TWI551349B - 液體/氣體反應器及其使用方法 - Google Patents
液體/氣體反應器及其使用方法 Download PDFInfo
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Description
本發明係關於一種液體/氣體反應器。更特定而言,本發明係關於一種利於控制反應器中之溫度的液體/氣體反應器。本發明亦係關於一種於該反應器中實施之方法。
經常在固體觸媒床上進行液體與氣體之間的化學反應。該反應可係放熱反應(即其產生熱量),或其可係吸熱反應(即其利用熱量且觀察到冷卻)。在某些反應中,反應之熱效應即使在此等反應中仍係適中,若不控制溫度,則仍可導致選擇性之損失。然而,對更多放熱或吸熱反應而言,有必要更嚴格地控制熱效應。在極端情況下,由劇烈放熱反應所產生之熱量可導致熱失控。類似地,劇烈吸熱反應之冷卻效應可導致該反應中止。
在其中發生放熱或吸熱反應之液體/氣體反應器中控制溫度的常用方法係藉由加熱或冷卻產物之再循環。該再循環具有限制溫度上升之效果。此等所謂之「液體再循環」反應器係廣泛用於商業中,例如用於使苯氫化、使烯烴選擇性氫化以移除炔烴及/或二烯烴、及使醛氫化成醇。
圖1顯示C2及C3流中之炔烴及二烯烴之選擇性氫化的典型流程圖。此配置係類似於AIChE 15th Ethylene Producer Conference 2003之報告,Session 64a「Overview on C2 and C3 Selective Hydrogenation」第560頁圖7中所示之配置。該氫化單元包括主反應器1及終止反應器2。經由管線3將
C3原料供應至主反應器1,其中該原料與已經由管線4供應之氫在觸媒上反應。在管線5中萃取產物,且在冷卻器6中冷卻,然後經由管線7傳遞至液體/氣體分離器8。在管線9中移除部份液體並使其再循環至主反應器1。在所述配置中,再循環流9在供應至主反應器1之前與原料流3組合。
在管線10中移除來自分離器之過量氣體。
在管線11中移除來自該氣體/液體分離器之剩餘液體,且將其進料至終止反應器2中。此反應器係塞流式反應器。在管線12中移除產物。應瞭解,由於進料經再循環產物流稀釋,因此該液體再循環反應器係部份反向混合型。
在將100%烯烴氫化成烷烴或將醛氫化成醇的情況下,通常需要為進料速率10至20倍之再循環速率,以避免溫度上升超過反應器(高於20℃)。此再循環產物顯著稀釋反應物,且因此減少於該液體再循環反應器中所實現之轉化。
需要終止反應器2(其亦可稱為加工反應器),以製造具有低濃度未反應進料組分之高品質產物。為獲得適用於良好分佈之液體速度,該終止階段之橫截面面積必須比該液體循環反應器小得多,且因此為實現足夠之觸媒體積,必須使用長終止反應器。
圖2顯示先前技術之液體再循環反應器之另一實例的示意圖。在此圖中,經由管線21將氣體進料添加至反應器22中。經由管線23添加新鮮進料,且與來自管線24之再循環產物混合,然後經由管線25將其供應至反應器22之頂部空間。然後,該混合液體及氣體向下流動通過觸媒床26,並
在其中發生反應。於管線27內移除未反應氣體,且於管線28內移除部份產物。在管線29中藉由泵30移除該產物流之剩餘部份,然後於加熱器/冷卻器45內加熱或冷卻至所需溫度,且然後經由管線24再循環至反應器22。
US 6693225描述具有多於一個觸媒床之液體再循環反應器,其中在第一觸媒床中及該等觸媒床之間添加氫。視需要添加第二外部塞流式反應器,以完成轉化。
另一配置係描述於US 4704492(其係關於選擇性氫化粗製丁二烯中之炔系雜質)及US 4937051(其係關於烴油之氫化)中。在此等案件中,描述具有自最終產物至第一床入口之液體再循環及自床出口至床入口之其他再循環的一連串床。於該等床之間添加氫,以提高選擇性。經常需要第二外部終止/加工階段,以獲得高效率及/或高品質產物。第一再循環反應器係用於提供一致的反應條件及良好的蒸氣/液體混合。然而,由於該第一再循環反應器係固有地經部份反向混合,因此其具有觸媒低效利用的缺點。
如US 7663006中所述,需要高液體速度以於此等填料床反應器內實現良好的蒸氣/液體接觸。在GB 1315217中,描述一種使醛氫化之方法,其中使用高液體流量以實現良好的觸媒利用率。另一配置係描述於US 4681674中。在此案中推薦再循環,以保持均勻的觸媒濕潤。然而,此方法具有以下缺點:產物至進料之再循環稀釋反應物並降低反應速率。
在US 5573736中,描述一種由一系列皆具有液體再循環
以移除反應熱之不同區域組成的反應器。該反應器中之最後床係無液體再循環之塞流式床。在此類型設計中,該最後塞流式部份內之速度由於相當低的液體速率而將極低,且因此蒸氣/液體分佈可能較差。
在US 4960960中,描述一種其中在一個反應器內或使用兩個串聯反應器以兩階段實施氫化之方法。該第二階段係描述為具有或不具有液體再循環之分離式反應器或置於主床下方且與該主床直徑相同之床。該設計具有以下缺點:需要第二容器或在低液體速度之部份中需要增加反應器高度;及降低液體速度導致低效之觸媒利用。
現已發現,藉由改良填料床反應器可使觸媒之有效性近乎加倍。此可用於提供更高品質之產物,且可無需終止反應器。即使保留該終止反應器,仍將降低裝置及觸媒成本,由此提高該方法之經濟性。
根據本發明提供一種液體/氣體反應器,其包括:(a)塊狀觸媒床及用於將新鮮進料及再循環之至少部份轉化之液體產物流供應至該塊狀觸媒床的構件;(b)用於自該塊狀觸媒床收集至少部份轉化之液體產物流並使其至少一部份再循環至步驟(a)的構件;(c)實質上垂直延伸通過該塊狀觸媒床的小型觸媒床及用於將再循環之至少部份轉化之產物流僅供應至該小型觸媒床的構件;及(d)在該塊狀觸媒床與該小型觸媒床之間的隔離壁。
通常在步驟(a)中將氣態反應物及新鮮液體進料供應至該塊狀觸媒床。
本發明反應器通常將適用於放熱或吸熱反應。
藉由本發明配置,僅對該小型觸媒床供應已經歷反應且因此將至少部份轉化之進料。因此,與在不具有該小型觸媒床之反應器中相比,離開該小型觸媒床之物流將提供更完全轉化之最終產物。
雖然該小型觸媒床可在該塊狀觸媒床內之任何適宜位置,但在一配置中可使其位於中央,以使該塊狀觸媒床環繞其形成。
可使用該小型觸媒床對該塊狀觸媒床之觸媒面積之任何適宜比例。通常該比例係經選擇,以維持所需之蒸氣/液體混合及實現所需之觸媒濕潤。較佳地,該小型觸媒床對該塊狀觸媒床之比例將係該小型床之再循環流速對該塊狀床之進料加再循環流速之比例的約一半至約兩倍。在一配置中,該比例將實質上係1:1。此意指該小型觸媒床將具有提供良好蒸氣/液體混合及良好潤濕之液體速度。通常,此可具有與在塊狀觸媒床內所實現者相同之水準。
在一配置中,將使來自該塊狀觸媒床之反應器底部物全部再循環,其中使一部份再循環至該塊狀觸媒床,並傳遞一部份至該小型觸媒床。
雖然可使用最高100%之過量(該過量係與來自該塊狀觸媒床之再循環結合)以便於控制,但是進入該小型觸媒床之流速較佳係等於最終產物速率。
該反應器較佳將包含用於調節再循環流之溫度的加熱器或冷卻器。
藉由本發明配置可獲得改良之轉化。在某些配置中,不需要另一加工反應器。此降低資本及操作成本。
可使用任何適宜之觸媒。通常,觸媒之選擇將取決於待實施之反應。該觸媒可呈任何適宜形式。實例包括顆粒、擠出物、樹脂或浸漬填料。所使用之觸媒實例包括鎳、銅/鉻或鈀。適宜之載體包括氧化鋁。在塊狀及小型觸媒床中可使用相同或不同的觸媒。位於該小型觸媒床及該塊狀觸媒床內之觸媒可係相同或不同。
該反應器可係由任何適宜之材料構成。該等床之操作溫度可係相同或不同。當該等溫度係不同時,該反應器將包括加熱或冷卻裝置。當意欲於不同溫度下操作該等床時,該兩個床之間的隔離壁將由絕緣材料製成。
該隔離壁可係任何適宜之結構。在一配置中,其可僅係其中將放置該小型觸媒床之內部管道。該管道可具有任何適宜之橫截面,但可係圓形橫截面。在另一配置中,該隔離壁可係由(例如)固定於反應器壁上的半管道形成。
本發明之一特定優點係可改良現有之單床或多床反應器以安裝垂直小型床。無論該反應器係新製成或現有反應器之改良物,當存在多個床時,可在一個、某些或所有床上提供該小型觸媒床。
本發明裝置可用於在固體觸媒床上之任何放熱或吸熱液體/氣體反應。放熱反應之實例包括醛、酮、炔烴、二烯
烴、或芳基化合物之氫化作用及氧化作用。吸熱反應之實例包括脫氫作用。特定而言,本發明適用於使丁二烯選擇性氫化成丁烯、自苯製造環己烷或自2-乙基-己-2-烯醛製造2-乙基己醇。
因此,根據本發明之第二態樣,提供一種用於氣體/液體反應之方法,其包括以下步驟:(a)將含有新鮮進料及再循環產物流之進料供應至上述第一態樣之裝置之塊狀觸媒床;(b)將氣體供應至上述第一態樣之反應器;(c)使反應在該塊狀觸媒床內發生;(d)收集至少部份轉化之液體產物流;(e)使該部份轉化之液體產物流之至少一部份再循環至該塊狀觸媒床;(f)將該部份轉化之液體產物流之至少一部份供應至上述本發明第一態樣之小型觸媒床;(g)使反應在該小型觸媒床內發生;及(h)自該小型觸媒床收集產物流。
當可以再循環至塊狀觸媒床之方式或以進料至小型觸媒床之方式使所有來自該塊狀觸媒床之部份反應流返回至反應器時,應瞭解可收集或回收該部份反應流之部份。
於再循環之前,可視需要加熱或冷卻該返回至反應器之部份反應流。
較佳流動方式通常將係產生正壓降之流動方式。然而,亦可使用低液體速率或滴流床。在意欲使用液體/氣體分
流器時,其可係任何適宜之設計。
本發明之裝置及方法通常係適用於下流式系統。然而,其亦可用於上流式系統及使用大量過量氣體的系統。在一配置中,該等氣體及液體流可係向下流動之並流。本發明之裝置及方法可用於放熱及吸熱反應。
本發明方法可係任何適宜之反應。在一配置中,該反應可係醛至醇之氫化作用。在另一配置中,該反應可係二烯烴(如丁二烯)或炔烴至烯烴的選擇性氫化作用。在另一配置中,該反應可係芳族化合物中之芳環的氫化作用。
所選定之觸媒及反應條件將取決於所實施之方法。舉例而言,當反應係醛之氫化作用時,可使用銅/鉻觸媒,且可在約140℃至200℃之溫度及大於10 barg之壓力下實施該反應。對二烯烴之選擇性氫化作用而言,可使用鈀或氧化鋁觸媒,且可在約20℃至130℃之溫度及約5 barg至約20 barg之壓力下實施該反應。
現將參考以下附圖以實例來描述本發明。
本發明裝置係描述於圖3中。反應器容器31包含塊狀觸媒床32及小型觸媒床33。經由管線34提供氣體。經由管線35供應新鮮進料,其在該管線35內與經由管線41再循環之再循環部份反應流混合。將新鮮進料及部份反應流之此混合物饋送至塊狀觸媒床32,其中此混合物與氣體發生反應。經由管線37移除廢氣,且經由管線38使用泵39回收部份反應產物流,然後藉由加熱器或冷卻器40調節溫度。使
此經溫度調節之物流36之部份與新鮮進料35及物流41之混合物合併,然後供應至塊狀觸媒床32。經由管線42將剩餘物傳遞至使用隔離壁43與塊狀觸媒床32隔開之小型觸媒床33。使此物流與經由管線34所供應之氣體發生進一步反應。經由管線44收集來自該小型觸媒床之產物。當與習知液體再循環反應器內所獲得之產物相比時,此產物將具有提高轉化率。
本發明反應器可用於使脂族C2-C20醛在CuCr觸媒上氫化成對應的醇。該兩個觸媒床中通常將使用相同觸媒。在此反應中,基於進料計之停留時間將係約0.1小時至約10小時。在約5 bar至約50 bar之壓力下,該等觸媒床之溫度將係約100℃至約200℃。或者,可在鎳觸媒上進行該反應,其中基於進料計之停留時間將係約0.1小時至約10小時。該反應將於約5 bar至約50 bar之壓力及約70℃至約150℃之溫度下進行。
通常將再循環速率選定為與先前技術方法中所使用之再循環速率類似或相同。雖然不希望受任何理論限制,但據信需要該再循環以限制溫度上升。藉由限制溫度上升,可限制出口溫度。此具有限制或避免副產物形成之效益,且可提供改良之選擇性。此外,此避免低入口溫度。此係有益,因為在反應可開始之前,低入口溫度將需要該反應器入口內具有大誘發區。然而,該再循環速率不應大於必需值,因為此會以產物過度稀釋反應物並降低觸媒之有效性。
無論使用何種觸媒系統,再循環速率將係進料速率之約5倍至約50倍。將確定該等觸媒床之尺寸,以使液體表面速度在約0.2 cm/s至約4 cm/s之範圍內。通常將以約等於化學計量要求值或最高約兩倍化學計量要求值之數量添加氫。由於此反應係放熱反應,因此將使用冷卻器40以移除反應熱。
在50 barg壓力下,使正壬醛與2%過量氫通過鎳觸媒床之上方。使用C出/C入=e-k/LHSV,可算出一級動力係數k。由於在兩個實例中獲得實質上相同數值,因此將看到一級模式係轉化率之良好預測。條件及結果係列於表1中。
為說明藉由使用本發明隔離式反應器所獲得的改良,將觸媒床分配在主床與第二塞流式床之間,以使停留時間及因此轉化率C出/C入將與在該等對照實例中相同。藉由C出/C入=
e-k/LHS計算轉化率。細節及結果係列於表2中。
與在相同體積之習知液體再循環反應器中獲得0.27重量%之殘餘未反應壬醛相比,本發明之分區床反應器實現僅0.012重量%之殘餘未反應壬醛。因此,將瞭解已實現提高轉化率。
為使用單一習知液體再循環床實現相同之性能改善,需要將床體積增加85%,即自0.4公升增加至0.73公升。
1‧‧‧主反應器
2‧‧‧終止反應器
3‧‧‧管線/原料流
4‧‧‧管線
5‧‧‧管線
6‧‧‧冷卻器
7‧‧‧管線
8‧‧‧液體/氣體分離器
9‧‧‧管線/再循環流
10‧‧‧管線
11‧‧‧管線
12‧‧‧管線
21‧‧‧管線
22‧‧‧反應器
23‧‧‧管線
24‧‧‧管線
25‧‧‧管線
26‧‧‧觸媒床
27‧‧‧管線
28‧‧‧管線
29‧‧‧管線
30‧‧‧泵
31‧‧‧反應器容器
32‧‧‧塊狀觸媒床
33‧‧‧小型觸媒床
34‧‧‧管線
35‧‧‧管線
36‧‧‧經溫度調節之物流
37‧‧‧管線
38‧‧‧管線
39‧‧‧泵
40‧‧‧加熱器/冷卻器
41‧‧‧管線
42‧‧‧管線
43‧‧‧隔離壁
44‧‧‧管線
45‧‧‧加熱器/冷卻器
圖1係先前技術之反應器系統之示意流程圖。
圖2係先前技術之液體/氣體反應器之示意圖。
圖3係本發明裝置之示意代表圖。
31‧‧‧反應器容器
32‧‧‧塊狀觸媒床
33‧‧‧小型觸媒床
34‧‧‧管線
35‧‧‧管線
36‧‧‧經溫度調節之物流
37‧‧‧管線
38‧‧‧管線
39‧‧‧泵
40‧‧‧加熱器/冷卻器
41‧‧‧管線
42‧‧‧管線
43‧‧‧隔離壁
44‧‧‧管線
Claims (15)
- 一種液體/氣體反應器,其包括:(a)塊狀觸媒床及用於將新鮮進料及再循環之至少部份轉化之液體產物流供應至該塊狀觸媒床的構件;(b)用於自該塊狀觸媒床收集至少部份轉化之液體產物流並使其至少一部份再循環至步驟(a)的構件;(c)實質上垂直延伸通過該塊狀觸媒床的小型觸媒床及用於將再循環之至少部份轉化之產物流僅供應至該小型觸媒床的構件;及(d)在該塊狀觸媒床與該小型觸媒床之間的隔離壁。
- 如請求項1之反應器,其中該小型觸媒床係置於環繞其形成之塊狀觸媒床的中央。
- 如請求項1或2之反應器,其中使所有部份轉化產物流再循環,其中一部份再循環至該塊狀觸媒床且一部份通過至該小型觸媒床。
- 如請求項1或2之反應器,其中該反應器另外包含在該至少部份轉化之再循環液體產物流上的加熱器或冷卻器。
- 如請求項1或2之反應器,其中在不同溫度下操作該等床。
- 如請求項5之反應器,其中該隔離壁係由絕緣材料製成。
- 如請求項1或2之反應器,其中該小型觸媒床對該塊狀觸媒床之比例係該小型床之再循環流速對該塊狀床之進料加上再循環流速之比例的約一半至約兩倍。
- 如請求項7之反應器,其中該小型觸媒床對該塊狀觸媒床之該比例實質上係1:1。
- 如請求項1或2之反應器,其中該小型觸媒床內之觸媒係不同於該塊狀觸媒床內之觸媒。
- 一種用於氣體/液體反應之方法,其包括以下步驟:(a)將含有新鮮進料及再循環產物流之進料供應至如請求項1至9中任一項之塊狀觸媒床;(b)將氣體供應至如請求項1至9中任一項之反應器;(c)使反應在該塊狀觸媒床內發生;(d)收集至少部份轉化之液體產物流;(e)使該部份轉化之液體產物流之至少一部份再循環至該塊狀觸媒床;(f)將該部份轉化之液體產物流之至少一部份供應至如請求項1至9中任一項之小型觸媒床;(g)使反應在該小型觸媒床內發生;及(h)自該小型觸媒床收集產物流。
- 如請求項10之方法,其中返回至該反應器之部份反應流於再循環之前係經加熱或冷卻。
- 如請求項10或11之方法,其係用於將醛氫化成醇。
- 如請求項10或11之方法,其係用於將二烯烴或炔烴選擇性氫化成烯烴。
- 如請求項13之方法,其中該二烯烴係丁二烯。
- 如請求項10或11之方法,其係用於芳族化合物中之芳環之氫化作用。
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FR2810991B1 (fr) | 2000-06-28 | 2004-07-09 | Inst Francais Du Petrole | Procede pour l'hydrogenation de coupes contenant des hydrocarbures et notamment des molecules insaturees contenant au moins deux doubles liaisons ou au moins une triple liaison |
WO2005087694A1 (ja) | 2004-03-16 | 2005-09-22 | Mitsubishi Chemical Corporation | 精製アルコールの製造方法 |
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2011
- 2011-02-14 GB GB201102551A patent/GB201102551D0/en not_active Ceased
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2012
- 2012-01-12 MX MX2012009393A patent/MX2012009393A/es active IP Right Grant
- 2012-01-12 US US13/583,335 patent/US9023299B2/en active Active
- 2012-01-12 EA EA201201106A patent/EA024857B1/ru not_active IP Right Cessation
- 2012-01-12 KR KR1020127021455A patent/KR101834912B1/ko not_active Application Discontinuation
- 2012-01-12 MY MYPI2012003846A patent/MY164037A/en unknown
- 2012-01-12 WO PCT/GB2012/050056 patent/WO2012110775A1/en active Application Filing
- 2012-01-12 SG SG2012058319A patent/SG183202A1/en unknown
- 2012-01-12 CN CN201280001128.9A patent/CN102844102B/zh active Active
- 2012-01-12 EP EP12700725.0A patent/EP2516050B1/en active Active
- 2012-01-12 BR BR112012019514-0A patent/BR112012019514B1/pt active IP Right Grant
- 2012-02-07 TW TW101103950A patent/TWI551349B/zh active
- 2012-08-06 ZA ZA2012/05924A patent/ZA201205924B/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3976713A (en) * | 1971-06-11 | 1976-08-24 | Sun Oil Company Of Pennsylvania | Isoparaffin-olefin alkylation utilizing recycle streams and multiple packed catalyst beds |
CN1793089A (zh) * | 2004-12-20 | 2006-06-28 | 凯洛格.布朗及鲁特有限公司 | α-甲基苯乙烯选择性加氢成枯烯 |
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TW201235104A (en) | 2012-09-01 |
MY164037A (en) | 2017-11-15 |
KR20130138645A (ko) | 2013-12-19 |
CN102844102B (zh) | 2015-06-10 |
CN102844102A (zh) | 2012-12-26 |
EP2516050A1 (en) | 2012-10-31 |
BR112012019514A2 (pt) | 2018-03-13 |
BR112012019514A8 (pt) | 2018-07-31 |
KR101834912B1 (ko) | 2018-04-13 |
GB201102551D0 (en) | 2011-03-30 |
US9023299B2 (en) | 2015-05-05 |
SG183202A1 (en) | 2012-09-27 |
BR112012019514B1 (pt) | 2019-08-06 |
MX2012009393A (es) | 2012-10-01 |
EA201201106A1 (ru) | 2013-05-30 |
WO2012110775A1 (en) | 2012-08-23 |
ZA201205924B (en) | 2013-10-30 |
EA024857B1 (ru) | 2016-10-31 |
EP2516050B1 (en) | 2016-08-10 |
US20140024863A1 (en) | 2014-01-23 |
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