TW201730099A - 基於atr的氨的方法及設備 - Google Patents
基於atr的氨的方法及設備 Download PDFInfo
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Abstract
本發明提供一種用於產生氨合成氣之方法,該方法包括以下步驟:- 在重整步驟中重整烴類饋料,從而獲得包括CH4、CO、CO2、H2及H2O之合成氣,- 在高溫變換步驟中經由促進的基於鋅鋁氧化物之高溫變換催化劑來變換該合成氣,其中該重整步驟中之蒸汽/碳比小於2.6。
Description
由於當今氨產生之需求及競爭性,已投入大量工作來開發針對氨設備之最佳化產生,目的為改良總體能效及降低資源成本。對更具成本效益之氨產生的需要已刺激開發針對大規模氨產生單元之技術及催化劑,以便受益於規模經濟。
Topsøe之氨產生技術的最近創新及目前先進技術催化劑之新一代的開發亦針對5000 MTPD之氨或更大的單線容量(其中當今標準僅高達3300 MTPD)確保高成本效益之氨產生及高設備可靠性。
在本發明之第一態樣中提供一種以低蒸汽/碳比操作來實現利用經證實重整技術之方法方案的方法。
在本發明之第二態樣中提供一種實現在與重整區段相同的低蒸汽/碳比下對在重整區段下游之高溫(high temperature;HT)變換之操作的方法。
在本發明之第三態樣中提供一種無需在甲烷化區段移除補充合成氣中之殘餘碳組分以供氨合成的方法方案。
在本發明之第四態樣中提供一種實現最大單線容量之整體方法佈局。
藉由用於產生氨合成氣之方法來達成此等優點及另外優點,該方法包括以下步驟:- 在重整步驟中重整烴類饋料,從而獲得包括CH4、CO、CO2、H2及H2O之合成氣,- 在高溫變換步驟中經由促進的基於鋅鋁氧化物之HT變換催化劑來變換該合成氣,其中- 該重整步驟中之蒸汽/碳比小於2.6。
HT變換被定義為含有CO、CO2、H2及H2O之合成氣在300℃至600℃之溫度範圍內經歷變換反應的方法步驟。
在習知氨設備中,對基於鐵之HT變換催化劑的標準使用要求為約3.0之蒸汽/碳比以避免/碳化鐵形成。
(1)5Fe3O4+32CO 3Fe5C2+26 CO2
碳化鐵之形成將弱化催化劑集結粒且可引起催化劑崩解及壓降增加。
碳化鐵將催化費-托(Fischer-Tropsch)副產物形成。
(2)nCO+(n+m/2)H2 CnHm+nH2O
費一托反應消耗氫氣,藉以降低變換區段之效率。
然而,根據本發明,使用非Fe催化劑,諸如促進的基於鋅鋁氧化物之催化劑。舉例而言,Topsøe SK-501 FlexTMHT變換催化劑,其實現重整區段及HT變換區段在降至0.3之蒸汽/碳比下的操作。
因此,在降至0.3之蒸汽/碳比下操作之本發明方法與當今傳統氨設備形成對比,當今傳統氨設備係基於在2.6或高於2.6之蒸汽/碳比下操作的重整區段及/或HT變換區段。在所述方法之有利具體實例中,呈其活性形式之基於鋅鋁氧化物之催化劑包括與選自由Na、K、Rb、Cs及其混合物組成之群的鹼金屬組合,且視情況與Cu組合的鋅鋁尖晶石與氧化鋅之混合物。催化劑可具有0.5至1.0範圍內的Zn/Al莫耳比,以經氧化催化劑之重量計,0.4至8.0wt%範圍內的鹼金屬含量及0至10%範圍內的銅含量。
根據本發明方法使用之HT變換催化劑不受對蒸汽與碳比之嚴格要求限制,其使得有可能在變換區段以及重整區段中降低蒸汽/碳比。
小於2.6之蒸汽/碳比具有若干優點。在一般基礎上降低蒸汽/碳比會產生貫穿重整區段以及下游冷卻及合成氣製備區段之經減少的饋料與蒸汽流量。
相比於高蒸汽/碳比,重整區段及變換區段上之低蒸汽/碳比實現較高合成氣產出率。相比於在重整區段中添加氮氣,經由氮氣洗滌添加氮氣實現高合成氣產出率。甲烷化區段不會減少壓力損耗,且在氨合成區段中使用無惰性氣體會實現在氨合成區段中之較高產出率。
貫穿此等區段之經減少質量流量意謂較小裝置及配管大
小。經減少質量流量亦引起低溫大卡(其可常常未經利用)之經減少產生。此意謂潛在地存在較低資本開支及運營開支兩者。
本發明方法可進一步包括以下步驟中之一或多者:
- 在一或多個中溫(medium temperature;MT)/低溫(low temperature;LT)變換步驟中變換HT變換出口氣體。相較於HT變換,MT/LT變換步驟可視情況在更高蒸汽/碳比下執行以限制諸如甲醇之副產物形成。
- 在水洗滌中視情況將甲醇自MT/LT變換出口氣體移除。
- 將CO2自MT/LT變換出口氣體/水洗滌出口氣體移除,以使CO2降至低於500ppm之含量,較佳地降至低於20ppm。
- 在分子篩乾燥器區段中將殘餘CO2及H2O自離開CO2移除區段之氣體移除。
- 在氮氣洗滌區段中將CH4、CO及諸如Ar及He之惰性物質自離開分子篩乾燥器區段之氣體移除,且按氨合成的需要調整N2/H2比以近似3。
- 在無惰性氨合成區段中將來自氮氣洗滌的經調整出口氣體轉換成氨。
在較佳具體實例中,重整步驟包括至少一個自發性熱重整器(autothermal reformer;ATR)。
因為相比於已知技術,本發明方法在HT變換步驟中對蒸汽/碳比的要求顯著降低,所以本發明有可能貫穿前端而使蒸汽/碳比降低至(例如)0.6或取決於可能的變換解決方案而儘可能低。低蒸汽/碳比對於ATR且在整體方法中之優點在於:歸因於貫穿設備之較低總質量流量,在前端中需要較小裝置。
將用於ATR之碳饋料與ATR中之氧氣及額外蒸汽混合,且至少兩種類型之反應的組合會發生。此兩種反應為燃燒及蒸汽重整。
燃燒區:
(3)2H2+O2 2H2O+熱
(4)CH4+3/2 O2 CO+2H2O+熱
熱及催化區:
(5)CH4+H2O+熱 CO+3H2
(6)CO+H2O CO2+H2+熱
甲烷燃燒成一氧化碳及水(4)係高度放熱方法。在所有氧氣已被轉換之後,餘量甲烷可存在於燃燒區出口處。
熱區係燃燒室之部分,其中烴類之進一步轉換藉由均相氣相反應繼續進行,主要為(5)及(6)。甲烷之吸熱蒸汽重整(5)消耗在燃燒區中產生之熱的一大部分。
在燃燒室之後,可存在固定催化劑床、催化區,其中最終烴類轉換經由異相催化反應發生。在催化區之出口處,關於反應(5)及(6),合成氣較佳地接近於穩態。
重整區段中之蒸汽/碳比可為2.6至0.1、2.4至0.1、2至0.2、1.5至0.3、1.4至0.4,諸如1.2、1.0或0.6。
蒸汽/碳比被定義為以莫耳計,添加至在HT變換區段上游之重整區段的所有蒸汽(亦即,可已經由添加至燃燒器的饋料氣、氧氣饋料等添加至重整區段之蒸汽)與至重整區段之饋料氣中的烴類之比。
因此,根據本發明,可能在不在重整步驟與高溫變換步驟之
間添加額外蒸汽的情況下執行該方法。
在有利具體實例中,ATR中之空間速度較低,諸如小於20.000Nm3 C/m3/h,較佳地小於12.000Nm3 C/m3/h,且最佳地小於7000Nm3 C/m3/h。空間速度可被定義為每催化劑體積之體積的碳流量,且因此與催化劑區中之轉換無關。
在較佳具體實例中,HT變換步驟中之溫度係在300℃至600℃之範圍內,諸如360℃至470℃。此意謂根據本發明方法,有可能以與藉由已知方法相比低得多的蒸汽/碳比對饋料執行高溫變換反應。舉例而言,高溫變換入口溫度可為300℃至400℃,諸如350℃至380℃。
較佳地,提供預重整器以作為在(例如)ATR上游之重整區段之部分。在預重整器中,所有高級烴類可轉換成碳氧化物及甲烷,且對於輕烴,預重整器亦係有利的。提供預重整器可具有若干優點,包含減少ATR中之所需的O2消耗及允許至ATR之較高入口溫度,此係因為藉由預加熱之裂解風險降至最低。從而達到引燃條件。此外,預重整器可提供高效硫防護,從而使實際無硫饋料氣進入ATR及下游系統。可在300℃至650℃,較佳地390℃至480℃之間的溫度下進行預重整步驟。
在各種具體實例中,燃式加熱器用於預加熱天然氣饋料、預重整器及ATR饋料且用於蒸汽過熱。可藉由燃燒天然氣、廢氣(來自N2洗滌)、尾氣(來自惰性排出氣體分離器)及閃蒸氣(來自CO2移除區段)之混合物而產生必要熱。
低蒸汽/碳比可引起低於最佳變換轉換,此意謂在一些具體實例中,提供一或多個額外變換步驟可為有利的。所述一或多個額外變換
步驟可包含MT變換及/或LT變換及/或HT變換。一般言之,在變換步驟中,經轉換CO愈多,則獲得的H2愈多,且所需的前端愈小。
此亦自下文給定之放熱變換反應可見
(7)CO+H2O CO2+H2+熱
可視情況在HT變換步驟之後,諸如在一或多個後繼MT或LT變換步驟及/或HT變換步驟之前,添加蒸汽,以便最大化該等後繼HT、MT及/或LT變換步驟之效能。
具有兩個或多於兩個連續的HT變換步驟(諸如包括兩個或多於兩個連續的變換反應器之HT變換步驟,例如,可能在其間進行冷卻及/或蒸汽添加)可為有利的,此係因為其可提供在高溫下增加的變換轉換,其產生所需變換催化劑體積之可能減小,且因此產生資本支出之可能降低。此外,高溫會減少甲醇之形成,甲醇為典型的變換步驟副產物。
較佳地,可經由促進的銅/鋅/鋁催化劑進行MT變換步驟及LT變換步驟。舉例而言,低溫變換催化劑類型可為LK-821-2,其表徵為高活性、高強度及對硫中毒之高耐受性。可安裝特殊催化劑之頂部層以捕獲氣體中之可能的氯氣及防止液滴到達變換催化劑。
可在190℃至360℃之溫度下進行MT變換步驟。
可在Tdew+15至290℃之溫度(諸如,200℃至280℃)下進行LT變換步驟。舉例而言,低溫變換入口溫度為Tdew+15至250℃,諸如190℃至210℃。
降低蒸汽/碳比會產生處理氣體之經降低露點,此意謂可降低至MT變換步驟及/或LT變換步驟之入口溫度。較低入口溫度可意謂較低
CO滑移離開變換反應器。
眾所周知,MT/LT變換催化劑易於產生作為副產物的甲醇。可藉由增大蒸汽/碳比來減少此類副產物形成。後繼MT/LT變換之CO2洗滌需要熱以用於再生CO2吸收溶液。此熱通常經提供為來自處理氣體之顯熱,但此未必總是足夠的。典型地,另外蒸汽燃式再沸器正提供損失的熱。視情況將蒸汽添加至處理氣體可替換此另外蒸汽燃式再沸器,且同時確保減少MT/LT變換區段中之副產物形成。
可視情況在置放於CO2移除步驟上游或CO2產物流上之水洗滌中,將由MT/LT變換催化劑形成之甲醇自合成氣移除。
在許多有利具體實例中,可在一或多個變換步驟之後/在一或多個變換步驟下游進行CO2移除步驟。在標準設計中,經處理氣中之CO2含量為500vppm。
在較佳具體實例中,CO2移除步驟可用以使CO2含量降至小於400vppm之CO2,諸如低於100vppm,或在一些較佳具體實例中降至20vppm或更低。
該方法可進一步包括洗滌步驟,較佳地為N2洗滌。N2洗滌可伺服若干目的,諸如純化合成氣,以及添加化學計量所需的氮氣以供下游氨合成。
用於N2洗滌單元(N2 wash unit;NWU)之氮氣可由空氣分離單元(air separation unit;ASU)供應,空氣分離單元(ASU)將常壓空氣分離成其主要組分氮氣及氧氣。氧氣用於ATR中,且氮氣用於NWU中。
在一或多個變換區段及CO2移除單元之後,該氣可含有殘餘
CO及CO2,以及少量CH4、Ar、He及H2O。
較佳地在N2洗滌之前移除CO2及H2O,此係因為否則其將在N2洗滌之低操作溫度下凍結。可(例如)藉由由至少兩個容器組成之分子篩乾燥器中之吸收來完成此移除,其中一個容器在操作中,而另一容器正再生。氮氣可用作乾燥氣以供再生。
在NWU中,藉由管柱中之液氮來洗滌合成氣,其中CH4、Ar、He及CO被移除。經純化合成氣較佳地僅含有ppm含量之Ar及CH4。
含有雜質以及一些丟失的氮氣之廢氣可有利地用作燃式加熱器中之燃料。
在NWU之後,可將氮氣添加至處理流以便在至氨合成迴圈之補充流中將N2含量調整至H2/N2比為3之較佳比。
因為經純化合成氣現在僅含有表示為正確化學計量比之H2及N2以供氨合成,以及ppm含量之Ar及CH4,所以氨合成區段可被認為無惰性。
氨合成迴圈被定義為無惰性,此時不需要來自迴圈之沖洗氣體,此係因為惰性物質之累積在無此類沖洗的情況下亦係可忽略的。
實施例
預重整器:Tin/Tout:450/449℃(△T=-1℃)
蒸汽/碳比,S/C=0.9進入預重整器
ATR:
處理氣體在650℃下進入ATR,且氧氣之溫度為約260℃。
蒸汽/碳比,S/C=1.0,按照本說明書中之定義
處理氣體離開處於約1025℃下之重整區段,穿過耐火內襯出口區段及輸送線,到達處理氣體冷卻區段中之廢熱鍋爐。
變換區段:
HT:Tin/Tout:360/469℃(△T=109℃)
LT:Tin/Tout:205/280℃(△T=75℃)
在重整之後,約26.7vol%之CO存在於氣體中(以乾重計)。在高溫CO轉換器中,CO含量降低至大致11.8vol%,且溫度自360℃增加至469℃。在廢熱鍋爐及鍋爐進料水預熱器中回收來自高溫CO轉換器之流出物的熱含量。
處理氣體從而冷卻至205℃,且繼續傳遞至低溫CO轉換
器,其中CO含量降低至大致3.8vol%,而溫度增加至280℃。
CO2移除區段
來自變換區段之出口流中的CO2含量降低至20ppm。進入CO2移除區段之合成氣中的所有甲醇將與處理冷凝液及CO2產物流一起離開此區段。對進入CO2移除區段之合成氣(參見圖2)或對CO2產物流之水洗滌可使CO2產物流中之甲醇含量降至最低。
N2洗滌區段
此區段中之第一步驟係在分子篩乾燥器中定量移除CO2及H2O。下一步驟係N2液體洗滌移除除了降至ppm含量之H2及N2以外的組分。第三步驟係使用氣態氮來將H2/N2比調整至大致為3。
合成氣壓縮機:
在離心類型的兩殼體式合成氣壓縮機中將合成氣自31.4kg/cm2g壓縮至185.5kg/cm2g。最後一個殼體之部分形成合成迴圈中之再循環壓縮機。
無惰性迴圈:該迴圈可被定義為在不需要沖洗氣體系統時為惰性的。
與補充合成氣一起進入迴圈之少量惰性氣體將在迴圈中累積,直至溶解於液氨中退出排放容器之惰性氣體之量等於進入迴圈之量為止。來自排放容器之尾氣再循環回至合成氣壓縮機。
經再循環惰性含量取決於溶解於液氨中離開氨分離器及排放容器之惰性物質之含量。
在需要時,可藉由對小氣流進行間歇沖洗而降低迴圈中之惰
性氣體的含量。
在此實施例中,離開N2洗滌之經純化氣體中的惰性含量係17ppm Ar,在補償氣體中為53ppm Ar(在添加來自排放容器之尾氣再循環流之後),且進入轉換器為0.30%之Ar。
在圖2中,展示另一實施例,其包含甲醇移除區段。
Claims (17)
- 一種用於產生氨合成氣之方法,該方法包括以下步驟:- 在重整步驟中重整烴類饋料,從而獲得包括CH4、CO、CO2、H2及H2O之合成氣,- 在高溫變換步驟中經由促進的基於鋅鋁氧化物之高溫變換催化劑來變換該合成氣,其中- 該重整步驟中之蒸汽/碳比小於2.6。
- 如申請專利範圍第1項之方法,其中該高溫變換步驟中之溫度為300℃至600℃,諸如345℃至550℃。
- 如前述申請專利範圍中任一項之方法,其中呈其活性形式之該促進的基於鋅鋁氧化物之HT變換催化劑包括0.5至1.0範圍內的Zn/Al莫耳比,及以經氧化催化劑之重量計,0.4至8.0wt%範圍內的鹼金屬含量以及0至10%範圍內的銅含量。
- 如前述申請專利範圍中任一項之方法,其中該重整步驟中之該蒸汽/碳比為2.6至0.1、2.4至0.1、2至0.2、1.5至0.3或1.4至0.4,諸如1.2或1或0.6。
- 如前述申請專利範圍中任一項之方法,其中該重整在自發性熱重整器(ATR)中發生。
- 如前述申請專利範圍中任一項之方法,其中該ATR中之空間速度小於20.000Nm3 C/m3/h,較佳地小於12.000Nm3 C/m3/h,且最佳地小於7000Nm3 C/m3/h。
- 如前述申請專利範圍中任一項之方法,其進一步包括預重整步驟。
- 如前述申請專利範圍中任一項之方法,其中該高溫變換步驟為連續的一或多個高溫變換步驟,較佳地可能在其間進行冷卻及/或蒸汽添加。
- 如前述申請專利範圍中任一項之方法,其進一步包括在該高溫變換步驟下游之一或多個額外變換步驟。
- 如前述申請專利範圍中任一項之方法,其中該一或多個額外變換步驟為一或多個中溫變換步驟及/或一或多個低溫變換步驟。
- 如前述申請專利範圍中任一項之方法,其中在該高溫變換步驟下游之該一或多個額外變換步驟之前視情況將蒸汽添加至該合成氣。
- 如前述申請專利範圍中任一項之方法,其中視情況用水洗滌離開在該高溫變換步驟下游之該一或多個額外變換步驟的該合成氣以降低甲醇含量。
- 如前述申請專利範圍中任一項之方法,其進一步包括CO2移除步驟,其將CO2自該合成氣移除,降至小於400vppm之CO2的含量,諸如低於100vppm,或在一些較佳具體實例中降至20vppm或更低。
- 如前述申請專利範圍中任一項之方法,其進一步包括N2洗滌步驟。
- 一種用於產生氨之方法,其中藉由如申請專利範圍第1項至第14項之方法來達成氨合成氣。
- 如申請專利範圍第15項之用於產生氨的方法,其中氨方法迴圈為無惰性迴圈。
- 一種設備,其經配置以執行如前述申請專利範圍第1項至第16項中任一項之方法。
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EP2631213A1 (en) | 2012-02-24 | 2013-08-28 | Ammonia Casale S.A. | Process for producing ammonia synthesis gas and a related front-end of an ammonia plant |
CA2876248C (en) | 2012-06-19 | 2019-03-26 | Haldor Topsoe A/S | Process for reforming hydrocarbons and process for starting up a gas-to-liquid process |
WO2014056535A1 (en) | 2012-10-11 | 2014-04-17 | Haldor Topsøe A/S | Process for the production of synthesis gas |
EP2801550A1 (en) | 2013-05-10 | 2014-11-12 | Ammonia Casale S.A. | A process for producing ammonia synthesis gas with high temperature shift and low steam-to-carbon ratio |
US9561968B2 (en) | 2013-08-07 | 2017-02-07 | Kellogg Brown & Root Llc | Methods and systems for producing and processing syngas in a pressure swing adsorption unit and making ammonia therefrom |
US20150203359A1 (en) * | 2014-01-17 | 2015-07-23 | Air Products And Chemicals, Inc. | System and Process for Producing Ammonia Using an Ion Transport Membrane, Gasifier, and Ammonia Synthesis Unit |
GB201501952D0 (en) | 2015-02-05 | 2015-03-25 | Johnson Matthey Plc | Process |
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2017
- 2017-02-02 CA CA3010549A patent/CA3010549C/en active Active
- 2017-02-02 PL PL17703715T patent/PL3411327T3/pl unknown
- 2017-02-02 WO PCT/EP2017/052247 patent/WO2017134162A1/en active Application Filing
- 2017-02-02 CN CN201780009261.1A patent/CN108883929B/zh active Active
- 2017-02-02 MY MYPI2018001374A patent/MY191228A/en unknown
- 2017-02-02 KR KR1020187023014A patent/KR102438434B1/ko active IP Right Grant
- 2017-02-02 EA EA201891734A patent/EA039544B1/ru unknown
- 2017-02-02 EP EP17703715.7A patent/EP3411327B1/en active Active
- 2017-02-02 AR ARP170100260A patent/AR107517A1/es active IP Right Grant
- 2017-02-02 TW TW106102907A patent/TWI732818B/zh active
- 2017-02-02 US US16/074,515 patent/US10941038B2/en active Active
- 2017-02-02 BR BR112018014726-5A patent/BR112018014726B1/pt active IP Right Grant
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EA039544B1 (ru) | 2022-02-09 |
EP3411327A1 (en) | 2018-12-12 |
PL3411327T3 (pl) | 2022-03-14 |
CA3010549A1 (en) | 2017-08-10 |
US20190039886A1 (en) | 2019-02-07 |
MX2018008598A (es) | 2018-12-10 |
CN108883929B (zh) | 2022-04-26 |
CN108883929A (zh) | 2018-11-23 |
WO2017134162A1 (en) | 2017-08-10 |
BR112018014726A2 (pt) | 2018-12-11 |
US10941038B2 (en) | 2021-03-09 |
AR107517A1 (es) | 2018-05-09 |
KR102438434B1 (ko) | 2022-09-01 |
EA201891734A1 (ru) | 2019-01-31 |
ZA201804078B (en) | 2021-10-27 |
BR112018014726B1 (pt) | 2023-04-18 |
CA3010549C (en) | 2023-01-17 |
MY191228A (en) | 2022-06-09 |
EP3411327B1 (en) | 2021-12-08 |
KR20180111842A (ko) | 2018-10-11 |
TWI732818B (zh) | 2021-07-11 |
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