CN102822124B - 制造用于mto工艺的包含磷改性沸石的催化剂的方法 - Google Patents
制造用于mto工艺的包含磷改性沸石的催化剂的方法 Download PDFInfo
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- CN102822124B CN102822124B CN201180015677.7A CN201180015677A CN102822124B CN 102822124 B CN102822124 B CN 102822124B CN 201180015677 A CN201180015677 A CN 201180015677A CN 102822124 B CN102822124 B CN 102822124B
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- zeolite
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 33
- 239000011574 phosphorus Substances 0.000 title claims abstract description 33
- -1 phosphorus modified zeolite Chemical class 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 title abstract description 36
- 230000008569 process Effects 0.000 title abstract description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000010457 zeolite Substances 0.000 claims abstract description 72
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 68
- 239000011230 binding agent Substances 0.000 claims abstract description 43
- 238000001035 drying Methods 0.000 claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 46
- 239000004927 clay Substances 0.000 claims description 24
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 16
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
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- 239000002184 metal Substances 0.000 claims description 5
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- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
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- RLUDBKMUNGUSSY-UHFFFAOYSA-N [Si](=O)=O.[Na] Chemical compound [Si](=O)=O.[Na] RLUDBKMUNGUSSY-UHFFFAOYSA-N 0.000 description 6
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- 150000001457 metallic cations Chemical class 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000011159 matrix material Substances 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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Abstract
本发明为催化剂在MTO工艺中将醇或醚转化成轻质烯烃的用途,其中所述催化剂包含磷改性沸石并且通过以此顺序包括以下步骤的方法制造:a)将主要部分的磷引入至在结构中包含至少一个十元环的沸石中,b)将步骤a)的磷改性沸石与选自一种或多种粘结剂、碱土金属盐、稀土金属盐、粘土和成型添加剂的至少一种组分混合,b)*由混合物b)制造催化剂形体,c)任选的干燥步骤、或者任选的干燥步骤和随后的洗涤步骤,d)煅烧步骤,d*)任选的洗涤步骤和随后的干燥,e)任选地,在步骤b)或b)*期间或在步骤b)或b)*结束时引入小部分的磷。
Description
技术领域
本发明涉及用于制造在MTO工艺中使用的包含磷改性沸石的催化剂的方法。更准确地说,其涉及催化剂在MTO工艺中将醇或醚转化成轻质烯烃的用途,其中所述催化剂包含磷改性沸石。烯烃传统上由石油原料通过催化裂化或蒸汽裂化工艺生产。这些裂化工艺(特别是蒸汽裂化)由多种烃原料生产轻质烯烃,例如乙烯和/或丙烯。乙烯和丙烯是在用于制造塑料和其它化合物的多种工艺中有用的重要的大宗(commodity)石化产品。
原油的有限供给和日益升高的价格已经促使寻找生产烃产品的替代工艺。MTO工艺产生轻质烯烃如乙烯和丙烯以及重质烃如丁烯。所述MTO工艺是将甲醇或二甲醚通过与分子筛接触而进行的转化。对甲醇到烯烃(MTO)工艺的兴趣基于如下事实:甲醇可由煤或天然气通过生产合成气,然后加工所述合成气以生产甲醇而得到。
背景技术
包含磷改性沸石(所述磷改性沸石也称作P-沸石)的催化剂是已知的。以下现有技术描述了所述催化剂的各种制造方法。
US 2006 106270涉及双功能(官能,function)催化剂体系在含氧物(oxygenate)转化为丙烯(OTP)的工艺的烃合成反应区中的用途,其中所述含氧物转化为丙烯(OTP)的工艺在相对高的温度优选地使用蒸汽稀释剂运行并且使用移动床反应器技术。所述双功能催化剂体系包括分散于包含活性磷和/或铝阴离子的磷改性氧化铝基质中的具有双功能性能的分子筛。据解释,在利用该磷改性氧化铝基质时观察到的水热稳定化作用是由磷和/或铝阴离子从该基质迁移或分散到所结合的分子筛中引起的。这些阴离子然后可用于抵抗由暴露于温度与在OTP反应区中和再生区中使用的温度对应的蒸汽引起的分子筛骨架破坏或变化(modification)的公知脱铝机理而修复、韧化(anneal)和/或稳定分子筛的骨架。
US 4,356,338公开了通过用蒸汽和/或含磷化合物对催化剂进行预处理而降低催化剂结焦和延长可用的催化剂寿命的方法。预处理可通过如下实现:用含磷化合物浸渍催化剂或催化剂/粘结剂组合,以在其上沉积基于被处理的催化剂或催化剂/粘结剂基质的重量的约4重量%的磷,且优选约2重量%-15重量%的磷。
US 5,231,064涉及包含粘土和沸石的流体催化剂(所述粘土和沸石的至少一种已用含磷化合物如磷酸二氢铵或磷酸处理和其在低的pH(优选低于约3)喷雾干燥)。所述催化剂被认为有利地表现出降低的磨损。
EP 511013 A2提供由高级烯烃或链烷烃原料或者混合的烯烃与链烷烃原料生产C2-C5烯烃的改进工艺。根据该现有技术,使所述烃原料与特定的ZSM-5催化剂在升高的温度、高的空间速度和低的烃分压下接触,以生产低级烯烃。所述催化剂在用于烃转化前用蒸汽处理。活性催化剂组分是具有在20-60范围内的表面Si/Al比的含磷ZSM-5。优选地,通过如下向所形成的ZSM-5添加磷:根据例如在美国专利3,972,832中描述的程序,用磷化合物浸渍ZSM-5。不太优选地,可将所述磷化合物添加至由其形成催化剂的多组分混合物中。所述磷化合物以足以提供具有0.1-10重量%、优选1-3重量%磷的最终ZSM-5组合物的量添加。
将所述含磷ZSM-5优选地与已知的粘结剂或基质如二氧化硅、高岭土、钙膨润土、氧化铝和硅铝酸盐(silica aluminate)等组合。所述ZSM-5通常占催化剂组合物的1-50重量%、优选5-30重量%和最优选10-25重量%。
EP 568913 A2描述了制备适合于在甲醇或二甲醚向轻质烯烃的催化转化中使用的基于ZSM-5的催化剂的方法,其中其包括以下相继步骤:
●将基于沸石ZSM-5的催化剂与二氧化硅溶胶以及硝酸铵溶液混合,
●对所述混合物进行捏合、成型、干燥和煅烧,
●在70-90℃用HCl溶液对该改性沸石进行交换,
●干燥并煅烧该H-改性沸石,
●在降低的压力下用磷酸浸渍该H-改性沸石,
●干燥并煅烧该P-改性沸石,
●在降低的压力下用稀土元素的溶液浸渍该P-改性沸石,
●干燥并煅烧该P-稀土-改性沸石,
●在500-600℃用水蒸汽对该P-稀土-改性沸石进行水热处理,和
●煅烧该改性沸石。
WO 03 020667涉及由含氧物进料生产烯烃特别是乙烯和丙烯的工艺,包括使含氧物进料与至少两种不同的沸石催化剂接触以形成烯烃组合物,其中第一沸石催化剂包含ZSM-5分子筛且第二沸石催化剂包含选自ZSM-22、ZSM-23、ZSM-35、ZSM-48及其混合物的沸石分子筛。所述ZSM-5可以是未改性的、磷改性的、蒸汽改性为微孔体积降低为不少于未汽蒸ZSM-5的微孔体积的50%、或其各种混合物。根据一个实施方案,所述沸石用含磷化合物改性以控制孔体积的下降。替代地,对沸石进行汽蒸,并在汽蒸之前或之后添加所述磷化合物。基于元素测量的磷的量为0.05重量%-20重量%且优选1重量%-10重量%,基于沸石分子筛的重量。优选地,磷对骨架铝(即在沸石骨架中)的原子比不大于4:1且更优选2:1-4:1。根据一个实施方案,磷改性剂结合到该发明的催化剂中是通过使单独的沸石分子筛或者与粘结剂组合的沸石与合适的磷化合物的溶液接触而实现的。将固体沸石或沸石催化剂从所述磷溶液分离,干燥并煅烧。在一些情况下,添加的磷在这样的条件下转化成其氧化物形式。与含磷化合物的接触通常在25℃-125℃的温度进行15分钟至20小时的时间。沸石中磷的浓度可为0.01重量%-30重量%。该现有技术公开了非配制的P-ZSM-5。
生产包含配制的P-沸石的催化剂的通常方法在于将已经预先配制的沸石(如沸石+粘结剂)用P-化合物浸渍,或将磷添加至反应介质中。
大量专利公开了通过沸石磷化而制备活性相(非配制的磷化沸石)的方案,及它们在甲醇转化中的用途。这些参考文献中的一些包括将所述活性相与粘结剂进一步共混的选项。然而,活性相本身在反应中是良好的。假定粘结剂仅起到稀释剂的作用(情况通常并非如此)。由于涉及制备配制的催化剂和在第一阶段实施磷化步骤,本发明的工艺不同于在本领域中已知的基于P-沸石的活性相的许多制备。此外,在第一步骤中沸石的磷化(活性相的形成)不一定导致合适的催化剂。相反,总体方案导致良好的催化剂。
本发明中涉及的催化剂包含沸石和至少一种选自一种或多种粘结剂、碱土金属盐、稀土金属盐、粘土和成型添加剂的组分。所述金属盐、粘结剂和粘土也可吸附磷,从而干扰沸石,甚至与沸石竞争,阻碍恰当的(proper)沸石磷化。优先吸附磷的痕量金属的存在可甚至更多地搅扰沸石磷化。这常常由于差的再现性和粘结剂孔堵塞而导致非选择性的催化剂。本发明的方法提供了使沸石选择性地磷化的方案,其克服了粘结剂、金属盐或粘土存在的副作用。因此,本发明公开了催化剂的制备需要在引入任何其它组分如粘结剂、金属、粘土和成型添加剂前使沸石磷化。该方法确保了制备的再现性、水热稳定性和良好的催化剂性能。
发明内容
本发明涉及催化剂在MTO工艺中将醇或醚转化成轻质烯烃的用途,其中所述催化剂包含磷改性沸石,并通过以此顺序包括以下步骤的方法制造,
a)将主要部分(essential portion)的磷引入至在结构中包含至少一个十元环的沸石中,
b)将步骤a)的磷改性沸石与选自一种或多种粘结剂、碱土金属盐、稀土金属盐、粘土和成型添加剂的至少一种组分混合,
b)*由混合物b)制造催化剂形体(主体,body),
c)任选的干燥步骤、或者任选的干燥步骤和随后的洗涤步骤,
d)煅烧步骤,
d*)任选的洗涤步骤和随后的干燥,
e)任选地,在步骤b)或b)*期间或在步骤b)或b)*结束时引入小部分的磷。
有利地,沸石(或分子筛)包含少于1000wppm的钠、少于1000wppm的钾和少于1000wppm的铁。
有利地,沸石包含少于200ppm的碱金属和碱土金属。
有利地,初始沸石的本体(bulk)Si/Al比低于20。有利地,沸石包含小于100ppm的氧化还原(red-ox)和贵重元素如Zn、Cr、Ti、Rh、Mn、Ni、V、Mo、Co、Cu、Cd、Pt、Pd、Ir、Ru、Re。
磷源有利地基本上不含金属化合物。其有利地选自H3PO4、铵磷酸盐或有机P-化合物。
在一个实施方案中,步骤e)的磷可作为粘结剂组分或粘土组分引入。
在步骤a)中引入至沸石中的磷的量可为0.5-30重量%,但优选为0.5-9%。
有利地,在步骤a)中,通过提供过量的磷化剂,P/Al摩尔比高于1。
配制步骤b)和c)可通过喷雾干燥、挤出、油滴等进行。
根据本发明,在步骤c)和d*)中,将催化剂用水处理有利地为0.5-48小时的时间、优选约1-36小时的时间和最优选约2-24小时的时间。水为约10℃-180℃、优选约15℃-100℃和最优选约20℃-60℃的温度。水处理后,将催化剂在约60-350℃干燥。任选地,水可包含铵或/和选自Li、Ag、Mg、Ca、Sr、Ba、Ce、Al、La、及其混合物的离子的至少一种。
在步骤a)结束时,将P-沸石从反应介质分离不是强制性的,可将粘结剂、碱土金属盐、稀土金属盐、粘土和成型添加剂直接添加至反应介质中。
在一个优选实施方案中,使用低钠含量的粘结剂和粘土。
在步骤a)的磷化之前,沸石可经历各种处理,包括离子交换、汽蒸、酸处理、通过二氧化硅沉积进行表面钝化等。
在一个优选实施方案中,粘结剂和粘土中的钠含量小于5000ppm钠。
优选的沸石结构选自MFI、MTT、FER、MEL、TON、MWW、EUO、MFS、ZSM-48。
具体实施方式
关于将醇或醚转化成轻烯烃的MTO工艺,该工艺已在许多专利申请中进行了描述。可列举WO 2004/016572、WO 2005/016856、WO 2008/110526、WO 2008/110528、WO 2008/110530、WO 2009/016153、WO 2009/156434和WO 2009/016154,将其内容结合在本申请中。
关于在结构中包含至少一个10元环的沸石,可列举结晶硅酸盐。其例如为由硅、铝、氧和任选的硼组成的MFI(ZSM-5、硅沸石-1、硼硅沸石(boralite)C、TS-1)、MEL(ZSM-11、硅沸石-2、硼硅沸石D、TS-2、SSZ-46)、FER(镁碱沸石(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ZSM-48系列的微孔材料。
三字母名称“MFI”和“MEL”各自表示如由国际沸石协会结构委员会所确定的特定的结晶硅酸盐结构类型。MFI型结晶硅酸盐的例子是合成沸石ZSM-5和硅沸石以及本领域中已知的其它MFI型结晶硅酸盐。MEL系列的结晶硅酸盐的例子是沸石ZSM-11和本领域中已知的其它MEL型结晶硅酸盐。其它例子是如国际沸石协会(Atlas of zeolite structure types,1987,Butterworths)所描述的硼硅沸石D和硅沸石-2。优选的结晶硅酸盐具有由十氧环限定的孔或通道。
结晶硅酸盐是基于通过阳离子的共享而彼此连接的XO4四面体的骨架的微孔结晶无机聚合物,其中X可为三价(如Al、B、...)或四价(如Ge、Si、...)。结晶硅酸盐的晶体结构通过这样的特定有序性(次序,order)限定:四面体单元的网络以所述特定有序性连接在一起。结晶硅酸盐孔开口的尺寸由形成孔所需的四面体单元或者氧原子的数量以及所述孔中存在的阳离子的性质决定。它们具有如下性质的独特组合:高的内表面积;具有一种或多种离散尺寸的均匀孔;可离子交换性;良好的热稳定性;和吸附有机化合物的能力。由于这些结晶硅酸盐的孔的尺寸与实际研究的许多有机分子类似,它们控制反应物和产物的进出,导致催化反应中特定的选择性。具有MFI结构的结晶硅酸盐具有拥有如下孔直径的双向交叉孔体系:沿着[010]的直通道:0.53-0.56nm和沿着[100]的正弦通道:0.51-0.55nm。具有MEL结构的结晶硅酸盐具有双向交叉直孔体系,其中沿着[100]的直通道具有0.53-0.54nm的孔直径。
在一个具体实施方案中,在磷化之前对结晶硅酸盐进行汽蒸,以从结晶硅酸盐骨架除去铝。蒸汽处理在优选在425-870℃范围内、更优选在540-815℃范围内的升高的温度下和在1-5巴绝对压力下和在13-200kPa的水分压下进行。优选地,蒸汽处理在包含5-100%蒸汽的气氛中进行。所述蒸汽气氛优选地包含5-100体积%蒸汽和0-95体积%惰性气体(优选氮气)。更优选的气氛包含72体积%蒸汽和28体积%氮气,即在1个大气压的压力下蒸汽为72kPa。蒸汽处理优选地实施1-200小时、更优选20小时-100小时。如上所述,蒸汽处理趋于通过形成氧化铝来降低结晶硅酸盐骨架中的四面体铝的量。
另外,如果在待磷化的沸石的制备期间,已经使用了碱金属或碱土金属,则可使分子筛经历离子交换步骤。常规地,离子交换使用铵盐或无机酸在水溶液中进行。
关于P向沸石中的引入,例如,所述P-改性沸石通过以如下顺序包括如下步骤的工艺制造:
-引入P;
-如果存在液体,则将固体与液体分离;
-任选的洗涤步骤,或任选的干燥步骤,或任选的干燥步骤以及随后的洗涤步骤;
-煅烧步骤;
任选地,与含磷化合物的接触在40℃-110℃的温度进行。P可通过任意方式或者例如根据US 3,911,041中描述的方案引入。
液体与固体的分离有利地通过在0-90℃的温度过滤、通过在0-90℃的温度离心、通过蒸发或等效方式进行。
任选地,可将沸石在分离之后洗涤之前干燥。有利地,所述干燥在40-600℃的温度下有利地进行1-10小时。该干燥可在静止条件下或在气流中进行。可使用空气、氮气或任意惰性气体。
洗涤步骤可在过滤(分离步骤)期间使用一部分冷水(<40℃)或热水(>40但<90℃)进行,或者可使固体经历水溶液(1kg固体/4升水溶液)并在回流条件下处理0.5-10h,随后蒸发或过滤。
根据一个具体实施方案,通过以如下顺序包括如下步骤的工艺制造磷改性沸石:
-选择沸石;
-在范围为400-870℃的温度汽蒸0.01-200h;
-任选地,用酸的水溶液在有效地从沸石除去显著部分Al的条件下浸提(leach);
-用含P源的水溶液在有效地引入有利地为至少0.05重量%P的条件下引入P;
-将固体与液体分离;
-任选的洗涤步骤,或任选的干燥步骤,或任选的干燥步骤以及随后的洗涤步骤;
-任选的煅烧步骤。
在蒸汽处理步骤中,温度优选为420-870℃,更优选480-760℃。压力优选为大气压并且水分压可范围为13-100kPa。蒸汽气氛优选地包含5-100体积%蒸汽和0-95体积%惰性气体(优选氮气)。蒸汽处理优选地实施0.01-200小时,有利地0.05-200小时,更优选0.05-50小时。蒸汽处理趋于通过形成氧化铝来降低结晶硅酸盐骨架中四面体铝的量。
浸提可使用有机酸例如柠檬酸、甲酸、草酸、酒石酸、丙二酸、琥珀酸、戊二酸、己二酸、马来酸、邻苯二甲酸、间苯二甲酸、富马酸、次氨基三乙酸、羟基乙二胺三乙酸、乙二胺四乙酸、三氯乙酸、三氟乙酸或这样的酸的盐(如钠盐)或两种或更多种这样的酸或盐的混合物进行。其它无机酸可包括无机酸例如硝酸、盐酸、甲烷硫酸、磷酸、膦酸、硫酸或这样的酸的盐(如钠盐或铵盐)或两种或更多种这样的酸或盐的混合物。
残留的P含量通过包含P源的酸的水溶液中的P浓度、干燥条件和洗涤程序(若存在洗涤程序的话)调节。可在过滤和洗涤步骤之间设想干燥步骤。
关于步骤b),和粘结剂,其选择成对于使用该催化剂的工艺中采用的温度和其它条件具有耐受性。所述粘结剂是选自二氧化硅、金属硅酸盐、金属氧化物如ZrO2和/或金属、或者包含二氧化硅和金属氧化物的混合物的凝胶的无机材料。提供具有良好抗碎强度的催化剂是期望的。这是因为在商业使用中,期望防止催化剂破碎成粉末状材料。这样的氧化物粘结剂通常仅用于改善催化剂的抗碎强度。用于本发明催化剂的特别优选的粘结剂包括二氧化硅。细粒状结晶硅酸盐材料和粘结剂无机氧化物基质的相对比例可宽泛地变化。
关于步骤b)*,除增强催化剂强度性质外,基质材料还允许分子筛微晶粉末结合成适合于商业催化工艺的较大颗粒尺寸。可将混合物b)的配方形成为多种形状,包括挤出物、球和丸片(pill)等。粘结剂材料通常在性质上在一定程度上是多孔性的并且对于促进甲醇向轻质烯烃的期望转化可为有效的或者可不是有效的。基质材料还可促进进料物流的转化并常常提供相对于催化剂降低的对期望产物的选择性。
用于形成在MTO工艺中使用的结合催化剂的二氧化硅溶胶的类型是作为包含分散的胶体二氧化硅颗粒的有机溶胶或水溶胶可商购获得的。例如,可使用硅酸钠作为二氧化硅溶胶。另外,还可使用硅胶、热解(fumed)或者火成(pyrogenic)二氧化硅以提供分子筛催化剂中的二氧化硅粘结剂。硅酸是另一种可能的二氧化硅来源。如果氧化镁粘结剂是期望的,则起始淤浆将包含经水解的烷氧基镁。当使用氧化锆粘结剂用于催化剂制备时,优选的起始酸性溶胶是乙酸锆水溶液,其优选地与脲胶凝剂组合。
关于粘土,优选的是,任选地将粘土添加至催化剂中。粘土通常在与分子筛和粘结剂混合之前添加至催化剂淤浆中,并将得到的淤浆混合并喷雾干燥。用于该工艺中以形成硬化产物的粘土包括但不限于高岭土、高岭石、蒙脱土、皂石、膨润土、绿坡缕石和多水高岭土。粘土像增强催化剂颗粒耐磨损性的粘结剂一样贡献强度,并且与粘结剂组合的粘土贡献颗粒硬度。粘土还以小颗粒的形式开始并且具有较高密度,使得当与分子筛和粘结剂组合时提供较致密的颗粒,从而赋予较高密度的期望特性。
关于碱土金属盐、稀土金属盐,金属有利地是Ca、Mg、Sr、Ce、La、或其组合。
关于P-沸石、所述一种或多种粘结剂、碱土金属盐、稀土金属盐、粘土和成型添加剂的比例,有利地,P-沸石的比例为催化剂的5-95重量%。催化剂包含P-沸石和选自一种或多种粘结剂、碱土金属盐、稀土金属盐、粘土和成型添加剂的至少一种组分。催化剂中包含的P-改性沸石的量更有利地为全部催化剂的15-90重量%,优选催化剂的20-70重量%。当添加粘土时,粘土形成经干燥的催化剂产物的约10-约80重量%。碱土金属盐和稀土金属盐的浓度以金属(Me)计可为催化剂的0.1-15重量%。有利地,催化剂中(Al+Me)/P的摩尔比在0.5-3范围内,其中Me是碱土或稀土。
在将P-沸石与选自一种或多种粘结剂、碱土金属盐、稀土金属盐和粘土的至少一种组分混合时,可将催化剂配制成丸粒(颗粒,pellet)、挤出成其它形状、或者形成为球或喷雾干燥粉末。典型地,将所有成分通过混合工艺混合在一起。例如,在这样的工艺中,将凝胶形式的粘结剂如二氧化硅与P-沸石混合,并将得到的混合物挤出成期望的形状,如圆柱形或多叶形棒。可在旋转造粒机中或通过油滴技术制成球形形状。可通过对催化剂悬浮液进行喷雾干燥而进一步制成小球。
此后,将催化剂在空气或惰性气体中、典型地在350-900℃的温度煅烧1-48小时。任选地,所述空气或惰性气体可包含10-90体积%浓度的蒸汽。
关于步骤c)和d*),经干燥或煅烧的成型催化剂颗粒可任选地通过使它们与水、或离子化合物的水交换溶液接触而整理(finish)。所述水交换溶液的特征在于,其对于除去可占据分子筛的离子交换位点(site)的不期望的金属阳离子、和/或引入期望的金属阳离子是有效的。所述不期望的金属阳离子是Na、K、Fe、Zn、Cr、Mn、Ni、V、Mo、Co、Cu、Cd。这些物质可源自分子筛中存在的无机模板材料,或更常见地,源于无机氧化物粘结剂源材料(如铝溶胶)。在所述催化剂所设计用于的操作使用(processing service)(例如,甲醇向烯烃的转化)中,这些金属阳离子可促进副反应,减缓期望的反应速率或使期望反应的催化复杂化。无机氧化物粘结剂的一些来源基本上不含不期望的金属阳离子,并且因此使用这样的来源生产的干燥颗粒不一定需要与交换溶液接触。在所述整理步骤之前和之后的水洗可为期望的,以从催化剂冲洗掉不期望的固体和/或残留的交换溶液。
根据本发明,在步骤c)和d*),将催化剂用水处理有利地为0.5-48小时的时间、优选约1-约36小时且最优选约2-24小时的时间。水为约10℃-180℃、优选约15℃-100℃且最优选约20℃-60℃的温度。水处理后,将催化剂在约60-350℃干燥。任选地,所述水可包含铵或选自Li、Ag、Mg、Ca、Sr、Ba、Ce、Al、La、及其混合物中的金属阳离子的至少一种,它们不促进副反应并使沸石抵抗蒸汽脱铝而稳定化。
实施例
实施例1
将H-型沸石ZSM-5(Si/Al=12)样品(包含445ppm Na、小于25ppm的K、178ppm Fe、17ppm Ca且在没有模板的情况下合成)在550℃在大气压下在100%H2O中汽蒸6h。以下将该样品记作样品A。
使经汽蒸的固体A与3.14M的H3PO4溶液(4.2ml/1g沸石)在回流条件下接触4h。然后,在室温下通过从溶液过滤将固体从液相分离。将得到的材料在200℃干燥16h。以下将该样品记作样品B。
使100g经汽蒸的固体A与31g85重量%的H3PO4在400ml H2O中在回流条件下接触4h。然后冷却所述溶液,并将10g硬硅钙石(硅酸钙)添加至该混合物中,随后在室温搅拌30分钟并蒸发。以下将该样品记作样品C。
使100g经汽蒸的固体A与109.1g 85重量%的H3PO4在320ml H2O中在回流条件下接触4h。然后将100g硬硅钙石(硅酸钙)添加至该混合物中,随后在室温下搅拌30分钟并蒸发。以下将该样品记作样品D。
实施例2(对比例)
该实施例说明了如下事实:对于含氧物的转化,磷化的活性相不一定是好的催化剂。权利要求书中所给出的步骤的结果(顺序)与、以及粘结剂的共混不止是简单的稀释作用。
将25g样品B(包含5重量%磷)额外地在400℃干燥3h,并用蒸馏水在80℃洗涤2h,随后在室温过滤(P=3.4重量%,Al=2.7重量%)。将得到的固体通过在600℃汽蒸2h而进行平衡。
在固定床、下流式不锈钢反应器中在2g催化剂(35-45目颗粒)上使用基本上纯的甲醇进料在Tin=550℃和在0.5巴表压的压力和WHSV=1.6h-1下进行催化剂试验。在催化运行(run)之前,将所有催化剂在流动的N2(5Nl/h)中加热至反应温度。通过装备有毛细管柱的气相色谱在线进行产物分析。表1中催化剂的催化性能是以碳计、以干重计且在无焦炭的基础上给出的。
表1
MeOH向HC的转化 | 6.64 |
C1 | 6.28 |
DME,以CH2计 | 55.00 |
CH3OH,以CH2计 | 38.36 |
乙烯 | 0.11 |
丙烯 | 0.11 |
C4烯烃 | 0.10 |
C5烯烃 | 0.02 |
实施例3(实施例)
将320g样品B与400g特定粘结剂(P=16.7重量%,Si=14.5,Mg=0.19,Al=0.018重量%,K=230ppm,Na=230ppm,Ca=20.3重量%)、165ml H2O、235ml包含34重量%SiO2的低钠二氧化硅溶胶和2-3重量%挤出添加剂共混。将该混合物搅拌30分钟并挤出。
所述特定粘结剂是通过将等质量的NH4H2PO4和硬硅钙石在水性介质中在室温共混而生产的(1g固体/4ml水)。在搅拌60分钟之后,磷化的硬硅钙石通过过滤与液体分离并将其干燥。使用该经干燥的产物作为挤出组分。
将所挤出的固体在室温干燥24h,然后在升高的温度下干燥16h,随后洗涤并在600℃汽蒸2h。以下将该样品记作E。
在固定床、下流式不锈钢反应器中在2g催化剂(35-45目颗粒)上使用基本上纯的甲醇进料在Tin=550℃和在0.5巴表压以及WHSV=1.6h-1下进行催化剂试验。在催化运行之前,将所有催化剂在流动的N2(5Nl/h)中加热至反应温度。通过装备有毛细管柱的气相色谱在线进行产物分析。表1中催化剂的催化性能是以碳计、以干重计并且在无焦炭的基础上给出的。所述结果是针对在8小时运行期间的平均催化剂性能给出的。
表2
实施例4(对比例,挤出,催化剂中40重量%沸石)
将356g样品A与338.7g Nyacol(40重量%SiO2溶胶)、311.3g热解二氧化硅(FK500)、480ml H2O和2-3%挤出添加剂一起挤出。将所挤出的固体在室温干燥24h,然后在110℃干燥16h,随后在500℃煅烧10h。最终样品包含40重量%沸石和60重量%SiO2粘结剂。使该挤出的样品经历与0.5MNH4Cl在回流条件下的离子交换18h,随后用水洗涤,在110℃干燥16h并在450℃煅烧6h。将该经成型且经交换的样品用3.1M H3PO4在回流条件下处理4h(1g/4.2ml),随后冷却,过滤并在110℃干燥16h。
将该磷化的样品在室温下用0.1M乙酸钙溶液洗涤2h(1g/4.2ml)。然后将该经洗涤的样品在110℃干燥16h,并在600℃在100重量%H2O中汽蒸2h。
实施例5(对比例,挤出,在催化剂中40重量%沸石)
将来自实施例4的样品在室温下用0.1M乙酸钙溶液再洗涤一次,洗涤2h(1g/4.2ml)。然后将经洗涤的样品在110℃干燥16h并在600℃在100重量%H2O中汽蒸2h。
实施例4和5说明当样品首先经历与粘结剂的接触,随后磷化时的方案。
实施例6(实施例,挤出,催化剂中40重量%沸石)
将4g样品B在室温下用0.1M乙酸钙溶液洗涤2h(1g/4.2ml),过滤并在110℃干燥16h。将4g经干燥的样品与6g特定粘结剂以及2-3重量%挤出添加剂以40/60的沸石/粘结剂比一起挤出。所述粘结剂通过如下获得:将40g硬硅钙石与10g氧化铝(Condea~75重量%Al2O3)、50g(NH4)H2PO4以及50mlH2O在60℃共混,随后过滤并在110℃干燥16h。该特定粘结剂中的钠含量为200ppm。
将所挤出的固体在110℃干燥16h,随后在600℃煅烧10h。
此实施例显示了预磷化的样品通过与低钠粘结剂一起挤出而用于制造配制的催化剂。
实施例7(实施例,喷雾干燥)
使356g样品A经历与288g 85重量%H3PO4+972ml H2O在回流条件下的接触4h。然后,将混合物冷却至室温,并添加336g低钠氧化铝溶胶(20重量%氧化铝)。将得到的溶液在搅拌下保持30分钟,随后缓慢添加NH4OH直至得到的溶液pH为约6.5。然后,将该混合物陈化(maturation)至少1h,随后添加48g高岭土和720g低钠二氧化硅溶胶(34重量%SiO2,200ppm Na)。淤浆的最终pH为约~6。将得到的淤浆在搅拌下保持至少30分钟并喷雾干燥。将经喷雾干燥的样品用水洗涤,将其干燥并在700℃煅烧2h。
实施例8(实施例,喷雾干燥)
使150g样品B与630ml包含1.5g分散的硬硅钙石的水溶液接触,随后添加450g低钠二氧化硅溶胶(在水中34重量%的SiO2,200ppm Na)。然后,搅拌该溶液1小时并喷雾干燥。将喷雾干燥的固体在室温下用水洗涤2h,随后过滤,在110℃干燥16h并在700℃煅烧。
实施例9(实施例,喷雾干燥)
使100g样品C与420ml包含1g分散的硬硅钙石的水溶液接触,随后添加300g低钠二氧化硅溶胶(在水中34重量%的SiO2,200ppm Na)。然后,搅拌该溶液1小时并喷雾干燥。将喷雾干燥的固体在室温下用水洗涤2h,随后过滤,在110℃干燥16h并在700℃煅烧。
实施例10(实施例,喷雾干燥)
使100g样品D与420ml包含1g分散的硬硅钙石的水溶液接触,随后添加150g低钠二氧化硅溶胶(在水中34重量%的SiO2,200ppm Na)。然后,搅拌该溶液1小时并喷雾干燥。将喷雾干燥的固体在室温下用水洗涤2h,随后过滤,在110℃干燥16h并在700℃煅烧。
实施例11(实施例,喷雾干燥)
使100g样品A与25g 85重量%H3PO4在回流条件下接触4小时,随后冷却,并添加120ml包含7g分散的硬硅钙石的水溶液。将得到的淤浆在搅拌下保持约1h,随后添加300g低钠二氧化硅溶胶(在水中34重量%的SiO2,200ppm Na)。然后,搅拌该溶液1小时并喷雾干燥。将喷雾干燥的固体在200℃干燥16h并在室温下用水洗涤2h,随后过滤,干燥,并在700℃煅烧2h。
实施例12(MTO性能)
在固定床、下流式不锈钢反应器中在2g催化剂(35-45目颗粒)上使用基本上纯的甲醇进料在Tin=550℃和在0.5巴表压以及WHSV=1.6h-1下进行催化剂试验。在催化运行之前,将所有催化剂在流动的N2(5Nl/h)中加热至反应温度。通过装备有毛细管柱的气相色谱在线进行产物分析。表1中催化剂的催化性能是以碳计、以干重计并且在无焦炭的基础上给出的。所述结果是针对在最初4小时运行期间的平均催化剂性能给出的。
表3
该数据说明在根据本发明制备的催化剂上获得了更高的丙烯产率。
Claims (8)
1.甲醇到烯烃(MTO)工艺,其包括:制造包含磷改性沸石的催化剂的方法,所述方法以此顺序包括以下步骤,
a)将磷引入至在结构中包含至少一个十元环的沸石中,其中引入至沸石中的磷的量为0.5-30重量%,其中沸石结构选自MFI,
b)将步骤a)的磷改性沸石与选自一种或多种粘结剂、碱土金属盐、稀土金属盐和粘土的至少一种组分混合,
b)*通过将步骤b)中获得的混合物喷雾干燥而由所述混合物制造催化剂形体,
c)任选的干燥步骤、或者任选的干燥步骤和随后的洗涤步骤,
d)煅烧步骤,
d*)任选的洗涤步骤和随后的干燥,
并且甲醇到烯烃(MTO)工艺包括在所获得催化剂的存在下将甲醇转化为轻质烯烃。
2.根据权利要求1的工艺,其中在步骤a)中引入至沸石中的磷的量为0.5-9%。
3.根据权利要求1-2任一项的工艺,其中沸石(或分子筛)包含小于1000wppm的钠、小于1000wppm的钾和小于1000wppm的铁。
4.根据权利要求1-2任一项的工艺,其中沸石包含小于100ppm的氧化还原和贵重元素即Zn、Cr、Ti、Rh、Mn、Ni、V、Mo、Co、Cu、Cd、Pt、Pd、Ir、Ru、Re。
5.根据权利要求1-2任一项的工艺,其中碱土金属和稀土金属盐是Ca、Mg、Sr、Ce、La、或其组合。
6.根据权利要求1-2任一项的工艺,其中P-沸石的比例为催化剂的15-90重量%。
7.根据权利要求1-2任一项的工艺,其中碱土金属盐和稀土金属盐的浓度以金属(Me)计为催化剂的0.1-15重量%。
8.根据权利要求7的工艺,其中催化剂中(Al+Me)/P的摩尔比在0.5-3的范围内,其中Me是碱土或稀土。
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EP2348004A1 (en) | 2010-01-25 | 2011-07-27 | Total Petrochemicals Research Feluy | Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO or a dehydration process |
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