TWI724250B - 氫甲醯化混合物之不含鉻及鎳的氫化 - Google Patents
氫甲醯化混合物之不含鉻及鎳的氫化 Download PDFInfo
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- TWI724250B TWI724250B TW106138464A TW106138464A TWI724250B TW I724250 B TWI724250 B TW I724250B TW 106138464 A TW106138464 A TW 106138464A TW 106138464 A TW106138464 A TW 106138464A TW I724250 B TWI724250 B TW I724250B
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Abstract
本發明涉及用於甲醯化之醛的非均相氫化的催化劑。本發明解決的問題是開發不含鉻及鎳之催化劑。此外,它還能夠以工業規模經濟活化源自工業甲醯化之醛混合物的氫化作用。出於此目的,催化劑不應該依賴昂貴的貴金屬,諸如Ru、Pd、或Pt。此問題藉由在製備習用的Cu/Ni/Cr系統時省去鉻及鎳,使得獲得催化劑而解決,其中該催化劑的載體材料上僅有銅作為氫化活性組分,而非鉻或鎳。這裡令人驚訝的是,儘管三種氫化活性金屬中的兩者被省略,仍然出現用於預期目的之功能性催化劑。然而,這需要以下作為必需條件:所使用的載體材料是二氧化矽,且活性催化劑中的Cu及SiO2含量被精確地設定在非常嚴格的限度內。
圖4與摘要有關
Description
本發明係關於一種藉由醛氫化來製備醇的方法,其中在氫存在下,使包含至少一種醛及至少一種伴隨組分的進料混合物與非均相催化劑接觸,提供一種產物混合物,其至少包含相應於經氫化之醛的醇和至少一種副產物,其中該催化劑包含載體材料,及施加至該載體材料的銅。
本發明進一步關於製備相應催化劑及相應前驅物、視情況活化該前驅物、及活性催化劑在該方法中的用途。
自醇消除氫(脫氫)會產生醛。相反地,可藉由氫化(添加氫)而由醛製備醇。
氫化通常為工業界極頻繁進行之反應。以工業規模實施的另一具體反應是醛氫化,即製備所謂甲醯化之醇的方法。
甲醯化之醇是藉氫甲醯化〔羰氧化反應(oxo reaction)〕方法所製備的醇。在氫甲醯化中,使烯烴(烯)與合成氣體(一氧化碳及氫氣之混合物)反應以提供醛;後續氫化則提供實際甲醯化之醇。甲醯化之醇充當生產用於塑膠之界面活性劑及/或塑化劑的中間產物。每年全球生產數百萬公噸的甲醯化之醇。
由於藉由氫甲醯化得到的醛氫化為甲醯化之醇的製備中必需的步驟,因此本發明涉及在工業規模上有實用性之製程。
在工業實務中,通常在非均相固定床催化劑上以液相來氫化甲醯化之醛。由於產出量很大,催化劑對加工具有重要意義,其原因在於決定了反應速率和氫化的選擇性。由於待氫化之醛從未以純的形式出現,而是以始結構異構醛之混合物形式出現,其始終伴隨大量麻煩之伴隨組分,其首先在氫化中帶來非所欲的二次反應,且其次損害氫化催化劑,因此選擇適合之催化劑並非無足輕重。由於包含待氫化之醛的進料混合物,其組成係由上游之氫甲醯化反應加以決定,因此必須針對特定氫甲醯化而精確調節氫化催化劑。
對於甲醯化之醛的氫化而言,已發現到有用的催化劑為包含載體材料的那些,已在該載體材料上面施加作銅、鉻、及鎳作為活性組分。
相應催化劑係經揭示於DE19842370A1中。它包含銅及鎳,其各在0.3重量%至15重量%濃度範圍內,且鉻在0.05重量%至3.5重量%的比例內。所使用之載體材料為多孔二氧化矽或氧化鋁。
US 4677234描述了一種用於在載體銅催化劑存在下製備乙二醇的方法。
儘管已證實這些催化劑適用於甲醯化之醛之工業實務氫化,但仍存在對替代物之需要。其原因在於這些催化劑的鉻含量。
根據REACH指示之附錄XIV,諸如上述催化劑之含鉻物質必須經歐盟委員會授權才能在歐盟境內使用。授權之准予涉及極高複雜性及高成本;此外,無法事先預期授權的准予。此外,必須每五年重複申請 程序。
有此等嚴格條件之原因為所使用的鉻的無疑致癌性,其和以下有關係:首先當去活化之後必須處理氫化催化劑時,以及其次當藉由用鹼金屬鉻酸鹽或鹼金屬二鉻酸鹽浸漬而新產生氫化催化劑時。
EP3037400A1中所揭示之催化劑已解決了鉻的問題,該催化劑幾乎不含鉻。然而,在該系統中還有需要改進之處,因為用於生產無鉻催化劑的鎳及鎳化合物同樣是致癌性的。
在這方面,所處理的問題是指定一種適用於工業醛氫化之催化劑系統,其不含鉻且不含鎳。
EP2488478B1描述了C10醛的兩階段氫化,其中在第二氫化階段使用不含銅、鉻、及鎳,但含有釕的催化劑。Ru的成本相對較高,且出於此原因,此方法在工業規模上並非總是經濟可行的。此外,該方法也不是無鎳的,其原因在於必須在第一階段使用含鎳催化劑以達到可接受的氫化結果。
WO95/32171A1描述了在其它元素存在或不存在(包括鉻)的情況下,包含銅及二氧化矽的各種氫化催化劑。可注意到特定無鉻變體的CuO含量非常高(遠高於20重量%)。這種富銅催化劑的原料成本相當高。
US 3,677,969描述了一種有機金屬氫化催化劑。此系統的一個缺點是其生產成本較高,其原因在於它需要額外的硫化(sulphidation),且其必須在非常高的溫度(400℉至1000℉)下被熱處理。此外,建議視情況的鉻及鎳的含量。
鑑於所有上述,迄今尚未能發現適合於以工業規模氫化氫甲 醯化混合物之無鉻且無鎳催化劑。
鑑於此先前技術,本發明解決的問題是開發不含鉻及鎳之催化劑,其他已知致癌物質同樣不存在。此外,它還能夠以工業規模經濟活化源自工業甲醯化之醛混合物的氫化作用。出於此目的,催化劑不應該依賴昂貴的貴金屬,諸如Ru、Pd或Pt。為了降低原料成本,催化劑的銅含量應該處於最低。以下也為了催化劑的生產成本的利益:可在低溫下進行製備,且催化劑不必被硫化。
此問題係藉由在製備習用的Cu/Ni/Cr系統時省去鉻及鎳,使得獲得催化劑而解決,其中該催化劑的載體材料上僅有銅作為氫化活性組分,而非鉻或鎳。這裡令人驚訝的是,儘管三種氫化活性金屬中的兩者被省略,仍然出現用於預期目的之功能性催化劑。然而,這要求以下作為必需條件:所使用的載體材料是二氧化矽,且活性催化劑中的Cu及SiO2含量被精確地設定在非常嚴格的限度內。SiO2特別適合作為載體的原因可能是因為其包括非常少的布朗斯特酸性或布朗斯特鹼性位點,其加速了副產物的形成。
本發明因而提供一種藉由醛氫化來製備醇的方法,其中在氫存在下,使包含至少一種醛及至少一種伴隨組分的進料混合物與非均相催化劑接觸,提供一種產物混合物,其至少包含相應於經氫化之醛的醇及至少一種副產物,其中該催化劑包含載體材料,及施加至該載體材料的銅,其中該載體材料係二氧化矽且其中呈活化形式的催化劑具有總計達100重量%的以下組成物: 二氧化矽:86重量%至90重量%;銅:10重量%至14重量%;鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm;氧化鋁:按重量計0ppm至按重量計1000ppm;其它物質:按重量計0ppm至1重量%。
一直將「其它物質」在這方面的含義理解為指存在於催化劑中,但在列舉中明確提到的化學元素或其化合物。在上述組成物的情況下,「其它物質」因此是除了SiO2、Cu、Ni、Cr、及Al2O3之外的所有組分的總稱。
「其它物質」的實例可為碳酸鹽、氫氧化物或單純插入的水。可痕量檢測到的貴金屬(諸如Pt、Ru或Pd)同樣被包含在「其它物質」一詞中。出於成本原因,根據本發明,省去了在製備催化劑時考慮加入的貴金屬。然而,不排除能以現有分析方法在所製備的催化劑中檢測到痕量的Pt、Ru、或Pd。然而,這些就像鎳及鉻殘留物一樣接著將被分類為無意的污染(來自裝置的材料或人員所佩戴的珠寶)。理想情況下,「其它物質」的含量為零。
已發現到用於氫化任務的特別適合催化劑是呈活化形式、具有總計達100重量%之以下組成物:二氧化矽:87重量%至89重量%;銅:11重量%至13重量%; 鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm;氫氧化物:按重量計0ppm至按重量計100ppm;釕:按重量計0ppm至按重量計50ppm;鈀:按重量計0ppm至按重量計50ppm;鉑:按重量計0ppm至按重量計50ppm;氧化鋁:按重量計0ppm至按重量計100ppm;水:按重量計0ppm至按重量計100ppm;碳酸鹽:按重量計0ppm至按重量計100ppm;其它物質:按重量計0ppm至0.5重量%。
根據本發明所使用的載體材料是二氧化矽。有可能使用氣相(fumed)SiO2或沉澱二氧化矽作為載體材料。毋論SiO2的合成,總是以在載體材料中具有更多或更少結晶組分的固體形式來使用催化劑。因此氫化中的催化劑是非均相催化劑,其原因在於它不溶於反應混合物中,而是存在於另一相中。
較佳使用以下載體材料:具有藉由環己烷浸沒法所決定、介於0.8cm3/g和1.2cm3/g之間的比孔隙體積(specific pore volumn);且具有藉由ISO方法9277所決定、介於130m2/g至170m2/g之間的比表面積(BET表面積)。可從來自Evonik Resource Efficiency GmbH的Aerolyst ® 3041獲得這種材料。其基於氣相二氧化矽。
為了高加工強度的利益,係在壓力介於15×105Pa和25×105Pa之間和溫度介於140℃和180℃之間進行氫化。在此應選擇壓力及溫度以 使得進料混合物及產物混合物呈液相。
較佳地,以超化學計算量供應氫氣,以保證實質上完全氫化。然而,應設定氫氣之濃度,使得至少一些氫氣溶解於液相中。有一些氫氣亦可處於氣相,且因而在反應混合物中形成氣泡。在彼情況下,使反應在所謂的「滴流床」操作中生效。
根據本發明之催化劑系統係為了源自氫甲醯化的進料混合物的氫化而開發,且確切而言包含複數種醛,其具有相同數目n個碳原子,以及相應的醇及高沸物,其中n為介於三與十八之間的自然數。
已對具有總計達100重量%之以下組成規格的C9醛混合物的氫化進行特別優化:具有九個碳原子之醛的總分率:25重量%至75重量%;具有九個碳原子之醇的總分率:10重量%至55重量%;縮醛之總分率:0.5重量%至5.5重量%;其他烴之總分率:0重量%至40重量%;水:0重量%至3重量%。
一般係在C8烯烴的鈷催化氫甲醯化中形成這種進料混合物。
其尤其適用於具有總計達100重量%之以下組成規格的C9醛混合物的氫化:具有九個碳原子之醛的總分率:15重量%至65重量%;具有九個碳原子之醇的總分率:20重量%至65重量%;縮醛之總分率:0.5重量%至5.5重量%; 其他烴之總分率:0重量%至40重量%;水:0重量%至1重量%。
一般係在C8烯烴的銠催化氫甲醯化中形成這種進料混合物。
關於催化劑的化學及物理性質、以及其因而對氫化任務的適用性,係藉由其製備而被確定到關鍵程度。
因此,催化劑的製備是本發明的重要態樣。這主要根據藉由以下步驟的請求項加以實現:a)提供含有至少99重量%二氧化矽之載體材料;b)提供氫氧化碳酸銅(II)、碳酸氫銨、及/或碳酸銨、氨及水;c)從氫氧化碳酸銅(II)、碳酸氫銨、及/或碳酸銨、氨及水來製備溶液,使得該溶液具有介於10重量%和15重量%之間的銅含量,其中該溶液裡的鉻比率介於按重量計0ppm和按重量計50ppm之間,且其中該溶液裡的鎳比率介於按重量計0ppm和按重量計50ppm之間;d)用該溶液浸漬該載體材料;e)在溫度介於50℃和150℃之間乾燥經浸漬的該載體材料;f)在溫度介於300℃和600℃之間對經乾燥、浸漬的該載體材料進行鍛燒以獲得前驅物;g)藉由用氫氣還原而活化該前驅物以獲得活性催化劑。
更具體言之,步驟a)至f)係關於前驅物之製備,且步驟g)係關於製備來自前驅物之實際催化劑。
這種區別是重要的,其原因在於活化通常與前驅物之製備在 不同位置進行。活化通常係在原位進行,即稍後進行氫化的位點,更具體言之係在反應器中。在這種情況下,係將無催化劑活性的前驅物安裝進氫化反應器中,接著出於還原之目的而使其與氫接觸,並因此被活化。此具有不藉由與大氣的氧氣接觸而再次形成氧化銅之優點。
可替代地,催化劑係在移地(ex situ)活化,即在氫化反應器外部還原,並以活性形式供應和安裝。然而,這必須接著在保護性大氣下進行,其相應地生產成本高且不方便。
在催化劑中需要銅作為氫化活性金屬。然而有關催化劑的成本,應將銅含量降到必要的最低點。出於此原因,建議的是在製備步驟c)中之溶液時,以使銅含量介於10.5重量%和11.5重量%之間的方式來配製溶液。已發現最佳溶液為具有11重量%銅含量的溶液。
進行用溶液浸漬載體材料可用不同方式來進行。使溶液滲透入孔隙並充分填充孔隙。已發現以下步驟在浸漬時是有用的:將載體引入轉鼓中;將溶液噴灑至載體上並填充孔隙。在噴灑期間,可使暖空氣穿過經浸漬之載體的旋轉床。暖空氣通常是在環境溫度範圍內的空氣。
步驟d)中之浸漬和步驟e)中之經浸漬載體材料的至少一些乾燥係相應地根據本發明而在鼓輪中進行,使得載體材料被引入鼓輪中以用於浸漬;使鼓輪旋轉;將溶液噴灑進鼓輪中;及在乾燥期間,使溫度介於50℃和100℃之間、較佳在溫度80℃下的空氣流穿過鼓輪。步驟d)和e)因而在設備(鼓輪)中極少用手工作業,此降低了生產成本。
在本發明的其它具體實例中,同樣有可能在乾燥完成之前從轉鼓移除經浸漬的載體材料,並在100℃至150℃溫度範圍內的空氣流裡、 在乾燥器中將其完全乾燥。從轉鼓至乾燥器之轉移為一道額外加工步驟,但可導致低水含量。
當所提供的載體材料包含具有直徑介於1mm和2mm之間的圓柱形擠出物時,在催化劑的製備和安裝進反應器時處理它是明顯有幫助的。接著可像對整體材料一樣地處理催化劑。在液相氫化中,圓柱形擠出物在流動力學方面來說是有利的。來自Evonik的Aerolyst® 3014可提供這種較佳的呈現形式。作為催化劑的替代形式,亦有可能使用直徑範圍介於1mm和2mm之間的球體。
在活化之前,前驅物較佳具有總計達100重量%的以下組成物:二氧化矽:84重量%至86重量%;氧化銅:14重量%至16重量%;鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm;氧化鋁:按重量計0ppm至按重量計1000ppm;其它物質:按重量計0ppm至1重量%。
重要的是此前驅物中的銅仍呈氧化形式。因為所鍵結的氧氣、前驅物及活性催化劑的總重量有差異;且出於此原因,相對的所述量亦有差異。
在活化時,係用H2來將CuO還原成Cu。同時所形成的水則被排出。因為銅催化劑現在是金屬性的,所以催化劑現在有氫化活性。在活化結束時氧已被除去,故活性催化劑具有本發明組成物。較佳地,係 用液態氫在原位還原催化劑。可替代地,催化劑可在氣相中被有效地活化。
本發明同樣提供了以這種方式所製備之催化劑的用途,其係用於藉由根據本發明之醛氫化來製備醇的方法。
所描述之前驅物製備、其活化、及活性催化劑在醛氫化中之的用途共同解決了所述的問題。
本發明因而亦提供了一種組合方法,其用於製備前驅物、活化前驅物以提供活性催化劑、及使用醛氫化之催化劑。用於醛氫化之根據本發明的方法因而包含以下步驟:a)提供含有至少99重量%的二氧化矽之載體材料;b)提供氫氧化碳酸銅(II)、碳酸氫銨、及/或碳酸銨、氨及水;c)製備包含氫氧化碳酸銅(II)、碳酸氫銨、及/或碳酸銨、氨及水之溶液,使得溶液具有介於10重量%和15重量%之間的銅含量,其中溶液裡的鉻比率介於按重量計0ppm和按重量計50ppm之間,且其中溶液裡的鎳比率介於按重量計0ppm和按重量計50ppm之間;d)用溶液浸漬載體材料;e)在溫度介於50℃和150℃之間乾燥經浸漬的載體材料;f)在溫度介於300℃和600℃之間對經乾燥浸漬的載體材料進行鍛燒以獲得前驅物,其尤其具有總計達100重量%之以下組成物:二氧化矽:84重量%至86重量%;氧化銅:14重量%至16重量%;鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm; 氧化鋁:按重量計0ppm至按重量計1000ppm;其它物質:按重量計0ppm至1重量%。
g)將前驅物轉移至反應器
h)藉由用氫還原而在反應器中活化前驅物,以得到活性催化劑,其尤其具有總計達100重量%的以下組成物:二氧化矽:86重量%至90重量%;銅:10重量%至14重量%;鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm;氧化鋁:按重量計0ppm至按重量計1000ppm;其它物質:按重量計0ppm至1重量%。
i)在反應器中在氫氣存在下使活性催化劑與進料混合物接觸,該進料混合物包含至少一種醛及至少一種伴隨組分,其尤其提供了包含至少相應於經氫化醛之醇及至少一種副產物的產物混合物,其中該浸漬和至少一些乾燥係在鼓輪中進行,使得載體材料被引入鼓輪中以用於浸漬;使鼓輪旋轉;將溶液噴灑進鼓輪中;及在乾燥期間,使溫度介於50℃和100℃之間的空氣流穿過鼓輪。
在環境溫度下用水性四胺碳酸銅溶液(根據本發明製備自氫氧化碳酸銅(II)、碳酸氫銨、及/或碳酸銨、氨、及水)浸漬SiO2載體。其隨後為在中等溫度下、在空氣流裡乾燥。最後,在450℃下、在空氣中進行鍛燒。
所使用的載體材料為來自Evonik的Aerolyst® 3041。其一般性質為SiO2含量高於99%、圓柱形擠出物的直徑約1.7mm,孔隙體積約1cm3/g、及BET表面積約150m2/g。
使用氫氧化碳酸銅、濃氨溶液、碳酸氫銨、及/或碳酸銨和水來製備包括約13重量%銅的四胺碳酸銅溶液。接著再次用水將溶液稀釋成約11重量%銅。
出於浸漬之目的,接著將稀四胺碳酸銅溶液噴灑至載體材料上。在浸漬時,載體係在鼓輪上旋轉。在噴灑操作期間,使一定量的空氣穿過固定床。在浸漬後,噴灑溶液的量係經施加,使得幾乎所有孔隙都被液體填充,且將銅鹽溶液分佈於整個晶粒。
在相同的鼓輪中進行乾燥。出於此目的,將穿過鼓輪和固定床的空氣流加熱至約75℃溫度。在這種特定情況下,使催化劑於煅燒之前 在空氣流裡、在120℃下、在其它反應器中經受進一步乾燥。
將銅鹽實質上轉化為氧化銅的煅燒係在連續空氣流流過的烘箱中進行;GHSV(氣體每小時空間速度)為2000h-1;及在空氣中、於450℃下煅燒催化劑10小時。
原則上,可藉由任何浸漬法製備催化劑,該浸漬法係用溶液來填充載體孔隙;此等實例亦包括真空浸漬或用過量溶液浸漬載體。
亦可在其它常見工業組件(軸式乾燥機、腔式烘箱、帶式乾燥機、鼓輪式乾燥機、及真空乾燥機)中進行乾燥;一般的乾燥溫度係介於50℃和150℃之間。
亦有可能在鍛燒時使用不同組件:軸式爐、腔式爐、及迴轉爐等。450℃溫度當然也不是極度關鍵;在此處亦可設想更低的溫度或更高的溫度。
以此方式所製備的前驅物包括15重量%的CuO和約85重量%的SiO2。
出於活化以提供催化劑之目的,使前驅物以60 l/h(STP)、在10*105Pa下與氣態氫氣流接觸。溫度在此以每小時30K之步驟從60℃提高到180℃,並保持恆定12小時。
所使用的催化劑A為含鉻催化劑,且亦被用於DE19842370A1中所描述的實驗。
為了實施批次氫化實驗,使用藉著外部電路攪拌的1升高壓 不銹鋼反應器。反應器具有用於催化劑填充的插件,其具有4cm的直徑和30cm的長度。圖1顯示了機具設備的簡化流程圖。
藉著纏繞加熱帶來加熱反應器和導管,且藉著PT100熱電偶來控制和調節溫度。以45 l/h的循環速率、藉著Gather DS2X30齒輪泵來循環液相。借助LAUDA LTH350s恆溫器來控制液相的溫度。所使用的熱載體為MARLOTHERM SH。為了相分離,安裝不銹鋼容器(容量2升)並連續用水將其冷卻。相分離器同時用作液體反應物的儲存器。藉著Bronkhorst F231M或F231C質量流量計來調節氫氣和氮氣供應器。在實施批次實驗之前,將90ml的催化劑A(乾燥的)引入催化劑容器並安裝在反應器中。以60 l(STP)/h、在10*105Pa下、在氫氣流裡還原新鮮的氫化催化劑。溫度在此以每小時30K之步驟從60℃提高到180℃,並保持恆定12小時。將1 l的反應物充入相分離器,且透過反應器旁路來循環加熱液相。在達到所需反應溫度時,取出旁路樣品並藉由打開反應器分接頭而開始反應。在反應期間,係在預定時間取樣,並藉由離線GC(7890B GC;來自Agilent Technologies)加以分析。
圖2以圖的形式顯示在此實驗中所達到的轉化率和選擇性。
如實施例1所述地其使用來自實施例0之無鉻且無鎳催化劑(「催化劑C」)進行批次氫化。在此用催化劑C取代催化劑A。轉化率和選擇性圖顯示用催化劑C可達到高得多的醇選擇性。
在用於測試非均相催化劑系統的連續操作16通道系統中,進行替代性氫化催化劑的併行評估。該16通道系統具有中央反應器嵌段,其具有16個分離的不銹鋼反應器,其具有96cm的長度和5mm的內徑。電加熱反應器嵌段,並允許以精確度±1℃來等溫操作反應器。使用毛細管限流器系統來分配並計量加入液體和氣態反應物;反應器的壓力維持係基於來自Equilibar的背壓膜模組。為了評估氫化催化劑,在由實施例1和2所描述的批次實驗預估催化劑活性之後,以篩分粒級(sieve fraction)(0.2mm至0.4mm)使用0.2g至0.6g的催化劑(呈乾燥形式),並用碎石英(0.3mm至0.5mm)加以稀釋。一直稀釋所使用的催化劑,使10cm之固定長度的催化性活性床得以產生。在滴流床操作中引入液相氫化;在此需以氣態形式將氫氣引入。氫氣接著被部分溶解於液相中,且部分在氣相中呈泡沫形式。此外,有一個排氣流以避免氣態副產物的積累。該測試因而在溫度180℃下;以及在LHSV(液體每小時空間速度)6h-1和GHSV(氣態氫的氣體每小時空間速度)為2000h-1下,25*105Pa的氫氣壓力進行。所有測量均以雙重測定進行。產物樣品係類似於根據實施例1和實施例2的氫化實驗、藉由離線GC(7890B GC;來自Agilent Technologies)加以分析。
如藉由圖4所顯示之轉化率和選擇性圖的比較所示,對本發明之無鉻且無鎳催化劑C而言,有可能在整個實驗過程中,不斷達到高於含鉻且含鎳比較性催化劑A之醇選擇性的高醇選擇性。同時,相較於催化劑A,可注意到催化劑C在轉化程度上的下降要小得多。
實施例的比較顯示,有可能使用根據本發明之無Cr且無Ni 的Cu催化劑,以氫化由工業氫甲醯化所獲得的C5、C9、C13、及C17醛混合物;同時獲得包括高相應醛比例的產物混合物,而不想要之副產物的比例少。
經過長期觀察,來自無鉻且無鎳實驗之醛產率並未顯著地比用習用Ni/Cu/Cr系統的比較性實驗差。
在製備無鉻且無鎳催化劑時,有可能避免處理致癌物質。使用貴金屬是非必需的。在製備催化劑時不需額外的作業步驟,例如硫化。在製備時,高溫是非必需的。氫化結果完全令人滿意。該催化劑似乎在工業上是經濟可用的。
現在將參考實施例而詳細闡明本發明。出於此目的,圖式顯示了:圖1:所使用之高壓批次氫化裝置的機具設備流程圖。
圖2:C9醛混合物與含鉻且含鎳催化劑之批次氫化的轉化率和選擇 性圖。
圖3:C9醛混合物與無鉻且無鎳催化劑(「催化劑A」)之批次氫化的轉化率和選擇性圖。
圖4:C9醛混合物與含鉻且含鎳催化劑A、以及無鉻且無鎳催化劑C之連續氫化的轉化率和選擇性圖。
Claims (13)
- 一種藉由醛氫化來製備醇的方法,其中在氫氣存在下使包含至少一種醛及至少一種伴隨組分的進料混合物與非均相催化劑接觸,提供一種產物混合物,其包含相應於經氫化醛之至少一種醇和至少一種副產物,其中該催化劑包含載體材料,及施加至該載體材料的銅,其特徵在於該載體材料是二氧化矽;且呈活化形式之該催化劑具有總計達100重量%之以下組成:二氧化矽:86重量%至90重量%;銅:10重量%至14重量%;鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm;氧化鋁:按重量計0ppm至按重量計1000ppm;其它物質:按重量計0ppm至1重量%。
- 根據申請專利範圍第1項之方法,其特徵在於呈活化形式之該催化劑具有總計達100重量%之以下組成:二氧化矽:87重量%至89重量%;銅:11重量%至13重量%;鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm;釕:按重量計0ppm至按重量計50ppm;鈀:按重量計0ppm至按重量計50ppm; 鉑:按重量計0ppm至按重量計50ppm;氧化鋁:按重量計0ppm至按重量計100ppm;水:按重量計0ppm至按重量計100ppm;碳酸鹽:按重量計0ppm至按重量計100ppm;氫氧化物:按重量計0ppm至按重量計100ppm;其它物質:按重量計0ppm至0.5重量%。
- 根據申請專利範圍第1項或第2項之方法,其特徵在於藉由環己烷浸沒法所決定的該載體材料之比孔隙體積(specific pore volume)介於0.8cm3/g與1.2cm3/g之間,且在於藉由ISO方法9277所決定的該載體材料之比表面積(BET表面積)介於130m2/g與170m2/g之間。
- 根據申請專利範圍第1項或第2項之方法,其特徵在於係在壓力介於15*105Pa與25*105Pa之間和溫度介於140℃與180℃之間進行,該壓力及溫度係經選擇,使得進料混合物及產物混合物呈液相。
- 根據申請專利範圍第4項之方法,其特徵在於該氫氣係以超化學計算量存在;該氫氣之濃度係經選擇,使得至少一些該氫氣被溶解於該液相中。
- 根據申請專利範圍第1項或第2項之方法,其特徵在於該進料混合物源自氫甲醯化反應,且確切而言包含複數種醛,其等具有相同數目n個碳原子,以及相應的醇及高沸物,其中n為介於三與十八之間的自然數。
- 根據申請專利範圍第6項之方法,其特徵在於該進料混合物具有總計達100重量%之以下組成: 具有九個碳原子之醛的總分率:25重量%至75重量%;具有九個碳原子之醇的總分率:10重量%至55重量%;縮醛之總分率:0.5重量%至5.5重量%;其他烴之總分率:0重量%至40重量%;水:0重量%至3重量%。
- 根據申請專利範圍第6項之方法,其特徵在於該進料混合物具有總計達100重量%之以下組成:具有九個碳原子之醛的總分率:15重量%至65重量%;具有九個碳原子之醇的總分率:20重量%至65重量%;縮醛之總分率:0.5重量%至5.5重量%;其他烴之總分率:0重量%至40重量%;水:0重量%至1重量%。
- 一種用於製備催化劑之方法,其包含以下步驟:a)提供包括至少99重量%的二氧化矽之載體材料;b)提供氫氧化碳酸銅(II)、碳酸氫銨及/或碳酸銨、氨、及水;c)從氫氧化碳酸銅(II)、碳酸氫銨及/或碳酸銨、氨、及水來製備溶液,使得該溶液的銅含量介於10重量%和15重量%之間,其中該溶液裡的鉻比率介於按重量計0ppm和按重量計50ppm之間,且其中該溶液裡鎳的比率介於按重量計0ppm和按重量計50ppm之間;d)用該溶液浸漬該載體材料;e)在溫度介於50℃和150℃之間乾燥經浸漬的該載體材料;f)在溫度介於300℃和600℃之間對經乾燥、浸漬的該載體材料進 行鍛燒以獲得前驅物;g)藉由用氫氣還原來活化該前驅物以獲得活性催化劑,其特徵在於該浸漬和至少部分乾燥係在鼓輪中進行,使得該載體材料被引入該鼓輪中以用於浸漬;使該鼓輪旋轉;將該溶液噴灑進該鼓輪中;及在乾燥階段,在溫度介於50℃和100℃之間使空氣流穿過該鼓輪。
- 根據申請專利範圍第9項之方法,其特徵在於該溶液的銅含量介於10.5重量%和11.5重量%之間。
- 根據申請專利範圍第9項至第10項中任一項之方法,其特徵在於所提供的該載體材料包含具有直徑介於1mm和2mm之間的圓柱形擠出物。
- 根據申請專利範圍第9項至第10項中任一項之方法,其特徵在於該前驅物具有總計達100重量%之以下組成:二氧化矽:84重量%至86重量%;氧化銅:14重量%至16重量%;鎳:按重量計0ppm至按重量計50ppm;鉻:按重量計0ppm至按重量計50ppm;氧化鋁:按重量計0ppm至按重量計1000ppm;其它物質:按重量計0ppm至1重量%。
- 一種用於醛氫化之方法,其包含以下步驟:a)提供含有至少99重量%的二氧化矽之載體材料;b)提供氫氧化碳酸銅(II)、碳酸氫銨及/或碳酸銨、氨、及水; c)從氫氧化碳酸銅(II)、碳酸氫銨及/或碳酸銨、氨、及水來製備溶液,使得該溶液具有介於10重量%和15重量%之間的銅含量,其中該溶液裡的鉻比率介於按重量計0ppm和按重量計50ppm之間,且其中該溶液裡的鎳比率介於按重量計0ppm和按重量計50ppm之間;d)用該溶液浸漬該載體材料;e)在溫度介於50℃和150℃之間乾燥經浸漬的該載體材料;f)在溫度介於300℃和600℃之間對經乾燥浸漬的該載體材料進行鍛燒以獲得前驅物;g)將該前驅物轉移至反應器;h)藉由用氫氣還原而在該反應器中活化該前驅物以獲得活性催化劑;i)在該反應器中在氫氣存在下使該活性催化劑與進料混合物接觸,該進料混合物包含至少一種醛及至少一種伴隨組分,其中該浸漬和至少部分乾燥係在鼓輪中進行,使得該載體材料被引入該鼓輪中以用於浸漬;使該鼓輪旋轉;將該溶液噴灑進該鼓輪中;及在乾燥階段,在溫度介於50℃和100℃之間使空氣流穿過該鼓輪。
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