TW201313315A - 製備包括磷改質沸石的觸媒的方法以及該沸石的用途 - Google Patents
製備包括磷改質沸石的觸媒的方法以及該沸石的用途 Download PDFInfo
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- TW201313315A TW201313315A TW101127924A TW101127924A TW201313315A TW 201313315 A TW201313315 A TW 201313315A TW 101127924 A TW101127924 A TW 101127924A TW 101127924 A TW101127924 A TW 101127924A TW 201313315 A TW201313315 A TW 201313315A
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- Prior art keywords
- zeolite
- catalyst
- steaming
- phosphorus
- carried out
- Prior art date
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- 239000010457 zeolite Substances 0.000 title claims abstract description 99
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- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/655—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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Abstract
本發明在第一實施例中有關製備磷改質沸石的方法,其包括以如下順序的步驟:a)提供在結構中包括至少一個十元環的沸石,任選進行離子交換,b)汽蒸上述沸石,c)在上述沸石上引入磷以引入至少0.1重量%的磷,上述引入通過幹浸漬或化學氣相沉積進行,d)混合步驟c)的上述沸石和至少選自以下的成分:一種或多種粘結劑和成形添加劑,e)使上述混合物成形,f)任選引入金屬,該步驟任選與步驟d)同時進行,g)任選清洗上述觸媒,h)任選煆燒上述觸媒,i)汽蒸上述觸媒,該步驟也稱作平衡步驟。在第二實施例中,磷可以通過任意手段引入,並且在步驟i)中汽蒸強度(X)是至少大約2。在上述第二實施例中,上述觸媒有利地在大於625℃、優選在700至800℃範圍的溫度汽蒸。步驟f)的金屬有利的為鈣。本發明還有關上述觸媒在醇脫水、烯烴裂解以製備更輕質的烯烴、MTO和利用含烯烴的醇類和/或醇類對芳族化合物進行烷基化中的用途。
Description
本發明係有關於製備包括磷改質沸石的觸媒的方法以及上述沸石的用途。該經改性的沸石可用於在蒸汽存在下高溫操作上述沸石的製程。例如可以引用,對醇進行脫水以將至少一種醇轉化成相應的烯烴,裂解C4+烯烴(也已知為OCP,烯烴轉化製程)以製備乙烯和丙烯的混合物,裂解甲醇或二甲醚(也已知為MTO)以生成輕質烯烴例如乙烯和丙烯以及重烴例如丁烯,通過醇類對芳族化合物進行烷基化,例如利用甲醇、乙醇或丙醇對苯或甲苯進行烷基化。
有效的觸媒是醇脫水的工業化以及上述其他製程中的關鍵。一種早期的用於乙醇脫水的觸媒是氧化鋁。該觸媒較便宜,但是需要低空速(space velocity)、高反應溫度以及會產生大量需要分離的乙烷。沸石,特別是磷酸鹽沸石解決了關於催化活性的問題以及提供接近聚合物等級的乙烯部分。沸石,特別是磷酸鹽沸石解決了關於催化活性的問題。已知包括磷改質沸石(磷改質沸石也稱作P-沸石)的觸媒。以下現有技術記載了多種製備上述觸媒的方法。
US 2006 106270有關雙功能觸媒系統在氧合物制丙烯(oxygenate to propylene,OTP)方法的烴合成反應區域中
的用途,上述氧合物制丙烯(OTP)方法在較高溫度下優選使用蒸汽稀釋劑操作以及使用移動床反應器技術。雙功能觸媒系統包括具有雙-功能能力的分子篩,其分散在磷改質氧化鋁基質中,其中所述基質包含不穩定的磷和/或鋁的陰離子。據解釋,利用該磷改質氧化鋁基質時所觀察到的熱液穩定作用是由於磷和/或鋁的陰離子從該基質中遷移或分散進入所連接的分子篩中而引起的。這些陰離子然後可用於修復、加強和/或穩定分子篩的結構對抗已知的分子篩結構破壞或變化的脫鋁機制,上述脫鋁機制是由暴露至相應於在OTP反應區域和再生區域中使用的那些溫度的溫度下的蒸汽所引起的。
US 5,231,064有關包括粘土和沸石的流體觸媒,上述粘土和沸石的至少一種已用含磷化合物例如磷酸二氫銨或磷酸處理過,以及其是在低pH(優選低於約3)噴霧乾燥的。認為上述觸媒有利地展示了減小的損耗。
EP 511013 A2提供了由高級烯烴或含石蠟的或混合的烯烴和石蠟原料製備C2-C5烯烴的改進方法。根據該現有技術,烴進料材料在升高的溫度、高空速和低烴分壓條件下接觸具體的ZSM-5觸媒以製備較低的烯烴。上述觸媒在用於烴轉化之前用蒸汽進行處理。優選的方法是在500至700℃優選550至600℃於1至5個大氣壓、優選1.5至3個大氣壓蒸汽中加熱上述觸媒1至48小時、優選15至30小時。活性觸媒成分是含磷的ZSM-5,其具有的表面Si/Al比在20-60的範圍。優選地,磷添加至所形成的ZSM-5,
根據例如U.S.專利3,972,832中所述的製程利用磷化合物浸漬ZSM-5。較少優選地,磷化合物可以添加至多成分混合物,由該多成分混合物形成上述觸媒。添加足夠量的磷化合物以提供具有0.1-10重量%、優選1-3重量%磷的最終ZSM-5組合物。
含磷的ZSM-5優選混合已知的粘結劑或基質例如二氧化矽、高嶺土、鈣膨潤土、氧化鋁、二氧化矽、矽鋁酸鹽(silica aluminate)等。ZSM-5通常包括1-50重量%、優選為5-30重量%以及最優選10-25重量%的觸媒組成。其中沒有向觸媒中引入金屬如Ca。ZSM-5的含量低於50%,沒有預汽蒸步驟。
EP 568913 A2記載了製備適用於將甲醇或二甲醚催化轉化成輕質烯烴的ZSM-5類觸媒的方法,其中該方法包括以下連續步驟:● 混合沸石ZSM-5類觸媒與矽溶膠和硝酸銨溶液,● 捏合、模制、乾燥和煆燒混合物,● 用HCl溶液在70-90℃交換改性的沸石,● 乾燥和煆燒H-改性的沸石,● 利用磷酸在減壓下浸漬H-改性的沸石,● 乾燥和煆燒P-改性的沸石,● 利用稀土元素溶液在減壓下浸漬P-改性的沸石,● 乾燥和煆燒P-稀土-改性的沸石,● 在500-600℃利用水蒸汽熱液處理P-稀土-改性沸石,以及
● 煆燒改性的沸石。
WO 03 020667有關由氧合物原料製備烯烴特別是乙烯和丙烯的方法,其包括使氧合物原料接觸至少兩種不同的沸石觸媒以形成烯烴組合物,其中沸石觸媒的第一種包含ZSM-5分子篩以及沸石觸媒的第二種包含選自ZSM-22、ZSM-23、ZSM-35、ZSM-48以及它們的混合物的沸石分子篩。ZSM-5可以是未改性的、磷改質的、蒸汽改性的,其具有的微孔體積減小至不小於未汽蒸的ZSM-5或它們各種混合物的50%。根據一實施方案,沸石由含磷化合物改性以控制孔體積的減小。或者,汽蒸沸石,以及在汽蒸之前或之後加入磷化合物。磷的量,如基於元素測量的,為0.05重量%至20重量%,優選地為1重量%至10重量%,基於沸石分子篩的重量。優選地,磷和結構鋁(即在沸石結構中)的原子比為不大於4:1以及更優選2:1至4:1。根據一實施例,將磷改質劑結合進入該發明的上述觸媒,通過使沸石分子篩單獨接觸合適的磷化合物的溶液完成,或者通過沸石組合粘結劑接觸合適的磷化合物的溶液完成。固體沸石或沸石觸媒從磷溶液中分離、乾燥和煆燒。在一些情況中,添加的磷在這樣的條件下轉化成它的氧化物形式。與含磷化合物的接觸通常在25℃至125℃的溫度進行15分鐘至20小時。沸石中的磷的濃度可以是0.01重量%至30重量%。該現有技術公開了非-配製的P-ZSM-5。
WO 2009 022990 A1公開了一種觸媒組合物用於醇的脫水以製備烯烴。上述觸媒組合物包括觸媒和改性劑,上
述改性劑是磷酸、硫酸或三氧化鎢,或它們的衍生物。其中沒有粘結劑。
EP 2348004 A1有關乙醇脫水製備乙烯。上述觸媒通過以下製程製備:汽蒸ZSM-5,在回流條件下利用H3PO4溶液接觸經汽蒸的沸石而引入P,P改性的沸石利用粘結劑擠出,引入鈣以及所得的觸媒在600℃汽蒸兩小時。或者,粘結劑可以在引入P之間被引入。
WO 2009-098262 A1有關乙醇的脫水以製備乙烯。上述觸媒通過以下製程製備:汽蒸ZSM-5,在回流條件下利用H3PO4溶液接觸經汽蒸的沸石而引入P,P改性的沸石與粘結劑一起擠出,無最後汽蒸。無鈣的引入。
EP 2082802 A1有關多種石油化學工藝,未敍述對醇進行脫水以製備具有與醇相同碳原子數的烯烴。敍述的工藝中包括烯烴的裂解以及氧合物如甲醇的轉化以製備乙烯、丙烯、丁烯以及多種烴的混合物。上述觸媒通過以下製程製備:汽蒸ZSM-5,經汽蒸的沸石利用粘結劑擠出,在回流條件下利用H3PO4溶液接觸經汽蒸的沸石而引入P,鈣以金屬矽酸鹽的形式引入以及所得的觸媒在600℃汽蒸兩小時。
US 4,356,338有關多種石化製程,未敍述醇的脫水以製備具有與醇相同碳原子數的烯烴。沸石(ZSM-5)可以組合粘結劑以及通過含P成分或蒸汽或蒸汽和含P成分兩者進行處理。未向上述觸媒中引入金屬例如Ca。上述觸媒具有減小的焦化(reduced coking)。
現在已經公開了用於製備P改性的沸石的新方法。
本發明在第一實施例中有關製備磷改質沸石的方法,其包括以如下順序的步驟:a)提供在結構中包括至少一個十元環的沸石,任選進行離子交換,b)任選汽蒸上述沸石,c)在上述沸石上引入磷以引入至少0.1重量%的磷,上述引入通過幹浸漬或化學氣相沉積進行,d)混合步驟c)的上述沸石和至少選自以下的成分:一種或多種粘結劑和成形添加劑,e)使上述混合物成形,f)任選引入金屬,該步驟任選與步驟d)同時進行,g)任選清洗上述觸媒,h)任選煆燒上述觸媒,i)汽蒸上述觸媒,該步驟也稱作平衡步驟。
本發明在第二實施例中有關製備磷改質沸石的方法,其包括以如下順序的步驟:a)提供在結構中包括至少一個十元環的沸石,任選進行離子交換,b)任選汽蒸上述沸石,c)在上述沸石上引入磷以引入至少0.1重量%的磷,d)混合步驟c)的上述沸石和至少選自以下的成分:
一種或多種粘結劑和成形添加劑,e)使上述混合物成形,f)任選引入金屬,該步驟任選與步驟d)同時進行,g)任選清洗上述觸媒,h)任選煆燒上述觸媒,i)以至少約2的汽蒸強度(X)汽蒸上述觸媒,該步驟也稱作平衡步驟。
上述“汽蒸強度(X)”對於本發明有用的步驟d)是處理條件的重要的、可測量的和關鍵定義。“大約”表示它可以是略微小於2。如下文中所解釋的,強度(severity)說明瞭實現脫鋁的汽蒸條件。
事實上,汽蒸的結果是觸媒的性質(沸石類型、粘結劑類型、Si/Al比、晶體大小、結晶度、結構缺陷、夾雜污染物的存在等)以及所使用的處理條件的函數。清楚的是最小強度不是絕對值,取決於上述參數,最小強度可以在不同的觸媒中變化。本領域熟練技術人員較易確定最小強度。為了確保起見,他可以例如延長處理持續時間和/或增加溫度。用於處理的關鍵參數主要包括蒸汽分壓(steam partial pressure)、溫度和處理的持續時間。如果處理的目標是類似的性質,處理的作用僅是“汽蒸強度”的函數。
高於500℃汽蒸或熱液處理沸石導致結構的脫鋁。脫鋁的程度可以通過27Al、29Si MAS NMR,通過酸度測量(如TPD MH3)或通過其他現有技術中的已知手段進行測量。脫鋁的速率主要通過上述參數,即蒸汽分壓、溫度以及處理
的持續時間來確定。
因此,“汽蒸強度(X)”定義為實驗條件對標準條件之間的脫鋁速率的比。
擇以下條件作為本發明的標準條件:在600℃汽蒸,在100%的大氣壓蒸汽中,2個小時期間。
本發明觸媒的脫鋁速率(V)通過以下方程給出:V÷常數×P(H2O)ˆ1.5×tst/EXP(-0.03×Tst),其中P(H2O)-蒸汽分壓(P/Patm);Tst-汽蒸溫度(℃);tst-處理的時間(持續時間),以小時計,以及÷表示成比例。
X(汽蒸強度)=V實驗條件/V標準條件
該方程在500℃至760℃的汽蒸範圍中是有效的。
因此,甚至可以在相對標準條件中所使用的溫度更低的溫度實現汽蒸強度值,但是持續時間會更長。
相對於相等時間蒸汽分壓和處理持續時間的標準條件,625℃的溫度提供大約2倍的汽蒸強度。
如果平衡步驟的溫度高於760℃(該範圍之外),汽蒸的持續時間至少為0.1小時以及蒸汽分壓至少為0.01 bar。
有利地,在第二實施例中,平衡步驟的溫度為625至870℃的範圍。
在一實施例中,在步驟c)之前的成形的沸石(或分子篩)包含小於1000 wppm的鈉。
在一實施例中,在步驟c)之前的成形的沸石(或分子篩)包含小於1000 wppm的鈉、小於1000 wppm的鉀以及小
於1000 wppm的鐵。
在一實施例中,在步驟c)之前的成形的沸石(或分子篩)包含小於100 wppm的鈉。
在一實施例中,在步驟c)之前的成形的沸石(或分子篩)包含小於100 wppm的鈉、小於100 wppm的鉀以及小於500 wppm的鐵。
本發明也有關根據上述製備的觸媒在以下製程中的用途,在上述製程中上述觸媒在蒸汽的存在下於高溫進行操作。“高溫”表示高於300℃至最高達800℃。例如可以引用,醇脫水以將至少一種醇轉化成相應的烯烴,烯烴裂解以製備更輕質的烯烴、MTO以及利用含烯烴的醇類和/或醇類對芳族化合物進行烷基化,上述方法例如生成對二甲苯、乙基苯和異丙基苯(cumene)。
關於步驟a)的在結構中包括至少一個十元環的沸石,可以引述結晶矽酸鹽。例如MFI(ZSM-5、矽沸石(silicalite)-1、硼矽沸石(boralite)C、TS-1)、MEL(ZSM-11、矽沸石-2、硼矽沸石D、TS-2、SSZ-46)、FER(鎂堿沸石(Ferrierite)、FU-9、ZSM-35)、MTT(ZSM-23)、MWW(MCM-22、PSH-3、ITQ-1、MCM-49)、TON(ZSM-22、Theta-1、NU-10)、EUO(ZSM-50、EU-1)、MFS(ZSM-57)和含矽、鋁、氧和任選硼的微孔材料的ZSM-48類材料。
優選的沸石結構選自MFI、MTT、FFR、MEL、TON、MWW、
EUO、MFS。
在一實施例中,沸石是Si/Al原子比在11至30範圍的ZSM-5,其在不直接添加有機範本(template)的情況下製備。
在一實施例中,沸石是Si/Al原子比在30至200範圍的MFI沸石。
三字母符號“MFI”和“MEL”分別表示具體的結晶矽酸鹽結構類型,由國際沸石協會結構委員會(Structure Commission of the International Zeolite Association)設定。MFI類型的結晶矽酸鹽的實例是合成沸石ZSM-5和矽沸石和其他本領域中已知的MFI類型結晶矽酸鹽。MEL類別的結晶矽酸鹽的實例是沸石ZSM-11和其他本領域中已知的MEL類型結晶矽酸鹽。其他的實例是硼矽沸石D和矽沸石-2,如國際沸石協會所述(沸石結構類型圖冊、1987,Butterworths)。優選的結晶矽酸鹽具有由10氧環定義的孔或通道。
結晶矽酸鹽是基於XO4四面體結構的微孔結晶無機聚合物,上述四面體借由共用氧離子相互連接,其中X可以是三價的(例如Al,B,...)或四價的(例如Ge、Si,...)。結晶矽酸鹽的晶體結構由四面體單元的網絡彼此連接的特定排序來定義。結晶矽酸鹽孔開口的尺寸通過四面體單元或者形成孔所需的氧原子數目和孔中存在的陰離子的性質確定。它們具有以下性能的獨特組合:高內表面積;具有一個或多個離散的尺寸的均勻孔;離子交換能力;好的熱
穩定性;以及吸收有機化合物的能力。由於這些結晶矽酸鹽的孔的尺寸在尺寸上類似於很多實際關注的有機分子,它們控制反應物和產物的進入和排出,引起催化反應中的特定的選擇性。具有MFI結構的結晶矽酸鹽具有雙向交叉的孔系統,其具有以下孔直徑:沿著[010]的直通道:0.53-0.56 nm以及沿著[100]的正弦式通道:0.51-0.55 nm。具有MEL結構的結晶矽酸鹽具有雙向交叉直孔體系,其具有沿著[100]的直通道,孔直徑為0.53-0.54 nm。
在一個實施例中,沸石通過汽蒸進行預處理。預處理在420至870℃的範圍進行,更優選地在480至800℃的範圍進行。水分壓可為13至100 kPa的範圍。蒸汽氣氛優選地包含5至100體積%的蒸汽,具有0至95體積%的氣體,優選氮或空氣。汽蒸處理優選地在0.01至200小時的時間段進行,更優選0.05至50小時,仍更優選至少0.1小時以及以優選的方式0.1至50小時以及以更優選的方式0.5至50小時以及仍更優選1至50小時。
汽蒸處理傾向於通過形成氧化鋁減小結晶矽酸鹽結構中的四面體鋁的量。優選地,沸石中的殘留四面體Al的量為60至95%。該值可以通過27Al MAS NMR或TPD NH3評定。任選上述氧化鋁可以利用酸通過瀝濾除去。
在一個實施例中,Si/Al原子比範圍為11至30的ZSM-5通過汽蒸進行了預處理,其中上述ZSM-5在不直接添加有機範本的情況下製備。
此外,如果在製備沸石期間已經使用了鹼金屬或鹼土
金屬,分子篩可經受離子交換步驟。常規地,離子交換在水溶液中利用銨鹽或無機酸進行。
在一個實施例中,沸石經受脫鋁,例如大約10重量%的鋁被除去。這樣的脫鋁可以通過任何本身已知的常規技術完成,但是有利地通過汽蒸以及任選之後進行的瀝濾(leaching)完成。Si/Al比率為至少大約30至200的結晶矽酸鹽可以如此合成以及它可以通過對具有更低初始Si/Al比的結晶矽酸鹽進行脫鋁而製備。
關於步驟a)的離子交換,其目的是在接觸磷酸化試劑之前有利地得到沸石,其具有小於1000 wppm的鹼金屬&鹼土金屬,Na,K,Fe以及小於200 ppm的氧化還原&貴金屬元素例如Zn、Cr、Rh、Mn,Ni,V,Mo,Co,Cu,Cd,Pt,Pd,Ir、Ru、Re。這可以通過已知的任選反離子交換(back ion-exchange)步驟實現。
該離子交換步驟在步驟b)的汽蒸步驟(如果有的話)之前進行。
在一個實施例中,上述分子篩已經處理以將鹼金屬含量減小至小於100 ppm。
關於步驟b)的汽蒸,也已知為相對最終步驟i)的汽蒸的預-汽蒸。處理在420至870℃範圍進行,更優選在480至800℃的範圍進行。水分壓可以在13至100 kPa範圍。汽蒸氛圍優選地包含5至100體積%的蒸汽,其中0至95體積%為氣體,優選氮氣或空氣。汽蒸處理優選地進行0.01至200小時,更優選0.05至50小時,仍更優選至少0.1
小時以及以優選的方式0.1至50小時以及以更優選的方式0.5至50小時以及仍更優選1至50小時。
汽蒸處理傾向於通過形成氧化鋁減小結晶矽酸鹽結構中的四面體鋁的量。優選地,沸石中的殘留四面體Al的量為60至95%。該值可以通過27Al MAS NMR或TPD NH3評定。
關於步驟c)的P的引入,上述磷的引入可以在減壓或大氣壓在10至400℃的溫度進行。可以在水性或非水性的介質中提供非限制性的磷源。
在一個實施例中,非水性介質選自乙醇、甲醇或其他的醇。
優選的技術是浸漬和化學氣相沉積。上述技術在本發明的第一實施例中是必需的。
這些技術表明最少的要處理的廢物和將基本上所有的磷維持在上述觸媒上。
在一個實施例中,通過注入蒸汽流中的磷源對上述觸媒前體(沸石)進行處理。在該情況中,磷酸化在溫和的汽蒸條件下使用100-400℃的含磷蒸汽流進行。
在一個實施例中,通過在含磷源的溶液中在25-100℃的溫度處理觸媒前體(沸石)0.1-96小時以及之後進行的過濾或蒸發而引入磷。
在一個實施例中,上述含P的酸溶液的量有利地為2至10升每kg沸石+粘結劑。典型的時間段約0.5至24小時。有利的是,含P源的水性酸溶液具有的pH為3,有利的是2或更小。有利地,上述含水酸溶液是磷酸、磷酸和
有機或無機酸的混合物、或磷酸和有機或無機酸的鹽的混合物。磷酸或相應的鹽可以是磷酸鹽([PO4]3-,三價的)、亞磷酸鹽([HPO3]2-,二價的)或次磷酸鹽([H2PO2]1-,一價的)類型。磷酸鹽類型中也可以使用二磷酸鹽或多磷酸鹽([PnO3n+1](n+2)-)。沸石+粘結劑與含P成分的接觸可以在回流條件下進行。
在優選的實施例中,使用初濕浸漬技術。在該情況中,磷通過浸漬引入,利用了受限量的液體水,其中水和觸媒接觸。該方法也已知為幹浸漬。
初始潤濕(IW)或初濕浸漬(IWI)是用於合成多相觸媒的常用技術。典型地,前體(含磷化合物)溶解於水性溶液或有機溶液中。用於溶解前體的溶液的體積基本上與觸媒前體的孔體積相同。然後將溶液添加至觸媒前體中。毛細管作用將溶液牽引進入各孔中。之後乾燥和煆燒上述觸媒以除去溶液中的揮發性成分,將磷沉積在上述觸媒表面上。
樣品在浸漬前可以乾燥或煆燒。浸漬可以在室溫或升高的溫度(300-100℃)進行。
吸附容量通常通過用水浸漬經乾燥擠出的沸石直到沸石完全潤濕進行測量。浸漬之前和之後稱量沸石得出吸收容量。
在一個實施例中,H3PO4溶液用於浸漬。
有利地,H3PO4和它的銨鹽的混合物用於浸漬,其中上述混合物向水溶液提供高於2.0的pH。
在一個實施例中,磷源是基本上不含金屬的成分,例
如H3PO4、磷酸銨或有機P-化合物。“基本上不含金屬”表示金屬比例不會對P引入造成不良影響。例如該比例可以是低於1000 wppm。
在上述觸媒上的磷的量可以是0.5至30重量%,但優選0.5至9重量%。
關於步驟d),以及粘結劑,進行選擇以抵抗溫度和在應用觸媒製程中所使用的其他條件。粘結劑可以是選自以下的無機材料:二氧化矽、金屬矽酸鹽、氧化鋯、硼酸鹽、氧化鋁、二氧化矽-氧化鋁、磷酸鹽如無定形磷鋁酸鹽、磷酸鈣、粘土、金屬氧化物例如ZrO2和/或金屬或包括二氧化矽和金屬氧化物的混合物的凝膠。
在一個實施例中,粘結劑基本上是中性(惰性)的以及選自以下的無機材料:二氧化矽、非酸性氧化鋁、無定形磷鋁酸鹽、金屬磷酸鹽、粘土或它們的混合物。粘結劑的中性性質限制了導致形成重氧合物(heavy oxygenates)和烴、乙烷、乙醛等的副反應。
用於本發明觸媒的特別優選的粘結劑包括二氧化矽(silica)。細分離的結晶矽酸鹽材料和粘結劑的無機氧化物的相對比例可以在很大範圍內變化。
矽源的非限制性實例包括矽酸鹽,沉澱二氧化矽(例如可從Rhodia獲得的Zeosil系列),火成二氧化矽(例如可從Degussa Inc.,New York,N.Y.獲得的Aerosil-200),矽化合物(例如四烷基正矽酸鹽例如四甲基正矽酸鹽(TMOS)和四乙基正矽酸鹽(TEOS)),膠體二氧化矽或其含水懸浮液
(例如可從E.I.du Pont de Nemours,Wilmington,Del)獲得的Ludox-HS-40 sol),矽酸、鹼金屬矽酸鹽或它們的任何組合。
無定形二氧化矽的其他合適形式包括二氧化矽粉末,例如Ultrasil VN3SP(可從Degussa購買)。
合適的固體二氧化矽源的其他非限制性實例是具體顆粒化的親水的火成二氧化矽、介孔二氧化矽級EXP &高表面積沉澱二氧化矽SIPERNAT,其來自Evonik、HiSil 233 EP(由PPG Industries可得)和Tokusil(由Tokuyama Asia Pacific可得)。
另外,合適的無定形二氧化矽源包括矽溶膠,其是無定形二氧化矽顆粒在水性或有機的液體介質中的穩定膠狀分散體,上述液體介質優選水。
可市購的矽溶膠(silica sol)的非限制性實例包括以如下商標名出售的那些:Nyacol(由Nyacol Nano Technologies、Inc.或PQ Corp.可得)、Nalco(由Nalco Chemical Company可得)、Ultra-Sol(由RESI Inc可得)、Ludox(由W.R.Grace Davison可得)、NexSil(由NNTI可得)。
許多矽溶膠由矽酸鈉製備,並且不可避免地含有鈉。但是發現鈉離子的存在會導致二氧化矽體在高溫下燒結和/或影響催化性能。因此,如果使用包含鈉的矽溶膠,需要離子交換的步驟以便減小或除去鈉。為了避免進行離子交換步驟,方便使用包含非常少的鈉或理想地不包含可檢測
的痕量鈉以及pH值小於7的矽溶膠。最優選地,用於該製程中的矽溶膠是弱酸性的,具有或不具有聚合穩定劑。不包含可檢測的痕量鈉的矽溶膠的非限制性實例包括Bindzil 2034DI、Levasil 200、Nalco 1034A、Ultra-Sol 7H或NexSil 20A。
在一些情況中,利用烷基銨製備的二氧化矽分散體可以是有用的。由氨或烷基銨陽離子穩定的低鈉矽溶膠的可市購的非限制性實例包括LUDOX TMA(由W.R.Grace Davison可得)或來自Evonik的VP WR 8520。
包含高於30%以及甚至高達50重量%的SiO2含量的矽溶膠是特別優選的,例如來自Evonik的W1250、W1836、WK341、WK7330。
優選的矽源是矽溶膠、或者矽溶膠和沉澱二氧化矽或火成二氧化矽的組合。
用於形成醇類去水製程中所使用的結合觸媒的矽溶膠的類型作為包含分散的膠體二氧化矽顆粒的水溶膠或有機溶膠市售。例如,矽酸鈉可以用作矽溶膠。此外,還可以使用矽膠(silica gel)、火成的或熱解的二氧化矽以提供分子篩觸媒中的二氧化矽粘結劑。矽酸是二氧化矽的另一個可能的來源。有利地,粘結劑包含低於1000 ppm的低鈉量。
已知粘土在廣泛的反應條件下基本上惰性的。合適的粘土包括可市購的產品例如高嶺土、高嶺石、蒙脫石、活性白土(attapulgite)、皂石和膨潤土。這些粘土可以它們
開采時的天然狀態使用或者它們也可以高度活性形式使用,典型地通過酸處理製程進行活化。這些粘土的供應商包括Thiele Kaolin Company、American Colloidal Co.和其他。
粘土作為粘結劑強化上述觸媒顆粒的抗磨損性能,以及粘土和粘結劑的組合有利於顆粒的硬度。粘土也作為小顆粒開始以及具有更高的密度,從而當與分子篩和粘結劑組合時可以提供更緻密的顆粒,賦予所需的更高密度的特徵。
粘土在該製程中用於形成經硬化的產物,包括但不限於高嶺土、高嶺石、蒙脫石、皂石、膨潤土和多水高嶺石(halloysite)。
在一個實施例中,粘結劑材料常常,在某種程度上,具有多孔性的性質,以及可有效地促進所需的乙醇至乙烯的轉化。粘結劑可以是單一的無定形物質,或兩種或更多種單獨的無定形化合物的摻混物。
在相關的實施例中,上述觸媒(沸石+粘結劑)具有的在30Å與1000Å之間的孔的體積至少為0.25 cc/g,有利地是0.25和1 cc/g之間,優選至少0.26 cc/g,以及最優選0.27-0.92 cc/g之間。“cc”表示cm3。
在一個實施例中,粘結劑材料具有酸性以及也可以促進乙醇的轉化。
關於可以使用的這些粘結劑的類型,應該注意術語二氧化矽-氧化鋁不表示二氧化矽和氧化鋁的物理混合物而
是表示共凝膠的或共沉澱的酸性無定形材料。該術語在本領域中是已知的,並記載於例如US-A-3,909,450 BI;US-A-3,274,124 B1和US-A-4,988,659 BI中。就此而言,可以形成其他共凝膠的或共沉澱的無定形材料,其也有效地用作粘結劑或填料材料。這些包括二氧化矽-氧化鋯、二氧化矽-氧化釷、二氧化矽-氧化鈹(berylias)、二氧化矽-氧化鈦、二氧化矽-氧化鋁-氧化釷、二氧化矽-氧化鋁-氧化鋯、磷鋁酸鹽以及這些的混合物等。
在另外的實施例中,觸媒包括氧化鋁材料,例如羥基氧化鋁、γ-氧化鋁、勃姆石(boehmite)、水鋁石和過渡型氧化鋁例如α-氧化鋁、β-氧化鋁、γ-氧化鋁、δ-氧化鋁、ε-氧化鋁、κ-氧化鋁和ρ-氧化鋁、氫氧化鋁(aluminum trihydroxide),例如三水鋁石、三羥鋁石、諾三水鋁石(nordstrandite)、督水鋁石(doyelite)以及它們的混合物。
期望提供具有好的壓碎強度(crush strength)的觸媒。這是因為在商業用途上,期望防止上述觸媒碎裂至粉末樣材料。這樣的氧化物粘結劑通常僅用於改進上述觸媒的壓碎強度的目的。
上述觸媒組合物可以如上述通過本領域中說明的任何方法製備。有利地,然而,上述觸媒顆粒通過初始與粘結劑材料幹混合,然後在液體(優選水)中優選地與增塑劑混合一起得到糊料。
針對增塑劑(成形添加劑),要注意的是在任何後續熱
處理例如煆燒期間會分解。適用於該目的的材料包括例如烷基化的纖維素衍生物、羥基乙基纖維素(HEC)、纖基乙酸鈉(Tyo0se)、藻酸銨、聚乙烯吡咯烷酮、甘油和聚乙二醇。
除了強化上述觸媒強度性能,粘結劑材料使得分子篩結晶粉末結合成適用於商業催化製程的更大的粒度。可以將混合物b)的製劑形成為各種形狀,包括壓出物、球狀物、片狀物(pills)等。
接著可以使經均勻混合的糊料成形,例如通過噴霧乾燥以得到微球體、通過微粒化(pelletizing)或優選通過擠出。
糊料然後被擠出例如在活塞式擠出機(piston extruder)中成綫狀物例如圓柱形的、乾燥的、再次煆燒的以及切割成所需長度的段。
關於P改性的沸石、一種或多種粘結劑和成形添加劑的比例,有利的是,沸石的比例為上述觸媒的5至95重量%。上述觸媒包括沸石和至少選自一種或多種粘結劑的成分和成形添加劑。觸媒中所含的沸石的量的範圍更優選的為全部觸媒的15至90重量百分比,優選地為上述觸媒的20至85重量百分比。
一旦分子篩觸媒組合物成形並且呈基本上乾燥的或經乾燥的狀態,則有利地進行熱處理例如煆燒從而硬化和/或活化該組合物。因此熱處理優選在至少400℃的溫度進行1至48小時。可以進行煆燒,例如在回轉煆燒窯、流動床煆燒窯或分批式爐中。
關於步驟f),引入金屬,它可以是一種或多種金屬。有利的是,上述金屬選自鹼土金屬或稀土金屬。鹼土金屬或稀土金屬M優選選自以下的一種或多種:Mg、Ca、Sr、Ba、La、Ce。更優選地,M是鹼土金屬。最優選地,M是Ca。特別是在通過汽蒸和瀝濾的P-改性的情況中,M可以是稀土金屬例如La和Ce。有利的是,金屬以可溶的形式引入。
含M的成分優選地呈有機化合物、鹽、氫氧化物或氧化物的形式。當接觸分子篩時化合物優選地呈溶解的形式。或者,含M的化合物的溶液可以在分子篩接觸上述化合物之後形成。
可能的含M化合物包括以下化合物:例如硫酸鹽、甲酸鹽、硝酸鹽、乙酸鹽、鹵化物、鹵氧化物、硼酸鹽、碳酸鹽、氫氧化物、氧化物和它們的混合物。可以引用碳酸鈣。
弱水溶性的這些含M的化合物可以通過加熱和/或通過加入磷酸、乙酸或硝酸或上述酸的相應銨鹽改變溶液的pH而溶解從而形成很好溶解的溶液。
關於步驟g),可以設想清洗步驟。根據本發明,上述觸媒利用水處理0.1至48小時,優選地大約0.5至36小時以及更優選地大約1至24小時。水的溫度為大約20℃至180℃,優選20℃至100℃以及更優選大約25℃至60℃。例如水可以是30℃。水處理後,上述觸媒在大約>60℃時乾燥。任選地,水可以包含至少一種選自以下的溶解固體:
氯化銨、磷酸銨、硫酸銨、乙酸銨、碳酸銨,硝酸銨和它們的混合物。
關於步驟h),上述煆燒可以在空氣或惰性氣體中進行,典型地在350至900℃的溫度進行1至48小時。任選空氣或惰性氣體可以包含的蒸汽濃度為10至90體積%。
關於步驟i),在本發明的第一實施例中,可以在420至870℃的範圍進行,優選在480至870℃的範圍進行,優選在625至870℃的範圍進行以及更優選在700至800℃的範圍進行,仍更優選在720至800℃的範圍進行。備選地可以在420至600℃的範圍進行,優選420至580℃。
在本發明的第二實施例中,通過汽蒸在汽蒸強度大於大約2或備選在高於625℃、優選在625至870℃以及更優選700至800℃仍更優選720至800℃範圍的溫度進行。水分壓可以在13至100 kPa的範圍。汽蒸氛圍優選包含5至100體積%的蒸汽以及0至95體積%的氣體,優選氮器或空氣。汽蒸處理優選進行0.01至200小時,優選0.05至50小時,更優選至少0.1小時以及以優選的方式0.1至50小時以及以更優選的方式0.5至50小時以及仍更優選1至50小時。
關於將醇轉化成烯烴的去水製程,該製程已記載在大量專利申請中。可以引用WO/2009/098262、WO/2009/098267、WO/2009/098268和WO 2009/098269,其全部內容引用在此作為參考。醇是可以脫水成相應烯烴的任何醇。有利的是,醇具有兩個或更多個碳原子。相應的
烯烴是與醇具有相同碳數目的烯烴。例如,可以體積具有2至10個碳原子的醇。本發明有利地關注乙醇、丙醇、丁醇和苯乙醇。
關於烯烴的裂解,更具體地,本發明有關裂解富烯烴的烴原料的製程,其中在流出物中對輕質烯烴有選擇性。尤其是,來自精煉廠或石油化工廠的烯烴原料可以選擇性地轉化以重新分佈所得流出物中的原料的烯烴含量。上述富烯烴原料的裂解在以下說明和申請專利範圍書中通常稱作OCP(烯烴裂解製程)。關於運送至OCP反應器的包含一種或多種烯烴的烴原料,根據本發明,在如下的意義上對烯烴進行裂解:烴流中的烯烴被裂解成更輕質的烯烴以及選擇性地裂解成丙烯。原料和流出物優選具有基本上相同的烯烴重量含量(olefin content by weight)。典型地,流出物的烯烴含量在原料的烯烴含量的±15重量%、更優選±10重量%以內。原料可以包含任何類型的含烯烴的烴流。原料典型地包括10至100重量%的烯烴,以及另外可以未稀釋的形式或由稀釋劑稀釋的形式給料,上述稀釋劑任選包括非烯烴類烴。尤其是,含烯烴的原料可以是烴混合物,其包含碳在C4至C10範圍、更優選碳在C4至C6範圍的正烯烴和支鏈烯烴,任選與碳在C4至C10範圍的正-和支鏈-石蠟和/或芳族化合物相混合。典型地,含烯烴的原流具有的沸點為約-15至約180℃。針對OCP製程,上述製程是已知的。該製程已記載於EP 1036133、EP 1035915、EP 1036134、EP 1036135、EP 1036136、EP 1036138、EP 1036137、EP
1036139、EP 1194502、EP 1190015、EP 1194500和EP 1363983中,其全部內容引用在此作為參考。
關於MTO,上述製程生成輕質烯烴例如乙烯和丙烯以及重烴例如丁烯。上述MTO製程是通過與分子篩接觸而轉化甲醇或二甲醚,上述分子篩可以是P改性的沸石。
關於利用烯烴和醇類對芳族化合物進行烷基化,上述製程生成例如對二甲苯、乙基苯和異丙基苯。芳族化合物的烷基化,例如,甲苯甲基化已經在酸性觸媒上發生,特別是在沸石上或沸石類型的觸媒上發生。尤其是,ZSM-5-類型沸石、沸石β以及矽鋁磷酸鹽(SAPO)觸媒已用於該製程。
本領域內的熟練技術人員也會理解通過本發明的去水製程製備的烯烴可以例如聚合。當烯烴是乙烯時,它會,例如,聚合形成聚乙烯,二聚化成丁烯以及然後異構體化成異丁烯,上述異丁烯與乙醇反應以產生ETBE,二聚化成丁烷,接著借由複分解與乙烯反應以產生丙烯;經金屬、酸或雙功能觸媒而轉化成丙烯用於苯的烷基化以形成乙基苯,二聚化成1-丁烯,三聚化成1-己烯或四聚化成1-辛烯,上述α-烯烴共聚單體進一步與乙烯反應以產生聚乙烯,
二聚化成1-丁烯,上述1-丁烯異構體化成2-丁烯以及上述2-丁烯與乙烯通過複分解反應進一步轉化成丙烯以及上述丙烯可以聚合成聚丙烯,轉化成環氧乙烷和乙二醇(glycol),或轉化成氯乙烯。
本發明也有關上述聚乙烯、聚丙烯、丙烯、丁烯、己烷、辛烯、異丁烯、ETBE、氯乙烯、環氧乙烷和乙二醇。
當烯烴是丙烯時,它可以,例如,聚合形成聚丙烯,用於芳族化合物的烷基化等……
以NH4-形式(包含250 ppm的Na &不用範本合成的)的沸石ZSM-5樣品(Si/Al=12)與二氧化矽粘結劑摻混,比率80:20,接著添加擠出添加劑和成形添加劑。在上述觸媒中的最終Na含量是320 ppm。
經擠出的樣品在140℃乾燥2小時,在600℃煆燒2小時,之後在550℃在100%蒸汽中汽蒸6小時。
經汽蒸的固體利用磷酸水溶液初濕浸漬以向上述觸媒引入大約3重量%的磷。經浸漬的固體在110℃乾燥16小時。
然後,經磷酸化的樣品利用通過溶解碳酸鈣而獲得的硝酸鈣溶液初濕浸漬以向固體中引入大約1重量%的鈣。經
浸漬的固體在110℃乾燥16小時。
含2.8重量%的磷和0.8%的鈣的所得的觸媒在100%的蒸汽中於600℃汽蒸2小時(汽蒸強度為1)。該樣品在下文中標為樣品A。
含大約2.8重量%的磷和0.8%的鈣的所得的觸媒在100%的蒸汽中於750℃汽蒸1小時(汽蒸強度為45)。該樣品在下文中標為樣品B。通過壓汞式孔隙分析儀測量的總孔體積是0.36 cm3/g。
在負載在管狀反應器中的1 ml觸媒顆粒(35-45篩目)上進行觸媒測試,其中上述管狀反應器的內直徑為11 mm。在380℃、WHSV=7h-1 P=2 bara的固定床反應器中,混合物25重量%EthOH/75重量% H2O接觸實施例1中上述的觸媒。結果給出在下表1中。數值是基於碳的重量百分比。
以NH4-形式(包含250 ppm的Na &不用範本而合成的)的沸石ZSM-5樣品(Si/Al=12)與二氧化矽粘結劑摻混,比率80:20,之後添加擠出添加劑和成形添加劑。在上述觸媒中的最終Na含量是320 ppm。
經擠出的樣品在110℃乾燥16小時,在600℃煆燒10小時,之後在550℃在100%蒸汽中汽蒸6小時。
經汽蒸的經成形的沸石然後在初始潤濕的條件下接觸H3PO4的水溶液(85重量%)。之後引入1 gCaCO3。在30分鐘的攪拌之後,系統在室溫冷卻以及通過過濾除去過量溶
液,不清洗。重新獲得的固體在110℃乾燥16小時,之後在600℃在100%的蒸汽中汽蒸2小時(汽蒸強度1)。
所得的觸媒包含大約1.7重量%的磷和0.4重量%的鈣。該樣品在下文中標為樣品C。
然後在與上述相同的操作條件下對上述觸媒的性能進行評估,使用負載在管狀反應器中的1 ml觸媒(35-45篩目),上述管狀反應器的內直徑為11mm。在380℃、WHSV=7h-1 P=2 bara的固定床反應中,在觸媒C上已經加工具有了25重量%EtOH/75重量%H2O的混合物。結果給出在表1中。數值是基於碳的重量百分比。
以NH4-形式(包含250 ppm的Na &不用範本而合成的)的沸石ZSM-5樣品(Si/Al=12)與二氧化矽粘結劑摻混,比率80:20,之後添加擠出添加劑和成形添加劑。在上述觸媒中的最終Na含量是320 ppm。
經擠出的樣品在110℃乾燥16小時,在600℃煆燒10小時,之後在550℃在100%蒸汽中汽蒸6小時。
12g經汽蒸的固體利用包含1.54g的NH4H2PO4的水溶液初濕浸漬。經浸漬的固體在110℃乾燥16小時。
然後,經磷酸化的樣品利用硝酸鈣溶液初濕浸漬,其中上述硝酸鈣溶液通過在硝酸中溶解0.3g碳酸鈣獲得。經浸漬的固體在110℃乾燥16小時之後在100%蒸汽中於600℃汽蒸2小時(汽蒸強度1)。
所得的觸媒包含大約2.54重量%的磷和0.82重量%的鈣。該樣品在下文中標為樣品D。
然後在與上述相同的操作條件下對上述觸媒的性能進行評定,使用負載在管狀反應器中的1 ml觸媒(35-45篩目),上述管狀反應器的內直徑為11mm。在380℃、WHSV=7h-1 P=2 bara的固定床反應中,在觸媒D上已經加工具有了25重量%EtOH/75重量%H2O的混合物,。結果給出在表1中。數值是基於碳的重量百分比。
以NH4-形式(包含250 ppm的Na &不用範本而合成的)的沸石ZSM-5樣品(Si/Al=12)與包含二氧化矽和高嶺土的粘結劑摻混,比率為70:10:20,之後添加擠出添加劑和成形添加劑。
經擠出的樣品在140℃乾燥2小時,在600℃煆燒10小時之後在550℃在100%蒸汽中汽蒸6小時。
經汽蒸的固體利用磷酸水溶液初濕浸漬以向上述觸媒引入大約3重量%的磷。經浸漬的固體在110℃乾燥16小時。
然後,經磷酸化的樣品利用通過溶解碳酸鈣而獲得的硝酸鈣溶液初濕浸漬以向固體引入大約1重量%的鈣。經浸漬的固體在110℃燥16小時。
所得的包含2.94重量%的磷和0.8%的鈣的觸媒在750℃在100%的蒸汽中汽蒸2小時(汽蒸強度為90)。該樣品在下文中標為樣品E。
以NH4-形式(不用範本而合成的)的沸石ZSM-5樣品(Si/Al=12)在600℃煆燒10小時之後在100%蒸汽中於550℃汽蒸6小時。
100g經汽蒸的固體利用包含9.86g磷酸的水溶液初濕浸漬(幹浸漬)。經浸漬的固體在110℃乾燥16小時。
然後,16g的磷酸化樣品與4g二氧化矽粘結劑和0.4g
CaCO3一起擠出。
所得的觸媒在600℃煆燒10小時之後在600℃在100%的蒸汽中汽蒸2小時(汽蒸強度為1)。樣品在下文中標為樣品F。
觸媒測試在負載於管狀反應器中的0.8g觸媒顆粒(35-45篩目)中進行。基本上包含非環烯烴C4(~60%)的原料在觸媒的存在下在固定床反應器中經受催化裂解,Tin-550℃,WHSV=16h-1,P=1.5 bara。結果在表2中。表2中的數值是1-10小時在運轉中(on-stream)的平均觸媒性能,以基於碳的重量百分比給出。
以下給出的數據示例性地說明瞭P-沸石在C4烯烴至丙烯和乙烯的轉化中的裂解活性好和選擇性高。
Claims (29)
- 一種製備磷改質沸石的方法,其包括以如下順序的步驟:a)提供在結構中包括至少一個十元環的沸石,任選進行離子交換,b)汽蒸上述沸石,c)在上述沸石上引入磷以引入至少0.1重量%的磷,上述引入通過幹浸漬或化學氣相沉積進行,d)混合步驟c)的上述沸石和至少選自以下的成分:一種或多種粘結劑和成形添加劑,e)使上述混合物成形,f)任選引入金屬,該步驟任選與步驟d)同時進行,g)任選清洗上述觸媒,h)任選煆燒上述觸媒,i)汽蒸上述觸媒,該步驟也稱作平衡步驟。
- 如申請專利範圍第1的方法,其中上述步驟c)的磷的引入通過初始潤濕(IW)或初濕浸漬(IWI)進行。
- 如申請專利範圍第1或2項的方法,其中上述步驟i)的汽蒸在420至870℃的範圍內進行。
- 如申請專利範圍第3項的方法,其中上述步驟i)的汽蒸在480至870℃的範圍內進行。
- 如申請專利範圍第4項的方法,其中上述步驟i)的汽蒸在625至870℃的範圍內進行。
- 如申請專利範圍第5項的方法,其中上述步驟i)的 汽蒸在700至800℃的範圍內進行。
- 如申請專利範圍第6項的方法,其中上述步驟i)的汽蒸在720至800℃的範圍內進行。
- 如申請專利範圍第3項的方法,其中上述步驟i)的汽蒸在420至600℃的範圍內進行。
- 如申請專利範圍第8項的方法,其中上述步驟i)的汽蒸在420至580℃的範圍內進行。
- 一種製備磷改質沸石的方法,其包括以如下順序的步驟:a)提供在結構中包括至少一個十元環的沸石,任選進行離子交換,b)任選汽蒸上述沸石,c)在上述沸石上引入磷以引入至少0.1重量%的磷,d)混合步驟c)的上述沸石和至少選自以下的成分:一種或多種粘結劑和成形添加劑,e)使上述混合物成形,f)任選引入金屬,該步驟任選與步驟d)同時進行,g)任選清洗上述觸媒,h)任選煆燒上述觸媒,i)以至少約2的汽蒸強度(X)汽蒸上述觸媒,該步驟也稱作平衡步驟。
- 如申請專利範圍第10項的方法,其中上述步驟i)的汽蒸在625至870℃的範圍內進行。
- 如申請專利範圍第11項的方法,其中上述步驟i) 的汽蒸在700至800℃的範圍內進行。
- 如申請專利範圍第12項的方法,其中上述步驟i)的汽蒸在720至800℃的範圍內進行。
- 如申請專利範圍第1至13項中任一項的方法,其中步驟b)的經成形的沸石(或分子篩)包含小於100 wppm的鈉。
- 如申請專利範圍第14項的方法,其中步驟b)的經成形的沸石(或分子篩)包含小於100 wppm的鈉、小於100 wppm的鉀以及小於500 wppm的鐵。
- 如申請專利範圍第1至13項中任一項的方法,其中步驟b)的經成形的沸石(或分子篩)包含小於1000 wppm的鈉。
- 如申請專利範圍第16項的方法,其中步驟b)的經成形的沸石(或分子篩)包含小於1000 wppm的鈉、小於1000 wppm的鉀以及小於1000 wppm的鐵。
- 如申請專利範圍第1至17項中任一項的方法,其中上述沸石選自MFI、MTT、FER、MEL、TON、MWW、EUO、MFS。
- 如申請專利範圍第18項的方法,其中上述沸石是Si/Al原子比範圍為11至30的ZSM-5,其在不直接添加有機範本劑時製備。
- 如申請專利範圍第18項的方法,其中上述沸石是Si/Al原子比範圍為30至200的MFI。
- 如申請專利範圍第1至20項中任一項的方法,其 中在上述觸媒上的磷的量為0.5至30重量%。
- 如申請專利範圍第21項的方法,其中在上述觸媒上的磷的量為0.5至9重量%。
- 如申請專利範圍第1至22項中任一項的方法,其中在步驟f),上述金屬是鹼土金屬或稀土金屬M,其優選地選自以下的一種或多種:Mg、Ca、Sr、Ba、La、Ce。
- 如申請專利範圍第1至23項中任一項的方法,上述觸媒(沸石+粘結劑)具有的在30Å與1000Å之間的孔的體積為至少0.25 cc/g。
- 如申請專利範圍第1至24項中任一項所製備的觸媒在以下製程中的用途,在上述製程中上述觸媒在蒸汽存在下在高於300℃以及最高達800℃的溫度進行操作。
- 一種對醇進行脫水以至少將上述醇轉化為相應的具有與上述醇相同碳原子數的烯烴項的方法,其中上述脫水在如申請專利範圍第1至24項中任一項製備的觸媒的存在下進行。
- 一種裂解烯烴以製備更輕質的烯烴項的方法,其中上述裂解在如申請專利範圍第1至24項中任一項製備的觸媒的存在下進行。
- 一種裂解甲醇或二甲醚以製造輕質烯烴例如乙烯和丙烯項的方法,其中上述裂解在如申請專利範圍第1至24項中任一項製備的觸媒的存在下進行。
- 一種通過醇或烯烴對芳族化合物進行烷基化項的方法,其中上述烷基化在如申請專利範圍第1至24項中任 一項製備的觸媒的存在下進行。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI649263B (zh) * | 2013-12-19 | 2019-02-01 | 美商巴地斯公司 | 包含氧化硼之fcc催化劑組合物 |
US10525451B2 (en) | 2013-12-19 | 2020-01-07 | Basf Corporation | FCC catalyst compositions containing boron oxide |
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