暴 露催化劑的表面及將催化劑去凝聚的效益增至最大,而另 一方面減少催化剤表面磨去的量以使催化劑的損失減至最小。 本發明的實施例以圓示説明。流體床反應器1#是流 流體床催化劑2。反進料氣體經由管線3進入反應器並 且通遇氣體分布檷4到達催化劑床。攜帶著催化粒子的氣 相反應産物進人抽氣裝置6,反應産物與催化劑即在此處 分離。氣相反窸産物經由管線5移出反器。催化劑經由 浸潰座7回到催化劑床2。高速氣體經由管線8供應至反 應器而經由噴嘴9導引至催化劑床。 本發明可用於任何催化性流醱床操作中,當其催化劑 表面被反應副産物或催化劑組成的物理或化學爱化所污染 時。在這種狀況下催化劑將會失去活性及/或流動性。經 由磨去催化劑表面以再暴露新鮮催化劑或將催化劑去凝聚 化,活性及/或流動性將會恢復.而催化劑的赛命就可延 長。本發明可被鼴用的代表性反應有油之催化裂解生成石 油及其他輕烴,殘餘物之煉焦.煤焦汽化,苯或正丁烷氣 化成順丁烯二酸酐,丙烯之氨氣化成丙烯丨S,及氛化氳氣 化成氣。 如本處所述,操作時高速氣體與流體化催化劑在反應 器内部接觭。本發明也可將噴嘴放置在浸潰座内部來操作 。再者,流體床反應器附有再生器,該再生器排除經過處 (請先閲讀背而之注意事項孙塡寫本頁) 本紙張尺度边用中a Η家楳準(CNS)>P4規怙(2丨0x297公¢) 81. 4. 10,000¾ (II) Λ 6 η 6 ^04305_ 五、發明説明() 理及再活化然後返回反軀器的催化劑,催化劑表面可被再 暴露且/或催化劑被去凝聚化於再生器之内或於反應器舆 再生器之間的催化劑轉移管線中。最後一點,本發明可被 «施經由從反褰器移走催化劑、再暴露催化劑表面、及/或 催化劑去凝聚化如本處所述,然後使催化劑回到反鼴器。 前面的敍述並非意欲完全包括_或限制此發明於所發 表之精確的形式,而且根據上述發表的觀點,顯然許多的 修正和變異是可能的。本叙述的目的是要解釋本發明的原 則及其實際應用,並且因之使他人熟習利用此發明於其不 同的實施例中之技術及適用於其所構思之特殊用途的不同 修正。本發明只打算定義於以下的範圍。 (請先閲請背而之注意事項再塥寫本頁) 經濟部屮央槛準而β工消"合作社印製 81. 4. 10,000¾ (II) 本紙張尺度逍用中a國家樣準(CNS)lM規怙(210x297公;tt)

Claims (1)

  1. 六、申請專利範面 補充 A7 B7 C7 D7 第81 103266號ffi請案申請專利範圍修正本 修正日期:82年1月 1 ..一種將流體床催化劑粒乎去凝聚或再暴露流體床催化 劑粒子的表的.方法’其表面在用於製造丙铺睛或丨噴 丁烯二酸酐時産生污染或物理或化學變化,該方法& 含在流體化狀態下使粒子大小為1 0至20 0 « m的流|| 床催化劑粒子與一速度介於β〇 · 98至366公尺/毎秒( 200到1 200吳呎/每秒)的氣體接觸,其足以使催化 劑粒子間産生充分碰撞,而去凝聚流體床催化劑粒子 ,或磨去催化劑粒子表面以除去污染或已變化的表面 (請先聞讀背面之注意事項再硯寫本頁 / .裝. 經濟部屮央標準局貝工消费合作社印製 2.如申誚專利範園第1項的方法,其中該氣體為空氣或 m*5$=r 氣° 3 .如申請專利範圍第1項的方法,其中該方法可在任何 設置使氣流與流體化催化劑接觸之装置的容器中進行 0 4. 一種將流體床催化劑粒子去凝聚或再暴露流體床催化 劑粒子表面的方法,該表面在用於製造丙烯請或順丁 烯二酸酐時産生污染或物理或化學變化,該方法包含 (a )在流體化狀態下維持催化劑粒子在流體床反 應器之内,Η中該催化_粒子大小為自1 〇至200 w m ’該流體床反應器附設至少-噴嘴,氣體從反應器夕卜 之源供應至此’而此噴嘴放置在反應器内部使得噴嘴 -10 - •訂· 本紙張尺度適用中Β國家櫺毕(CNS)甲4規格(210x297公釐) A7 C7 六、申請專利範圊 沈浸於催化劑粒子間.巨從噴嘴出來的氣體ώ:即與催化 劑粒子接觸; (bi ·氣體以60.98至366公尺/每秒( 200到12 00英呎/每# i的逃脫速度自噴嘴通過,在此處該氣 體在催化劑粒f間引起許多碰撞,其衝量足以使流體 床催化劑粒F去凝聚,或磨去催化劑粒子的表面以除 去受污染的戎己變化的表面。 5 .如申請專利範圍第4項之方法,其中該氣體為空氣或 6.如申請專利範圍第4項之法,其中流體床反應器設 有一抽氣装置以fif氣體排出物中分離催化劑,U其中 該抽氣裝置備有…浸潰座以使催化劑回到反應器a該 噴嘴就位於催化劑離開浸凟座的出口附近… 7 .如申請專利範圍第4項之方法,其中再暴露催化劑表 面的方法是W於當流體床反應器在製造順丁烯二酸酐 成丙烯睛的過程中' 8 .如申請專利範圍第4項之方法 > 其屮噴嘴管Π開口大 小為介於Μ择〇. 75公分(0.125英时)與0.47625 (請先聞請背面之注意事頊再填寫本頁 k. 經濟部屮央標準局貝工消费合作社印製 分 ι·-χ 寸 Π 11 11 本紙張尺度逋用中闺Η家標準(CNS)甲4規格(210x297公釐)
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US5124291A (en) 1992-06-23
EP0566785B1 (en) 1997-02-26
DE69217650D1 (de) 1997-04-03
DE69217650T2 (de) 1997-06-12
CN1046639C (zh) 1999-11-24
ATE149099T1 (de) 1997-03-15
EP0566785A1 (en) 1993-10-27
CN1077399A (zh) 1993-10-20

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