TW201323083A - 使用雙催化劑系統之芳香族化合物異構化 - Google Patents
使用雙催化劑系統之芳香族化合物異構化 Download PDFInfo
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- TW201323083A TW201323083A TW101141938A TW101141938A TW201323083A TW 201323083 A TW201323083 A TW 201323083A TW 101141938 A TW101141938 A TW 101141938A TW 101141938 A TW101141938 A TW 101141938A TW 201323083 A TW201323083 A TW 201323083A
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本發明係關於一種利用催化劑系統使包含高濃度非芳香族化合物之二甲苯及乙苯的非平衡混合物異構化的方法,該催化劑系統的特徵為可轉化非芳香族化合物並可相對於已知技術方法自該混合物獲得提高產率的對二甲苯。
Description
本發明係關於催化性烴轉化,及更明確言之改良分子篩催化劑系統於芳香族化合物異構化之用途。
本申請案主張2011年11月14日申請之美國臨時申請案第61/559,226號之優先權。
二甲苯(對二甲苯、間二甲苯及鄰二甲苯)係在化學合成中具有廣泛及多種應用的重要中間物。對二甲苯在氧化時產生用於製造合成紡織纖維及樹脂的對苯二甲酸。間二甲苯係用於製造塑化劑、偶氮染料、木材防腐劑等。鄰二甲苯係生產鄰苯二甲酸酐的原料。
來自催化重整或其他來源之二甲苯異構體一般不符合作為化學中間物所要求的比例,且另外包括難以分離或轉化之乙苯。特定言之,對二甲苯係需求快速增長之主要化學中間物,但含量僅為典型C8芳香族化合物流之20-25%。可藉由組合二甲苯異構體回收(諸如用於對二甲苯回收之吸附)與異構化以產生額外量之所需異構體來實現按需要調整異構體比例。異構化係將缺乏所需二甲苯異構體之二甲苯異構體之不平衡混合物轉化成達到平衡濃度之混合物。
已開發不同的催化劑及方法以進行二甲苯異構化。在選擇適宜的技術上,需要使異構化處理實際上接近平衡以使對二甲苯產率最大化;然而,與此相關的係由於副反應所引起的更大環狀C8損失。所用之達到平衡的方法係在高轉
化率下(即極接近平衡)之高環狀C8損失與由於未轉化C8芳香族化合物之高再循環速率所引起之高效用成本之間的最佳折中法。因此,基於活性、選擇性及安定性之有利平衡評估催化劑。
近幾十年來,包含分子篩之催化劑已在二甲苯異構化中變得突出。例如,US 3,856,872教示利用包含ZSM-5、-12或-21沸石之催化劑進行二甲苯異構化及乙苯轉化。US 4,899,011教示利用兩種沸石(各與強氫化金屬結合)進行C8芳香族化合物異構化。US 6,142,941、US 7,297,830 B2及US 7,525,008 B2揭示用於C8芳香族化合物異構化之沸石催化劑且係藉由引用之方式併入本文中。儘管此等參考文獻教示本發明之個別元素,但沒有技術提出該等元素之組合以獲得本發明催化劑系統之關鍵特徵。
通常藉由處理與二甲苯異構體相關之乙苯的方式對用於C8芳香族化合物異構化的催化劑進行分類。乙苯不易異構化成二甲苯,但其通常在異構化單元中轉化,因為藉由超精餾或吸附自二甲苯分離係極其昂貴。一種廣泛使用的方法係在使二甲苯異構化成近平衡混合物時,使乙苯去烷基化以主要形成苯。另一方法係在具有氫化-脫氫功能之固體酸催化劑存在下,經由轉化成環烷烴及由其再轉化而使乙苯反應形成二甲苯混合物。前一方法通常產生更高的乙苯轉化率及更有效的二甲苯異構化,因此降低在異構化/對二甲苯回收之回路中的再循環量及減少相伴的處理成本。
本發明之一主要目的在於提供一種用於烷基芳香族烴之異構化之新穎催化劑及方法。更具體言之,本發明係關於一種用於包含高濃度非芳香族化合物之C8芳香族烴之異構化以生成高純度產物之催化劑系統。
因此,本發明之一廣泛實施例係關於一種用於轉化包括高濃度不平衡C8芳香族化合物及低濃度非芳香族化合物之烴進料混合物之方法,其係藉由使該混合物與雙催化劑系統(其包括含有鎢組分及至少一種沸石鋁矽酸鹽中之一或兩者之第一催化劑及基於元素計含有0.01至0.2質量%之至少一種鉑族金屬組分之第二催化劑)於包括300℃至550℃之溫度、100 kPa至5 MPa之壓力及就該雙催化劑系統而言為0.5至50 hr-1之液體每小時空間速度的烴轉化條件下接觸,以獲得包括比在該進料混合物中濃度減小之乙苯及濃度減小之非芳香族化合物的轉化產物。
在一個實施例中,本發明包括一種用於轉化包括高濃度不平衡C8芳香族化合物及低濃度非芳香族化合物之烴進料混合物之方法,其係藉由使該混合物與雙催化劑系統(其包括含有10至99質量%之至少一種沸石鋁矽酸鹽之第一催化劑及基於元素計含有0.01至0.2質量%之至少一種鉑族金屬組分之第二催化劑)於包括300℃至550℃之溫度、100 kPa至5 MPa之壓力及就該雙催化劑系統而言為0.5至50 hr-1之液體每小時空間速度的烴轉化條件下接觸,以獲得包括比在該進料混合物中比例更高之至少一種二甲苯異構體、
濃度減小之乙苯及濃度減小之非芳香族化合物的轉化產物。
在另一實施例中,本發明包括一種用於轉化包括高濃度不平衡C8芳香族化合物及低濃度非芳香族化合物之烴進料混合物之方法,其係藉由使該混合物與雙催化劑系統(其包括含有鎢組分之第一催化劑及基於元素計含有0.01至0.2質量%之至少一種鉑族金屬組分之第二催化劑)於包括300℃至550℃之溫度、100 kPa至5 MPa之壓力及就該雙催化劑系統而言為0.5至50 hr-1之液體每小時空間速度的烴轉化條件下接觸,以獲得包括比在該進料混合物中濃度減小之乙苯及濃度減小之非芳香族化合物的轉化產物。
此等以及其他目的及實施例將自本發明之以下詳細描述變得明晰。
芳香族化合物異構化之原料包括具有通式C6H(6-n)Rn之可異構化烷基芳香族烴,其中n為2至5的整數且R為CH3、C2H5、C3H7或C4H9,其可呈任何組合及包括其所有異構體以獲得更具價值的烷基芳香族異構體。適宜的烷基芳香族烴包括例如(但不限制本發明)鄰二甲苯、間二甲苯、對二甲苯、乙苯、乙基甲苯、三甲基苯、二乙基苯、三乙基苯、甲基丙基苯、乙基丙基苯、二異丙基苯及其混合物。
包含乙苯及二甲苯之C8芳香族混合物之異構化係本發明催化劑系統之一特別佳應用。該混合物一般具有位於1至50質量%範圍內之乙基苯含量、位於0至35質量%範圍內之
鄰二甲苯含量、位於20至95質量%範圍內之間二甲苯含量及位於0至30質量%範圍內之對二甲苯含量。前述C8芳香族化合物較佳包括不平衡混合物,即至少一種C8芳香族異構體係以實質上不同於在異構化條件下之平衡濃度的濃度存在。該不平衡混合物通常係藉由從獲自芳香族化合物製備方法之新鮮C8芳香族混合物中除去對-、鄰-及/或間二甲苯而製得。
該等烷基芳香族烴可以如在來自各種精煉石油流之適宜餾分中所見之形式(例如呈藉由催化裂化或重整烴之選擇性分餾及蒸餾所獲得之個別組分或某一沸點範圍內的餾分)用於本發明中。不必濃縮該等可異構化芳香族烴;本發明方法允許含烷基芳香族化合物流(諸如催化重整物)異構化(進行或不進行後續芳香族化合物之萃取),以產生特定二甲苯異構體及尤其產生對二甲苯。本發明方法之C8芳香族化合物進料可包含最多30質量%之含量的非芳香族烴,即萘及石蠟。本發明尤其可用於處理含有在其他方法中會帶來問題之非芳香族化合物濃度的原料。
根據本發明之方法,使較佳與氫氣混合之烷基芳香族烴進料混合物與下文所述類型之兩種或更多種催化劑在烷基芳香族烴異構化區中接觸。可利用呈固定床系統、移動床系統、流化床系統、漿液系統或沸騰床系統之催化劑系統或以分批操作方式進行接觸。鑒於有價值催化劑之磨耗損失的風險及更簡單操作,較佳係使用固定床系統。在該系統中,藉由適宜的加熱方式將富氫氣體及該進料混合物預
熱至所需反應溫度且接著使其進入包含一或多個兩種或更多種催化劑之固定床的異構化區。該轉化區可為一或多個獨立反應器,其間具有適宜的裝置,以確保在各區域之入口處維持所需異構化溫度。該等反應物可以向上、向下或輻射流動方式與該催化劑床接觸,且當與催化劑接觸時,該等反應物可呈液相、混合液-氣相或氣相形式。
該等第一及第二催化劑可包含於不同的反應器中、在相同的反應器中按序排列、物理混合或複合成單一催化劑。該等催化劑較佳係按序排列,其中該進料接觸第一催化劑以轉化非芳香族化合物而產生中間物流,其可藉由第二催化劑處理以轉化乙苯及使芳香族化合物異構化而產生異構化產物。
將催化劑放置於不同的反應器中容許獨立控制操作條件,尤其係溫度及空間速度。然而,藉由利用單一反應器,可實現節約管道、儀器及其他附屬設備。催化劑之物理混合可促進催化劑之協同反應,但催化劑組分之分離及回收會更困難。可視需要在一或多個其他階段重複該催化劑系統,即在另一序列之該兩種催化劑中處理來自接觸該進料之反應物。
因此,在本發明之另一實施例中,該反應器包含第一及第二催化劑之物理混合物。在此實施例中,顆粒係經機械混合以提供本發明之催化劑系統。可利用已知技術(諸如研磨)完全混合該等顆粒以緊密地摻合該物理混合物。儘管第一及第二顆粒可具有相似尺寸及形狀,但該等顆粒較
佳係具有不同尺寸及/或密度以便於分離以在其用於烴處理後再生或復原。
在本發明之又一實施例中,第一及第二催化劑之物理混合物係包含於相同催化劑顆粒內。在此實施例中,可將分子篩一起或分開研磨或磨碎以形成具有適宜尺寸(較佳小於100微米)的顆粒,並使該等顆粒負載於適宜的基質中。該基質最佳係選自上述無機氧化物。
該烷基芳香族進料混合物(較佳係C8芳香族化合物之不平衡混合物)係與該催化劑系統在適宜的烷基芳香族轉化條件下接觸。該等條件包括100℃至600℃或更高及較佳位於300℃至550℃範圍內的溫度。壓力一般為100 kPa至5 MPa絕對壓力,較佳小於3 MPa。異構化區中包含足量之該催化劑系統所包含之兩種催化劑以提供就烴進料混合物而言為0.5至50 hr-1及就該催化劑系統所包含之各催化劑而言較佳係0.5至25 hr-1之液體每小時空間速度,空間速度係在1至100 hr-1之範圍內。最佳地,使該烴進料混合物以與氫氣以0.5:1至25:1之氫氣/烴莫耳比混合之形式反應。可存在其他惰性稀釋劑,諸如氮氣、氬氣及輕質烴。若兩種或更多種催化劑係包含於不同的床中,則可在各床內使用以上限制範圍內之不同操作條件以實現最佳總體結果。
用於從該異構化區之反應器之流出物中回收異構化產物的特定方案對於本發明而言被視為不關鍵,且可使用此項技術中已知的任何有效的回收方案。通常,將濃縮該反應器流出物並藉由快速分離從中移除氫氣及輕質烴組分。然
後使濃縮液體產物分餾以除去輕質及/或重質副產物並獲得異構化產物。在一些情況下,可藉由選擇性分餾從該異構化產物中回收某些產物種類(諸如鄰二甲苯)。通常,視需要藉由結晶作用處理來自C8芳香族化合物異構化之產物以選擇性回收對二甲苯異構體。根據US 3,201,491,以利用結晶型鋁矽酸鹽之選擇性吸附較佳。該較佳吸附回收方法之改良及替代方法係描述於以引用之方式併入本文中之US 3,626,020、US 3,696,107、US 4,039,599、US 4,184,943、US 4,381,419及US 4,402,832中。
在與乙苯/二甲苯混合物之處理相關之分離/異構化處理組合中,將新鮮C8芳香族進料與來自異構化反應區之包含C8芳香族化合物及萘的異構化產物組合並饋入對二甲苯分離區中;將包括C8芳香族化合物之不平衡混合物的貧對二甲苯流饋入異構化反應區中,其中使C8芳香族異構體異構化至近平衡程度以獲得異構化產物。在此處理方案中,未回收之C8芳香族異構體較佳係經再循環直到其轉化成對二甲苯或因副反應而損失耗盡。亦可在對二甲苯分離之前對新鮮C8芳香族進料或異構化產物或其組合進行鄰二甲苯分離(較佳係藉由分餾)。
第二催化劑可為適用於乙苯轉化及二甲苯異構化的已知技術中之催化劑。較佳催化劑係如US 6,143,941中所揭示之包括沸石鋁矽酸鹽、鉑族金屬組分及非晶型磷酸鋁黏合劑之球體催化劑。藉由第一催化劑轉化含於原料中之非芳香族化合物允許使用該等催化劑。
第一催化劑對第二催化劑之莫耳比係主要取決於原料組成及所需產物分佈,其中第一:第二催化劑之莫耳比較佳係1:20至50:1且尤其佳係1:10至20:1。本發明之催化劑系統可包括其他分子篩型或非晶型催化劑。
當存在於該第一及第二催化劑中時,沸石之相對比例可在10至99質量%之範圍內,較佳係20至90質量%。
黏合劑應為具有25至500 m2/g之表面積、組成均勻及在烴轉化處理中所用之條件下相對耐火之多孔吸附載體。術語「組成均勻」表示該載體未分層,不具有組成中之固有物質的濃度梯度,及在組成上係完全均質。因此,若該載體為兩種或更多種耐火物質的混合物,則該等物質之相對含量在整個載體中將係恆定及均一。在本發明之範圍內意欲包括已傳統地用於烴轉化催化劑中之載體物質,諸如:(1)耐火無機氧化物,如氧化鋁、二氧化鈦、氧化鋯、氧化鉻、氧化鋅、氧化鎂、氧化釷、氧化硼、矽石-氧化鋁、矽石-氧化鎂、氧化鉻-氧化鋁、氧化鋁-氧化硼、矽石-氧化鋯等;(2)陶瓷、瓷器、鋁礬土;(3)矽石或矽膠、碳化矽、黏土及矽酸鹽(包括彼等經合成製備及天然生成者,其可經或不經酸處理,例如凹凸棒石黏土、矽藻土(diatomaceous earth)、漂白土、高嶺土、矽藻土(kieselguhr)等;(4)天然生成或合成製備之結晶型沸石鋁矽酸鹽,諸如FAU、MEL、MFI、MOR、MTW(IUPAC Commission on Zeolite Nomenclature),其可呈氫形式或呈已與金屬陽離子交換之形式;(5)尖晶石諸如MgAl2O4、
FeAl2O4、ZnAl2O4、CaAl2O4,及其他具有式MO-Al2O3(其中M為2價金屬)之類似化合物;及(6)來自該等群組中一或多個之物質的組合。
用於本發明之較佳耐火無機氧化物為氧化鋁。適宜的氧化鋁材料係稱為γ-、η-及θ-氧化鋁之結晶型氧化鋁,其中γ-或η-氧化鋁產生最佳結果。理想地,該無機氧化物為氧化鋁,諸如γ-氧化鋁。該γ-氧化鋁可來自勃姆石或擬勃姆石氧化鋁(下文可統稱為「勃姆石氧化鋁」)。該勃姆石氧化鋁可與沸石混合並擠出。在氧化(或煅燒)期間,該勃姆石氧化鋁可轉化成γ-氧化鋁。一種用作初始材料之所需勃姆石氧化鋁為UOP,LLC of Des Plaines,III出售之VERSAL-251。另一勃姆石氧化鋁可由Sasol North America of Houston,Tex以商標名稱CATAPAL C出售。氧化鋁結合球體之製法一般包括將分子篩、鋁溶膠及膠凝劑之混合物滴入維持在高溫下之油浴中。可用於該方法中之膠凝劑之實例包括六亞甲基四胺、尿素及其混合物。該等膠凝劑可在高溫下釋放氨,其使得水溶膠球體轉變或轉化成水凝膠球體。接著可從該油浴中回收該等球體且通常在油及氨溶液中進行特定老化處理以進一步改善其物理特性。一示例性油滴法係揭示於US 2,620,314中。
另一黏合劑係非晶型矽石形式。有利的非晶型矽石係分類為濕法水合矽石之合成白色非晶型矽石(二氧化矽)粉末。此類型矽石係藉由在水溶液中之化學反應產生,並自該水溶液沉澱為超細球狀顆粒。該矽石之BET表面積較佳
係在120至160 m2/g之範圍內。希望具有低硫酸鹽含量,較佳係小於0.3重量%。尤佳地,該非晶型矽石黏合劑為非酸性,例如,5%水懸浮液之pH為中性或鹼性(pH 7或更大)。
該複合物之一較佳形狀為藉由熟知的油滴法連續製造的球體。氧化鋁結合球體之製法一般包括將分子篩、氧化鋁溶膠及膠凝劑之混合物滴入維持在高溫下之油浴中。或者,可利用油滴法進行矽石水溶膠之膠凝作用。一種使該混合物膠凝之方法包括將膠凝劑與該混合物組合及接著將所得之組合混合物分散於已加熱至高溫之油浴或塔中,以使得凝膠作用伴隨形成球體顆粒而發生。在該方法中可使用之膠凝劑為六亞甲基四胺、尿素或其混合物。該等膠凝劑在高溫下釋放氨,其使水溶膠球體定型或轉化成水凝膠球體。接著從該油浴中連續回收該等球體且通常在油及氨溶液中進行特定老化處理以進一步改善其物理特性。
催化劑複合物之一種替代形狀為擠出物。熟知的擠出法起初包括在添加金屬組分之前或之後將非沸石分子篩與黏合劑及適宜的膠溶劑混合以形成具有恰當水含量之均質膠糊或稠糊劑,從而允許形成具有可接受完整性之擠出物以經受直接煅燒。可擠出性係由該膠糊之水含量分析而測定,其中以位於30至50重量%範圍內之水含量較佳。然後,經由刺穿有多個孔之模具擠出該膠糊且根據此項技術中熟知的技術切割該意大利麺形擠出物以形成顆粒。可容許多種不同的擠出物形狀,其包括(但不限於)圓柱體、苜蓿葉、啞鈴及對稱及非對稱多葉形。在本發明之範圍內亦
可進一步藉由一步製粒法或此項技術中已知的任何其他方法使該等擠出物形成任何所需形式,諸如球體。
接著,較佳地,洗滌所得複合物並在50℃至200℃之相對低溫下乾燥並在450℃至700℃之溫度下進行煅燒步驟達1至20小時。
各催化劑可經蒸汽處理以調節酸活性。可在處理之任何階段進行蒸汽處理,但通常在併入鉑族金屬之前對沸石及黏合劑之複合物進行。蒸汽處理條件包括5至100體積%之水濃度、100 kPa至2 MPa之壓力及介於600℃與1200℃之間之溫度;蒸汽處理溫度較佳係介於650℃與1000℃之間,更佳係至少750℃及視需要可係775℃或更高。在一些情形中,可使用800℃至850℃或更高之溫度。該蒸汽處理應進行至少1小時,且以6至48小時較佳。另外或除該蒸汽處理之外,可利用硝酸銨溶液、無機酸及/或水中之一或多者洗滌該複合物。可在製備之任何階段進行洗滌,且可使用兩或多階段洗滌。
鎢為第一催化劑之較佳組分。鎢酸根離子係藉由(例如)利用濃度通常係0.1至20質量%之鎢及較佳1至15質量%之鎢的偏鎢酸銨處理而併入催化複合物中。可使用可在煅燒時形成鎢酸根離子之化合物(諸如偏鎢酸、鎢酸鈉、鎢酸胺、仲鎢酸銨)作為替代性來源。較佳地,利用偏鎢酸銨提供鎢酸根離子並形成固體強酸催化劑。最終催化劑之鎢酸根含量基於元素計通常係位於0.5至30質量%及較佳1至25質量%之範圍內。該鎢酸鹽複合物係經乾燥,接著較佳
在450℃至1000℃之溫度下進行煅燒(尤其若欲在鎢酸鹽處理之後併入鉑族金屬)。
包括鉑、鈀、銠、釕、鋨及銥中之一或多者之鉑族金屬為本發明各催化劑複合物之極佳組分。較佳鉑族金屬為鉑。該等第一及第二催化劑之各者的相對鉑族金屬含量為本發明之一特徵。若存在,該鉑族金屬基於元素計算一般係佔最終第一催化劑之0.01至0.5質量%,較佳0.5至0.3質量%;該第二催化劑基於元素計算較佳包括0.01至0.5質量%,較佳小於0.2質量%及尤其0.02至0.08質量%之鉑族金屬。
該鉑族金屬組分可呈化合物(諸如氧化物、硫化物、鹵化物、氧硫化物等)或呈元素金屬或以與該催化劑複合物之一或多種其他成份組合之形式存在於最終催化劑複合物中。據信當實質上所有鉑族金屬組分係以還原態存在時,可獲得最佳結果。可以任何適宜的方式將該鉑族金屬組分併入催化劑複合物中。一種製備該催化劑之方法包括利用鉑族金屬之水溶性可分解化合物浸漬煅燒的分子篩/黏合劑複合物。或者,可在複合分子篩組分及黏合劑時添加鉑族金屬化合物。可用於浸漬溶液、與分子篩及黏合劑共擠出或藉由其他已知方法添加之鉑族金屬的錯合物包括氯鉑酸、氯鈀酸、氯鉑酸銨、溴鉑酸、三氯化鉑、四氯化鉑水合物、二氯羰基二氯化鉑、四胺氯化鉑、二硝基二胺基鉑、四硝基鉑(II)酸鈉、氯化鈀、硝酸鈀、硫酸鈀、氫氧化二胺鈀(II)、氯化四胺鈀(II)等。較佳地,該鉑族金屬組
分係藉由此項技術中已知的任何方法集中於該催化劑之黏合劑組分上。一種進行該較佳金屬分佈之方法係藉由在共擠出該分子篩及黏合劑之前複合該金屬組分與該黏合劑。
在本發明之範圍內,本發明催化劑複合物可包含已知用於改良該鉑族金屬組分之作用的其他金屬組分。該等金屬改質劑可包括錸、錫、鍺、鉛、鈷、鎳、銦、鎵、鋅、鈾、鏑、鉈、及其混合物。可藉由此項技術中已知的任何方法將催化有效量之該等金屬改質劑併入該催化劑中以實現均質或分層分佈。
本發明之催化劑可包含鹵素組分,其包括氟、氯、溴、碘或其混合物,較佳係氯。然而,較佳地,該催化劑不包含除與其他催化劑組分有關之鹵素以外之添加鹵素。
各催化劑複合物係在100℃至320℃之溫度下乾燥2至24或更多小時,且通常在400℃至650℃之溫度下及空氣氛圍中煅燒0.1至10小時。若需要,可藉由在該空氣氛圍中併入鹵素或含鹵素化合物來調節可選鹵素組分。
最佳地,對所得之煅燒複合物進行實質上無水的還原步驟,以確保特定金屬組分之均勻及微細分散液。該還原作用可視需要在本發明之處理設備中進行。較佳地,使用實質上純的乾燥氫氣(即小於20體積ppm H2O)作為該步驟中之還原劑。該還原劑係在可有效將實質上所有VIII族金屬組分還原成金屬態的條件(包括200℃至650℃之溫度及0.5至10小時之時間)下與該催化劑接觸。在一些情形中,亦可藉由此項技術中已知的方法對所得之還原催化劑複合物
有利地進行預硫化作用,以將基於元素計算為0.05至1.0質量%之硫併入該催化劑複合物中。
以下實例僅為了說明本發明之某些具體實施例而提供,且不應被視為限制申請專利範圍內所闡明之本發明範圍。一般技術者將認識到在本發明之主旨範圍內存在許多可能的其他變化。
製備與C8芳香族化合物混合物之非芳香族化合物之轉化有關的第一催化劑的樣品並在試驗工廠中進行對比測試。
根據US 7,525,008 B2製備包括與氧化鋁複合之MTW沸石之擠出顆粒的催化劑。利用氯鉑酸溶液浸漬該等顆粒,乾燥,氧化,還原並硫化,以產生包含0.05質量%鉑之催化劑。將該催化劑命名為催化劑A。
利用US 6,143,941之教示製備催化劑。使根據實例I製備之包括沸石及非晶型磷酸鋁黏合劑之滴油型球體催化劑參照物與硫酸銨(0.82 g硫酸銨+10 g去離子水載體)在60℃下進行離子交換;在傾析之後,重複該離子交換並利用10 g去離子水/g載體洗滌所得球體4次。在120℃乾燥該等球體1小時且在350℃及550℃下於乾燥空氣中煅燒2小時。利用四胺氯化鉑浸漬具有0.7質量%之硫含量的球體以達到0.04質量%之鉑含量,在525℃下於空氣中利用3%蒸汽煅燒2小時且在425℃下於氫氣中還原4小時。將所得催化劑命名為
催化劑B。
根據US 2,620,314製備球體氧化鋁顆粒並利用添加有pH9-10之NH4OH之偏鎢酸銨進行金屬浸漬,以形成包含10質量%鎢的固體強酸催化劑。乾燥該複合物並在乾燥空氣中於350℃及550℃下煅燒3小時。利用pH9至10之氯鉑酸及鹽酸之水溶液浸漬該複合物,在350℃下乾燥,以50℃/小時斜升至550℃,用氮氣吹掃,在565℃下於氫氣中還原1小時並將其命名為催化劑C。
根據US 7,297,830製備在1/16英寸γ-氧化鋁核上包含MTW沸石活性層之顆粒,以產生10%MTW(40Si/Al2比)之150微米層。另外,利用添加有pH10之NH4OH之偏鎢酸銨浸漬該等顆粒,以形成包含10質量%鎢之固體強酸催化劑,其經蒸汽處理及在乾燥空氣中於350℃及550℃下煅燒3小時。根據US 7,297,830之實例III,利用pH9至10之氯鉑酸及鹽酸之水溶液浸漬該複合物,以產生超過90%之鉑係集中於外部沸石層中的催化劑。乾燥及煅燒該複合物,然後根據US 7,297,830之實例III,利用氯鉑酸及鹽酸之水溶液浸漬,以產生超過90%之鉑係集中於外部沸石層中之含有0.28質量%鉑的催化劑。煅燒及還原該等顆粒以產生催化劑D。
利用處理具有以質量%表示之以下組成之不平衡C8芳香
族進料之試驗工廠流動反應器評估該四種催化劑A-D對C8芳香族化合物中之非芳香族化合物之轉化的作用:
在以下條件下測試該四種催化劑:12每小時重量空間速度
4氫氣/烴莫耳比
在385℃/395℃/405℃下各持續1-2小時
Claims (9)
- 一種用於轉化包括高濃度不平衡C8芳香族化合物及低濃度非芳香族化合物之烴進料混合物之方法,其係藉由使該混合物與雙催化劑系統(其包括含有鎢組分及至少一種沸石鋁矽酸鹽中之一或兩者之第一催化劑及基於元素計含有0.01至0.2質量%之至少一種鉑族金屬組分之第二催化劑)於包括300℃至550℃之溫度、100 kPa至5 MPa之壓力及就該雙催化劑系統而言為0.5至50 hr-1之液體每小時空間速度的烴轉化條件下接觸,以獲得包括比在該進料混合物中濃度減小之乙苯及濃度減小之非芳香族化合物的轉化產物。
- 如請求項1之方法,其中該等非芳香族化合物之濃度為該進料混合物之0.5至10質量%。
- 如請求項1之方法,其中該第一催化劑基於元素計包括0.01至0.3質量%之鉑。
- 如請求項1之方法,其中該至少一種沸石鋁矽酸鹽包括MTW。
- 如請求項1之方法,其中該第一催化劑包括分層球體。
- 如請求項1之方法,其中該等第一及第二催化劑係按序堆疊。
- 如請求項1之方法,其中該催化劑系統為該等第一及第二催化劑之物理混合物。
- 如請求項1之方法,其中該等第一及第二催化劑係含於相同催化劑顆粒上。
- 如請求項8之方法,其中該第一催化劑包括在該第二催化劑之表面上之層。
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