CN100374202C - 分层微孔隙固体 - Google Patents
分层微孔隙固体 Download PDFInfo
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- CN100374202C CN100374202C CNB998117501A CN99811750A CN100374202C CN 100374202 C CN100374202 C CN 100374202C CN B998117501 A CNB998117501 A CN B998117501A CN 99811750 A CN99811750 A CN 99811750A CN 100374202 C CN100374202 C CN 100374202C
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- oxide material
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
本发明涉及一种微孔氧化物材料ITQ-6,具有特征X衍射图,其表面积至少20m2/g为微孔表面积,至少350m2/g为外表面积和至少400m2/g为总表面积。其制备可通过凝胶的制备、凝胶水热处理及用膨胀溶液对所得材料进行处理,接着通过如超声波处理进行至少部分分层的方法。对该最后氧化物材料进行焙烧,并以酸形态或与金属尤其与贵金属的结合态作为催化剂,用于正丁烯异构化为异丁烯的过程,或脱蜡及异构脱蜡的过程,以及作为催化裂化催化剂,或在FCC催化剂中的添加剂。
Description
技术领域
本发明涉及一种无机氧化物、其制备方法、包含它的催化剂及其对烃类进行转化过程,诸如异构化、脱蜡、异构脱蜡及裂化过程的应用。
技术背景
层状材料,诸如在水存在下膨胀的黏土,在适宜条件下能够与有机及/或无机物质形成夹层(intercalated),可显著减弱使它们聚集一起的作用力到靠搅拌就能分隔即分散它们的程度,以达到分离这些片层的目的。
发明内容
本发明提供一种氧化物材料,其焙烧后的形态具有包括如表3所示数值的X衍射图,并具有用N2吸附脱附法确定的表面积特征,即微孔表面积至少20m2g-1,外表面积至少350m2g-1或含微孔并具有总表面积至少400m2g-1,如至少450m2g-1和外表面积至少350m2g-1,如至少400m2g-1。该材料,此后称为ITQ-6,具有微孔结构及高外表面积,能够负载Bronsted及Lewis酸中心,并以其X衍射图及其吸附特性和任选它的催化性质来表征。
本发明称为ITQ-6的氧化物材料通常化学组成以下式表示:
(XO2)n(Y2O3)m(H2O)pM2m/v
式中X表示四价元素,Y表示三价元素,XO2对Y2O3摩尔比为至少5∶1,n为至少5,m可以基本为0或至少0.5,和p为0-3n,X与Y之原子比优选至少5∶1,M表示阳离子,如氢及/或碱金属,如钠或碱土金属如价键数为v的钙。
优选地是,XO2中X表示至少一个四价元素,选自硅、锗,更优选为硅,并可任选含与Si及/或Ge相混合的钛。
优选地,Y2O3中Y表示至少一种三价元素,选自铝、硼、铁、铬及镓的四价元素,更优选为铝。
n优选为5至无穷大,如5-2000,诸如10-1000,20-800,60-200,诸如80-200或60-1000,同时m可优选为1-5或优选为1,但可基本为零(在这种情况下ITQ-6主要是硅质的)。
本发明的微孔氧化物具有一种通常由氧和四价元素原子如X原子所组成的四面体结构,有可能通过三价金属原子如Y原子替代晶格中某些X原子引入表面酸性,产生可通过质子补偿导致Bronsted酸性的荷负电网络,及/或导致Lewis酸性的高电荷半径比的阳离子,诸如Al离子。
本发明还提供一种制备本发明氧化物材料的方法,该方法包括将一种具有下表2所示基部间隔及相对强度数值的前体层状氧化物材料转化成所述氧化物材料,以及包括通过机械搅拌或超声波处理方法,对所述前体层状材料的溶胀产物,即产物1进行至少部分分层,而经干燥后该产物1的X衍射图如图2所示,其基部间隔(basal spacings)及相对强度如表2中所汇总。
产物1优选为溶胀(此后也称为膨胀)层状(laminar)组合物,它可通过包括使称之为PREITQ6的前体与进行溶胀的溶胀化(bulkingswelling)溶液接触的方法制得,该前体具有如图1所示的X衍射图及如表1所汇总的基部间隔及相对强度。
按照本发明的上述方法,其中所述溶胀产物已通过将所述前体层状材料分散在一种如下的溶胀溶液中的方法获得,该溶胀溶液包括带长链烃基和质子接受基团的有机化合物及能够对分散体提供羟基离子的化合物;其中前体层状材料是被分散在包括十六烷基三甲基氢氧化铵及四丙基氢氧化铵的溶胀溶液中的;其中前体层状氧化物材料是通过一种如下合成混合物的结晶而获得的,该合成混合物包括氧化硅源、一种氟化物盐及氟化氢以及4-氨基,2,2,6,6-四甲基哌啶及水;其中至少部分分层后接着进行酸处理。
将该PREITQ6通过一种合成方法适当地制备成结晶固体,该合成方法包括在压力釜中混合一种四价的金属源,如此后所定义的X,尤其是硅,(任选但优选为一种三价的金属源,如此后所定义的Y,尤其是铝),至少一种氟化物盐与氟化氢源、和一种有机氮化合物及水,并维持高温以使结晶为PREITQ6的过程发生。
在进行生产ITQ-6的第一阶段,可按适宜配比由氧化硅源,优选铝源,氟化物盐与HF源(或数源)及一种有机化合物(一种有机模板剂)及水来制备该PREITQ6。氧化硅源可以是如氧化硅粉末或含水氧化硅浆液,诸如市售商标为“Aerosil”、“Cabosil”或,“Ludox”的,或四乙基原硅酸酯(TEOS)或任何已知制备硅铝酸盐的其它氧化硅源。铝源如可以是一种铝盐,诸如其水溶性盐,尤其与强酸构成的铝盐,诸如硝酸铝Al(NO3)3、硫酸铝Al2(SO4)3或氯化铝AlCl3或铝氧化物诸如一水软铝石、拟薄水铝石或任何已知制备硅铝酸盐的铝源。氟化物盐优选为一种水溶性盐,尤其带有在焙烧时能热分解的阳离子的盐,诸如氟化铵。氟化氢可单独为HF或可为与氟化物盐结合的如双氟化物盐。有机化合物通常为含氮的,如有1-4尤其2-4个氮原子的,特别有2-10个碳原子,尤其4-8个碳原子的化合物。含氮化合物可以是脂肪二胺或三胺,诸如1,4二氨基丁烷、乙二胺,或可以是环脂二胺或三胺,诸如1,4二氨基环己烷,但优选为具有1-3个环氮原子和任选0-2取代氨基的杂环化合物。杂环可以是饱和或不饱和的,熔融的或非熔融的,可以有5或6个环原子的,尤其仅带若干环碳原子及一个或多个如1或2个环氮原子的,如在吡咯烷酮、吡啶、哌嗪或哌啶中的。环上可带0-5个烷基如1-6个碳原子的取代基,诸如甲基或乙基,尤其对称位于环上的2-4个碳原子的取代基。这样的杂环化合物的实例有1,4二甲基哌嗪、六亚甲基亚胺、吡咯烷酮、吡啶或优选4-氨基-2,2,6,6-四甲基哌啶。用于制备PREITQ6的组分可按适宜的比例加以混合,如具有氧化硅对氧化铝的摩尔比(尤其Si/Al原子比)至少5∶1,如5-1000∶1,诸如10-500∶1或20-400∶1如大于5∶1、10∶1、30∶1或40∶1诸如30-500∶1(具体按X∶Y的原子比,尤其Si∶Al)。
氟化物盐量通常为使氧化硅/NH4F摩尔比在0.4-0.9,如0.55-0.75诸如约0.65,而同时氟化氢量通常要使氧化硅/HF的摩尔比为0.5-8,如1-3诸如约2。有机化合物对氧化硅的摩尔比通常为0.3-3,诸如0.5-2如0.7-1.5或约1。
PREITQ6的合成可在温度80-250℃范围如100-200℃间进行,连续搅拌形成的凝胶,时间1-30天如1-18天,并优选在2-12天之间,在此期间使PREITQ6进行结晶。合成过程优选在自压下进行。此期间结束得到一种其pH在9-10之间内含白色固体反应产物的浆液,对该固体产物过滤前一般用蒸馏水加以洗涤,然后加以干燥,干燥优选在300℃以下的温度进行,尤其200℃或100℃以下。
所得产物PREITQ-6具有如图1所示的结晶固体X衍射图特征,而具有如表1所汇总的基部间隔及相对强度。
表1
d(_) | I/I<sub>0</sub>*100 | d(_) | I/I<sub>0</sub>*100 |
12.71±0.25 | mf | 3.55±0.07 | m |
12.00±0.24 | d | 3.47±0.07 | m |
7.31±0.14 | d | 3.37±0.07 | d |
7.07±0.14 | d | 3.33±0.07 | d |
6.93±0.14 | d | 3.22±0.06 | d |
6.47±0.13 | d | 3.13±0.06 | d |
6.12±0.12 | d | 3.08±0.06 | d |
5.82±0.12 | d | 3.01±0.06 | d |
5.61±0.11 | d | 2.95±0.06 | d |
4.97±0.10 | d | 2.91±0.06 | d |
4.86±0.10 | d | 2.88±0.06 | d |
4.75±0.10 | m | 2.84±0.06 | d |
4.60±0.09 | d | 2.76±0.06 | d |
4.38±0.09 | d | 2.71±0.05 | d |
4.26±0.09 | d | 2.62±0.05 | d |
4.09±0.08 | d | 2.52±0.05 | d |
3.93±0.08 | d | 2.47±0.05 | d |
3.78±0.08 | d | 2.43±0.05 | d |
3.69±0.07 | m | 2.38±0.05 | d |
3.64±0.07 | m | 2.26±0.05 | d |
如所周知,结晶硅酸盐材料的d间隔实际值可依诸如晶粒大小、Si/Al比及水合水平等因素而略有变化。这种变化通常在数值±2%内。因此,表1中数值12.71埃为12.71±0.25埃,故表1数值及以后的表2、3中那些数值也可表示为12.71、12.00、7.31等,而省略了±2%范围。
在此描述中,除非特意说明之外,X衍射峰的相对强度均以如下定义符号表示:
d....... 弱...... 0-20%相对强度
m....... 中等.... 20-40%
f....... 强...... 40-60%
mf.......很强.... 60-100%
一旦得到了PREITQ-6,就将该材料悬浮于一种溶液中使该材料溶胀或溶胀。该溶胀化溶液通常为水溶液,包括长链烃有机化合物(a)它可有质子接受基团,诸如带至少一个氧或氮原子的基团,例如含3以上至少8个链碳原子的季烷基铵、胺或醇,或季铵盐,另外,该溶液在pH超过10之前可含(b)一种数量受控的能对反应介质提供OH-的化合物,例如,诸如季烷基氢氧化铵或碱金属氢氧化物,诸如氢氧化钠。所用有机化合物(a)可以为任何胺或季烷基铵化合物,如辛基三甲基铵、十二烷基三甲基铵,但优选为十六烷基三甲基铵(CTMA+OH-)的如氢氧化物及/或氯化物及/或溴化物。该有机化合物可含1-4,如1个含8-30个诸如10-20个碳原于的长链基团,如十六烷基或十八烷基,和3-0个如3个短链基团,如烷基基团诸如带有1-7个碳原子的基团,如甲基或乙基。对反应介质提供氢氧化物的化合物优选是有机的,如有机季烷基氢氧化铵,尤其是带有至少1个,如1-4个,诸如4个含不多于8个如1-4个碳原子的烷基,如甲基、乙基、丙基或异丙基、或正丁基的基团;四烷基氢氧化铵,诸如四丙基氢氧化铵是优选的。
在制备溶胀化溶液之后,即将其与前述PREITQ6材料混合,尤其溶胀化溶液对PREITQ-6的重量比为4-200∶1如10-50∶1。连续搅拌优选用回流方法,保持所得悬浮液,优选温度在40-120℃,或80-110℃,时间不少于1小时如1-40小时诸如7-25小时,直至获得溶胀后材料。所得产物经用水充分洗涤后,在300℃以下的温度下进行干燥,优选在150℃以下干燥。经洗涤及干燥之后,该溶胀后材料具有如图2所示的X衍射图特征,其基部间隔及相对强度汇总于表2中。
表2
d(_) | I/I<sub>0</sub>*10 |
28.20±0.56 | mf |
14.45±0.29 | f |
9.81±0.20 | d |
6.46±0.13 | d |
4.31±0.09 | m |
4.10±0.08 | m |
3.93±0.08 | m |
3.65±0.07 | d |
3.49±0.07 | m |
2.87±0.06 | d |
2.62±0.05 | d |
如上所述,这些间隔d可表示为如28.20,而省略了±2%。
该溶胀后材料分离了片层,接着对该溶胀后材料片层进行分散。最后,在水/溶胀后材料重量比4-200∶1,优选在10-100∶1如20-60∶1范围之下制备出该溶胀后材料在水中的分散体系。将该悬浮体系在控制搅拌下进行处理,使该溶胀后材料受到至少部分分层。分层可采用机械方法,如带搅拌机或其它叶轮的强烈搅拌,采用如超声波电子器件、喷雾干燥或任何本领域已知的其它分层方法,或采用冷冻干燥法或这些方法的任意组合来完成,时间在0.5-100小时范围,优选1-20小时之间。至少部分分层导致处理最后时系统胶凝,使过滤困难明显增大。通常添加絮凝剂诸如酸类如HCl、醋酸或HNO3,以利于分散固粒的回收。分层之后,并在任何此后的酸处理后,对所得产物通常进行后来的水热(蒸汽)焙烧和任选的在氟或氟化合物存在下的后焙烧,或用磷化合物处理的阶段。因此,对在分层中所得的材料,尤其结合酸的絮凝作用,可在如80-150℃下干燥,然后在300-800℃之间温度下焙烧,优选在400-600℃温度范围,使所谓ITQ-6的产品增加。材料ITQ-6的X衍射图如图3所示,其基部间隔及相对强度汇总于表3中。
表3
d(_) | I/I<sub>0</sub>*100 |
9.50±0.19 | f |
7.10±0.14 | f |
6.62±0.13 | m |
5.68±0.11 | d |
3.97±0.08 | f |
3.73±0.07 | f |
3.53±0.07 | mf |
3.16±0.06 | m |
如上所述,这些d间隔可表示为如9.5,而省略了±2%。
ITQ-6具有层状特征,其片层具有由8-10员T原子环构成孔道的内微孔结构。该片层表面有比PREITQ6更高的外表面积。ITQ-6因有微孔部分和增高的外表面积而具有独特的结构性质。表4汇总了将BET方程用于焙烧后ITQ-6在液氮温度下的氮吸附等温线与未焙烧PREITQ6进行比较所获得的数值。由表可以看出,ITQ-6的外表面积比PREITQ-6的高8倍。
表4
S<sub>TOT</sub>(m<sup>2</sup>/g) | S<sub>MIC</sub>(m<sup>2</sup>/g) | S<sub>EXT</sub>(m<sup>2</sup>/g) | V<sub>TOT</sub>(cm<sup>3</sup>/g) | V<sub>MIC</sub>(cm<sup>3</sup>/g) | |
PREITQ6 | 278 | 225 | 53 | 0.1952 | 0.1126 |
ITQ6 | 512 | 78 | 434 | 0.6474 | 0.0340 |
表4中STOT为总表面积,SMIC为微孔表面积,为SEXT外表面积、VTOT为总孔容积,VMIC为微孔容积。表4中微孔按孔径小于15埃或1.5纳米定义。
本发明氧化物材料通常总表面积为至少400m2/g,诸如400-700,如450-650m2/g,尤其500至600m2/g以上如500-650m2/g。通常它的外表面积为至少350m2/g或至少380m2/g或至少400m2/g,诸如400至至少540,如400-500m2/g。通常其微孔表面积为至少20m2/g,但尤其至少40m2/g,如至少45或至少50m2/g,诸如50-200m2/g,如50-120或50-100m2/g,但尤其最多150或最多100m2/g。外(或内)表面积可以直接确定,或通过总表面积与内(或外)表面积之差分别加以确定。
本发明氧化物材料可用于有机反应的非均相催化剂。本发明也可包括一种包括本发明氧化物材料的催化剂组合物,如ITQ-6与催化活性过渡金属一起,如与第VA、VIA、VIIA、VIII族尤其V、Mo、W一起,或与第VIII族,如Ni、Co、Ru、Rh、Pd或Pt一起或与它们的各种组合一起;贵重金属是优选的。过渡金属量可以为该组合物重量的0.001-50%诸如0.1-5重量%(以金属表示)诸如1-40%如5-30%的族VIA金属及0.05-10%如1-7%的第VIII族金属。该金属优选是能够满足催化加氢功能的。催化剂组合物可以采用本领域众所周知的技术如浸渍法来制备。可将金属结合进或沉淀至该催化剂组合物的氧化物材料中。该催化剂组合物也可包括载体,尤其高表面积的载体,如总表面积至少250m2/g,诸如氧化铝、氧化硅、或氧化硅/氧化铝。可将金属结合进载体中或沉积到载体上。
本发明也提供一种包括本发明氧化物材料的催化剂组合物及一种与该氧化物材料进行混合的基质;该基质材料可以是活性的或无活性的材料,并可以是合成或天然形成的材料。可用于本发明催化剂组合物中的基质材料的实例包括黏土(如膨润土及高岭土)及无机耐热氧化物(如氧化硅、氧化铝、氧化镁、氧化钛、氧化锆、氧化硅-氧化铝、氧化硅-氧化镁、氧化硅-氧化钛、氧化硅-氧化锆、氧化硅-氧化钍、氧化硅-氧化铍、以及三元组合物如氧化硅-氧化铝-氧化钍、氧化硅-氧化铝-氧化锆、氧化硅-氧化铝-氧化镁,及氧化硅-氧化镁-氧化锆)。本发明氧化物材料与基质材料在该催化剂组合物中的相对比例变化范围宽。因此,例如,催化剂组合物可包括0.5-95%如1-80%的氧化物材料,和5-99.5%,优选20-99%的基质材料,所有的百分数均以该氧化物材料及基质的干重量的总重量为基准。优选的是,在与基质的后一催化剂组合物中,氧化物材料至少部分为呈酸形态的。
本发明催化剂组合物可用于烃类的许多转化方法。例如一种对烃类进料进行异构脱蜡的方法,包括将所述进料与本发明的上述催化组合物,在临氢条件下,在升高的温度下及压力下进行接触。还有例如一种对正烯烃催化异构化为分支链烯烃的方法,包括将所述正烯烃与本发明的上述催化剂组合物在升高的温度进行接触。还有例如一种烃类裂化的方法,包括将所述烃类与本发明的上述组合物,在有水蒸气或无水蒸气的存在下,在升高的温度及压力下进行接触。其中有烯烃如烷烯烃的骨架异构化为分支链的烯烃及烃,如烷烃,非临氢或临氢(加氢裂化)的裂化,尤其用其中氧化物材料至少部分呈酸形态的催化剂组合物,以及用于烃类脱蜡及异构脱蜡及用于裂化烃类的流化催化裂化(FCC)操作,如与包括过渡金属的催化剂组合物一起作为添加剂使用。受异构化的烯烃实例为有4-8个碳原子的正-烯烃,诸如正-丁烯及正-戊烯,异构化生成分支链的烯烃如异丁烯及异戊烯。异构化在升高温度下如至少200℃,诸如200-500℃,或300-500℃,和在诸如0.1-1MPa的压力下进行。在加氢裂化过程中烃可以是沸点较低的石油馏分诸如煤油或沸点较高的馏分,诸如减压馏分或常压馏分如常压或减压瓦斯油或残油,而且操作是在升高的温度下如在至少300℃如300-450℃和通常升高的压力下如1-20MPa的条件下进行的。VGO是优选的加氢裂化烃类,可以是那些含氮100或50ppm以下的VGO如HTVGO,或可以是一种有至少100ppm或至少0.05%N化合物的VGO,诸如未被加氢处理减低其N或S含量的瓦斯油。裂化可以在水蒸汽或基本无水蒸汽存在下进行,如水含量(按烃重量计)0-10%如0或0.1-10%诸如0.1-1%。
本发明的催化组合物也可与如作为反应中的添加剂、作为FCC催化剂组份或作为其中添加剂的组合物一起用于FCC操作。FCC操作及催化剂在本领域是众所周知的。该催化剂可以流动于上流或下流催化剂床中,如狄莫佛催化裂化(Thermofor Catalytic Cracking)或FCC过程。FCC反应通常在升高温度下,诸如400-900如450-800或500-650℃及升高压力诸如0.1-1MPa或0.2-0.75MPa和催化剂/进料油的重量比0.1-150∶1如20-100∶1下用流动的催化剂来完成。
本发明含过渡金属的催化剂也可用于进料烃类的脱蜡和进料烃类的异构脱蜡,即涉及将直链脂肪烃异构化为1-4个分支链烃类。进料烃的实例有8-30个碳原子诸如10-20个碳原子的直链烷烃,尤其润滑油馏分。
本发明催化剂组合物可改善进料油的转化率或对目的产物的选择性,如对来自异构化的支链烯烃,来自加氢裂化操作的沸点在410℃以下的裂化馏分,以及来自烃类异构脱蜡的分支链烷烃。例如,其对煤油及VGO的选择性高于用已知加氢处理催化剂,但这与加氢处理减压瓦斯油VGO,尤其未加氢过的VGO相关。
本发明通过下述实施例加以说明。
实施例1
(i)膨胀层状混合氧化物的制备
本实施例描述在初始凝胶中Si/Al原子比为5∶1的层状混合氧化物的制备。采用在压力釜中混合10克Si02(Aerosil 200,德古斯(Degussa)公司产品)、2.3克Al2O3(一水软铝石,Catapal B,威斯塔(Vista)公司,含73.7% Al2O3)、9.2克氟化铵(NH4F,阿德里奇(Aldrich)公司产品,纯度98%)、3.1克氢氟酸(HF,阿德里奇公司产品,浓度49.8%)、26克4-氨基-2,2,6,6-四甲基哌啶(氟鲁卡(Fluka)公司产品,纯度98%)和27.9克密利奇公司(MiliQ)的去离子水的方法制备该层状氧化物。,在环境温度下对所得pH8-9之间的合成凝胶剧烈搅拌保持1小时。再将所得混合物放入压力釜中,保持其温度175℃5天,5天结束时过滤所得产物,用3升去离子水洗涤至pH≤9,然后在炉中60℃下进行干燥。所得产物为层状材料(PREITQ6),其X衍射图如图1所示,基部间隔及相对强度汇总于表1中。
取所得层状材料(PREITQ-6)1克,用由20克CTMA+OH-(29%水溶液)、6克四丙基氢氧化铵(40%的TPA+OH-水溶液)及4克去离子水制备的一种水溶液进行交换。在95℃下对所得悬浮体系保持回流及剧烈搅拌16小时。最后,用水充分洗涤该悬浮体系,直至液相与所得固体分离。该溶胀层状材料(1.8克)的衍射图汇总于表1中。
(ii)本发明焙烧后层状材料的制备
将75毫升去离子水加至在实施例1(i)中所得的溶胀层状材料(1.8克)中,并对经层烈搅拌后所得的悬浮体系超声波处理1小时,超声频率50Hz,功率50瓦。此后进行离心(1200转/分,20分钟),重复4次,回收该溶液。然后于100℃下干燥所得固体材料16小时,并最后于580℃空气气氛中焙烧7小时,以获得本发明材料(1克),其衍射图形类似图3,基部间隔及相对强度汇总于表3中,按照BET方法以氮作为被吸附物测定的比表面积为450m2/g,按照t-线图法所得数据其中400m2/g相当于外表面积。
实施例2
重复实施例1方法,但不同的是,为获得Si/Al原子比30∶1的凝胶在(i)阶段所用的试剂量有变化。
在(ii)阶段结束时所得氧化物具有类似图3的X衍射图及如表3中的强度,总表面积在500m2/g以上(即562m2/g),外表面积超过400m2/g,(即485m2/g),内表面积为77m2/g。
实施例3
按照实施例2方法重复,但不同的是,只有一种结构原子源用于阶段(i)中,即硅与氧,而未添加铝源,因此,在第(ii)阶段结束时得到纯硅氧化物,没有酸性,产生的X衍射图及相对强度如图3及表3所示。这种纯氧化硅材料总表面积超过600m2/g,其中80-90%的面积相当于外表面积,10-20%面积相当于内表面积。
实施例4
按照实施例1方法重复,但不同的是,用6N HCl酸化(ii)阶段超声波处理后所得产物悬浮体系,以利于分离液相与固相之前对悬浮体系中的固体进行絮凝。
在该氧化物焙烧后,产物X衍射图类似于图3的,相对强度与表3所示相差无几。总比表面积为580m2/g,其中500m2/g相当于外表面积。
实施例5
按照实施例1方法重复,但不同的是,在进行超声波处理的(ii)阶段中,在焙烧处理之前对该悬浮体系进行冷冻干燥。
实施例6
重复实施例1所述方法第一阶段,制得一种溶胀层状氧化物,其X衍射图类似表2所示。
在第二阶段,加入去离子水(对1.8克氧化物材料加75毫升),并采用Cowles型搅拌器对系统连续搅拌,保持3小时。用6N HCl(pH≌2)酸化所得悬浮体系,用水洗涤及离心数次至最终pH≥6。经过滤、干燥及580℃焙烧之后,所得层状氧化物X衍射图类似表3,总表面积在500m2/g以上(外表面积>400m2/g,内表面积>100m2/g)。
实施例7
催化试验
ITQ-6样品,其Si/Al原子比=30∶1如按实施例2制备,用H2PtCl6加以浸渍,使之结合0.5重量%的铂(以金属计)。将最后的材料经500℃焙烧3小时后置于固定床反应器中,在十六烷存在下通入氢气(300毫升/分)进行还原,H2/正-十六烷摩尔比为50∶1。反应条件是:总压40大气压,反应温度在290-370℃范围。收集并分析反应器流出物,如图4及5所示所得结果表明,基于ITQ-6的催化剂适宜于进行烃类的异构脱蜡。图4中的方块、圆圈及三角形符号分别表示转化率、异构化率及裂化率。
表5
温度℃ | 转化率<sup>*</sup>% | 异构化率% | 裂化率% | 单分支% | 双分支% | 三分支% | 选择性% |
298 | 12.07 | 10.33 | 2.37 | 9.09 | 1.13 | 0.11 | 81.33 |
319 | 37.02 | 26.97 | 5.75 | 22.04 | 4.44 | 0.49 | 82.43 |
332 | 56.72 | 41.75 | 15.15 | 30.76 | 7.99 | 2.82 | 73.29 |
340 | 75.22 | 48.54 | 26.68 | 30.71 | 13.95 | 3.87 | 64.53 |
348 | 87.41 | 51.60 | 35.81 | 27.56 | 15.62 | 8.42 | 59.03 |
368 | 93.84 | 37.49 | 56.35 | 16.14 | 11.43 | 9.92 | 39.95 |
*:所有百分数均以摩尔百分数表示
表5中单分支%、双分支%和三分支%指的是在直链上有1、2及3个分支的烃类产物的百分数。
实施例8-10
催化剂
工业催化剂:
A工业NiMo加氢处理催化剂
B工业非贵重金属温和加氢裂化催化剂(CoMo)
C工业非贵重金属第二段加氢裂化催化剂
这三种催化剂,均为颗粒状,经研碎及过筛为粒度0.25-0.42的细粒。
催化剂D
重复实施例2的过程。用2M NH4Cl溶液(毫升溶液/克催化剂=16)在80℃下对焙烧后样品进行离子交换2小时。然后,对交换后的样品过滤及洗涤,脱除Cl-,并于100℃下干燥12小时。
该离子交换后样品经干燥后,将其与20重量%的γ-Al2O3(Merck公司)混合,并分两步用Ni及Mo加以浸渍。第一步浸渍按初湿法用12重量%的MoO3(如(NH4)6Mo7O24·4H2O,>99%,默克(Merck)公司)进行。将浸渍后样品于硅胶上干燥12小时,再于100℃下进一步干燥2小时。然后用3重量%NiO(如Ni(NO3)2 6H2O,>99%,默克公司)按初湿法进行第二步浸渍。再将样品于硅胶上干燥12小时,接着于100℃下干燥2小时。
最后在空气流(150毫升/分)中用程序升温方法以3℃/分由室温升至500℃对NiMoITQ-6焙烧,接着在500℃下保持3小时,然后令其冷却至室温。
将最后样品颗粒化、研碎及筛分至粒度为0.25-0.42毫米的范围。
该原生ITQ-6及最后催化剂的表面积及微孔孔径列于表6。ITQ-6的外表面积为576m2/g。
表6BET表面积(m2/g)
样品 | 总计 | 微孔 |
浸渍前ITQ-6 | 598 | 22 |
NiMo/(ITQ-6+20%γ-Al<sub>2</sub>O<sub>3</sub> | 324 | 46 |
进料
采用两种进料油C及D,即Ca(加州)减压瓦斯油和常规未处理过的直馏减压瓦斯油(∽370-530℃真沸点(TBP)切割)(VGO),其氮含量在500ppm以上,D是一种直馏VGO(∽370-530℃真沸点(TBP)切割)氢预处理至氮含量<20ppm(HTVGO)。
这些油的沸点范围分布经模拟蒸馏如下:
进料 | <140℃ | 140-240℃ | 240-380℃ | 380-410℃ | >410℃ |
VGO | 0.1 | 0.0 | 7.5 | 9.1 | 83.1 |
HTVGO | 0.8 | 3.1 | 18.0 | 11.0 | 67.0 |
反应系统及反应条件
反应在计算机控制的反应系统中完成。各进料储存于各单独的储罐中并于60℃下加热。用活塞泵将它们引入至系统中,并在进入固定床管式反应器之前通过一预热器,用带有三个独立加热器区的电炉加热。在反应器出口用另一罐收集液体样品,同时气体通过按“气体量累加器”使用的标定后质量流量计。反应在6MPa压力下进行,压力用Bader Meter 0ptipac阀来控制。
所用催化剂体积为10毫升,进料流率为10毫升/分,空速LHSV为1。
在催化剂床层以下采用4毫升的惰性CSi床(5毫米高)。
完成了下述试验:
催化剂(10毫升) | 催化剂重量(克) | 进料 | 温度(℃) |
空白试验 | - | VGO/HTVGO | 390,420 |
A | 7.91 | VGO/HTVGO | 370,390,420 |
B | 6.51 | VGO | 370,390,420 |
C | 8.14 | HTVGO | 370,390,420 |
D | 5.63 | VGO/HTVGO | 370,390,420 |
氢气流率为180毫升/分,气体流率为1000标立方米/立方米(nm3/m3),和LHSV=1。
反应前在液相中用轻直馏瓦斯油中1容积/容积%的二甲基硫醚(DMDS)按下述程序对催化剂进行预还原:
(a)175℃及3MPa下在氢气流(90毫升/分)中干燥催化剂2小时;
(b)开始泵入油流(第一小时为40毫升/时,以后为20毫升/时);
(c)提高反应器温度至230℃,并保持该温度直至H2S穿透(>1000ppm);
(d)提高反应器温度至300℃,并保持DMDS流过夜(约12小时)。
各种产物分析
气体:
用标定后流量控制器测定气体总量。气流中的烃组成在标绘-Al2O3毛细管柱(Plot-Al2O3 capillary column)中分离后用火焰电离检测器(FID)加以确定。氢含量采用连接热导池检测器的分子筛柱单独加以确定。H2S浓度用脉冲火焰光度检测器(PFPD)确定。
液体:
按照D2887 ASTM方法用连接FID的10米长WCOT Ultimetal柱进行模拟蒸馏,得出下述切割:Tb<140℃、140-240℃、240-380℃、380-410℃及Tb>410℃。
用元素分析确定液体的S及N的含量。这种分析器对S及N的灵敏度范围在0.2重量%。
结果
空白试验
在这些试验中,用10毫升CSi床替代反应器中的催化剂床。结果包括于表7中。
表7:空白试验
进料温度℃ | VGO390 | VGO420 | HT-VGO390 | HT-VGO420 |
H2S(wt%)C1+C2(wt%)C3(wt%)i-C4(wt%)n-C4(wt%)C5-140℃(wt%)140-240℃(wt%)240-380℃(wt%)380-410℃(w%)410℃+(wt%) | 0.00050.0200.0440.0000.0360.1460.5999.9859.98579.184 | 0.01090.0390.0410.0020.0350.9523.69315.97110.58168.675 | ----0.0030.0080.0000.0050.8143.79920.59412.09662.682 | ----0.0430.0930.0000.0581.1705.08623.03812.26758.244 |
C1-C4(wt%)C5-410℃(wt%)140-410℃(wt%) | 0.10020.71620.570 | 0.11731.19730.245 | 0.01637.30336.489 | 0.19541.56240.392 |
工业催化剂
对催化剂预硫化后,在各温度下对各进料分别进行反应直至达到稳定态。稳定建立之后,测定转化率及收率,接着将反应温度由370℃先升至390℃,后升至420℃,和取产品样进行分析。
表8表明用工业催化剂A及C在温度370、390及420℃下VGO反应所得稳定态的结果。
表8:NiMo加氢处理催化剂(A)与CoMo温和加氢裂化催化剂(B)的比较。
进料:未处理过的直馏VGO。
催化剂温度(℃) | A370 | A390 | A420 | B370 | B390 | B420 |
H2S(wt%)C1+C2(wt%)C3(wt%)i-C4(wt%)n-C4(wt%)C5-140℃(wt%)140-240℃(wt%)240-380℃(wt%)380-410℃(wt%)410℃+(wt%) | 1.500.170.100.010.060.643.3419.4213.0561.71 | 2.290.480.270.050.162.076.4725.6112.1850.44 | 2.281.020.550.100.315.0414.6137.7110.3128.07 | 1.430.220.130.020.080.691.8618.9214.1162.54 | 1.520.200.120.020.071.253.9222.7313.3356.83 | 1.830.930.600.130.336.2015.3339.5810.6424.44 |
C1-C4(wt%)C5-410℃(wt%)140-410℃(wt%) | 0.3536.4535.81 | 0.9546.3344.26 | 1.9967.6762.63 | 0.4535.5834.89 | 0.4241.2339.98 | 1.9871.7565.55 |
H2S(g/h)C1+C2(g/h)C3(g/h)i-C4(g/h)n-C4(g/h)C5-140℃(g/h)140-240℃(g/h)240-380℃(g/h)380-410℃(g/h)410℃+(g/h) | 0.12810.01460.00870.00130.00500.05460.28491.65911.11455.2706 | 0.19050.03950.02260.00380.01610.17250.53932.13311.01434.2019 | 0.18430.08240.04480.00840.02540.40831.18273.05340.83492.2726 | 0.12100.01820.01110.00170.00690.05790.15711.59551.19055.2744 | 0.11700.01540.00940.00160.00560.09600.30091.74521.02314.3631 | 0.14250.07210.04700.00980.02550.48241.19283.07890.82751.9010 |
总计(g/h)质量平衡 | 8.5413100.2324 | 8.30797.7604 | 8.097195.0198 | 8.434298.9752 | 7.677390.0931 | 7.779791.2949 |
%S(E.A.)%N(E.A.) | 2,00E-016,51E-02 | 4,73E-025,29E-02 | 01,98E-02 | 4,47E-027,60E-02 | 4,88E-036,80E-02 | 2,96E-01n.d |
加氢脱氮(%)加氢脱硫(%) | 92,3472,81 | 98,2578,80 | 100,0092,38 | 98,3168,72 | 99,8374,53 | 89,89n.d. |
沿催化床层检测温度分布,420℃时获得的最大温差为温差4℃。
用加氢处理的进料HTVGO所得的结果列于表9中。
表9:NiMo加氢处理催化剂(A)与第二段加氢裂化沸石催化剂(C)的比较。进料:HTVGO。
催化剂温度(℃ | A370 | A390 | A420 | C370 | C390 | C420 |
H2S(wt%)C1+C2(wt%)C3(wt%)i-C4(wt%)n-C4(wt%)C5-140℃(wt%)140-240℃(wt%)240-380℃(wt%)380-410℃(wt%)410℃+(wt%) | ----0.0650.0660.0170.0541.8966.97926.51913.55950.845 | ----0.1990.1720.0520.1182.7287.25027.31113.60648.564 | ----0.4040.2530.0640.1466.19315.44038.10611.18428.209 | ----0.5740.5190.3230.26712.01523.84832.4497.91722.089 | ----1.3721.1190.6560.49130.57338.20925.5681.3410.670 | ----2.9461.7741.1040.70954.07035.0404.0790.1850.093 |
C1-C4(wt%)C5-410℃(wt%)140-410℃(wt%) | 0.20248.95347.057 | 0.54150.89548.167 | 0.86770.92464.731 | 1.68176.23064.214 | 3.63995.69165.118 | 6.53393.37539.304 |
H2S(g/h)C1+C2(g/h)C3(g/h)i-C4(g/h)n-C4(g/h)C5-140℃(g/h)140-240℃(g/h)240-380℃(g/h)380-410℃(g/h)410℃+(g/h) | ----0.00530.00530.00140.00440.15450.56882.16131.10504.1438 | ----0.01550.01340.00410.00920.21220.56392.12431.05833.7775 | ----0.03380.02120.00540.01230.51891.29383.19300.93722.3637 | ----0.04800.04340.02700.02231.00611.99692.71700.66291.8496 | ----0.11130.09080.05320.03992.48063.10022.07460.10880.0544 | ----0.23310.14030.08730.05614.27772.77210.32270.01470.0073 |
总计(g/h)质量平衡 | 8.1499100.2201 | 7.778395.6502 | 8.3793103.0410 | 8.3732102.9660 | 8.113899.7767 | 7.911397.2861 |
ITQ-6
表10及11为用ITQ-6催化剂D与用加氢处理催化剂(A)及用温和加氢裂化催化剂(B)对VGO转化所得结果的比较,及另外与用加氢处理催化剂(A)及第二段加氢裂化催化剂(C)对HTVGO转化的比较。
由实施例8-10的这些结果可对催化剂A-D在三个温度下2种进料得出下述结论。
对于未处理过的VGO,并考虑产品的净产率÷净转化率,ITQ-6催化剂与催化剂A及催化剂B相比,得到了相同产生石脑油(bp120-380℃)及产生柴油(bp 120-380℃)的选择性,但对煤油(bp120-240℃)的选择性更高,对VGO(bp 380-410℃)的选择性较低(后者是有利的)。
对于处理后的HTVGO,并基于同样的考虑,ITQ-6与加氢裂化催化剂C相比得出了同样大小的对石脑油、煤油及柴油,以及对VGO的选择性。
表10:ITQ-6 D与NiMo加氢处理催化剂(A)及与CoMo温和加氢裂化催化剂(B)的比较。进料VGO
催化剂温度(℃) | A370 | A390 | A420 | B370 | B390 | B420 | D370 | D390 | D420 |
H2S(wt%)C1+C2(wt%)C3(wt%)i-C4(wt%)n-C4(wt%)C5-140℃(wt%)140-240℃(wt%)240-380℃(wt%)380-410℃(wt%)410℃+(wt%) | 1.500.170.100.010.060.643.3419.4213.0561.71 | 2.290.470.270.050.162.076.4725.6112.1750.44 | 2.281.020.550.100.315.0614.6637.8410.3528.17 | 1.430.220.130.020.080.691.8618.9214.1162.54 | 1.520.200.120.020.071.253.9222.7313.3356.83 | 1.830.930.600.130.336.2015.3339.5810.6424.44 | 0.7470.0130.0170.0000.0090.2131.29013.5909.92074.202 | 1.0920.0600.0340.0060.0200.5112.66717.48310.96467.165 | 1.3080.3720.2630.0540.1392.71310.94129.89310.45343.863 |
C1-C4(wt%)C5-410℃(wt%)140-410℃(wt%) | 0.3536.4535.81 | 0.9546.3344.25 | 2.0067.9162.85 | 0.4535.5834.89 | 0.4241.2339.98 | 1.9871.7565.55 | 0.03825.01324.800 | 0.11931.62431.113 | 0.82854.00051.287 |
%S(E.A.)%N(E.A.) | 2,00E-016,51E-02 | 4,73E-025,29E-02 | 01,98E-02 | 4,47E-027,60E-02 | 4,88E-036,80E-02 | 2,96E-01n.d. | 7,05E-011,11E-01 | 3,86E-011,17E-01 | 9,17E-021,12E-01 |
加氢脱氮(%)加氢脱硫(%) | 92,3472,81 | 98,2578,80 | 100,0092,38 | 98,3168,72 | 99,8374,53 | 89,89n.d. | 73,0153,86 | 86,4955,61 | 96,7056,04 |
表11,ITQ-6D与NiMo加氢处理催化剂(A)及与第二段加氢裂化催化剂(C)的比较。进料HTVGO.
催化剂温度(℃) | A370 | A390 | A420 | C370 | C390 | C420 | D370 | D390 | D420 |
H2S(wt%)C1+C2(wt%)C3(wt%)i-C4(wt%)n-C4(wt%)C5-140℃(wt%)140-240℃(wt%)240-380℃(wt%)380-410℃(wt%)410℃+(wt%) | ----0.0650.0660.0170.0541.8966.97926.51913.55950.845 | ----0.1990.1720.0520.1182.7287.25027.31113.60648.564 | ----0.4040.2530.0640.1466.19315.44038.10611.18428.209 | ----0.5740.5190.3230.26712.01523.84832.4497.91722.089 | ----1.3721.1190.6560.49130.57338.20925.5681.3410.670 | ----2.9461.7741.1040.70954.07035.0404.0790.1850.093 | ----0.040.140.050.101.836.4725.6812.0453.64 | ----0.170.410.220.253.249.5621.888.5855.69 | ----0.581.280.640.5410.5823.4032.166.7424.07 |
C1-C4(wt%)C5-410℃(wt%)140-410℃(wt%) | 0.20248.95347.057 | 0.54150.89548.167 | 0.86770.92464.731 | 1.68176.23064.214 | 3.63995.69165.118 | 6.53393.37539.304 | 0.3446.0244.19 | 1.0543.2640.02 | 3.0572.8862.30 |
Claims (25)
1.一种氧化物材料,其具有由下式表示的化学组成:(XO2)n(Y2O3)m(H2O)pM2m/v,式中X为Si,Y为Al,n为至少5,m基本为0或至少0.5,和p为0-3n,M表示价键数为v的阳离子,其特征在于其焙烧后形态的X射线衍射图包括如下表所示的数值,
d(_) I/I0*100
9.50±0.19 f
7.10±0.14 f
6.62±0.13 m
5.68±0.11 d
3.97±0.08 f
3.73±0.07 f
3.53±0.07 mf
3.16±0.06 m
d:弱,0-20%相对强度 m:中等,20-40%相对强度
f:强,40-60%相对强度 mf:很强,60-100%相对强度并具有通过N2吸附及脱附法确定的总表面积至少400m2/g及外表面积至少350m2/g的微孔和表面积特征。
2.按照权利要求1的氧化物材料,其中价键数为v的阳离子是氢和/或碱金属或碱土金属。
3.按照权利要求1的氧化物材料,其中总表面积至少450m2/g及外表面积至少400m2/g。
4.按照权利要求1的氧化物材料,其具有通过N2吸附及脱附法确定的微孔表面积至少20m2/g的表面积特征。
5.按照权利要求4的氧化物材料,其中微孔表面积至少50m2/g,和外表面积至少400m2/g。
6.按照权利要求1的氧化物材料,其中SiO2对Al2O3摩尔比为至少5∶1。
7.按照权利要求1的氧化物材料,其中Si对Al的原子比为至少5∶1。
8.按照权利要求7的氧化物材料,其中Si对Al的原子比大于10∶1。
9.按照权利要求1的氧化物材料,其中Si对Al的原子比在30-500的范围。
10.按照权利要求1的氧化物材料,其微孔表面积为50-100m2/g和其外表面积为450-600m2/g。
11.一种制备权利要求1的氧化物材料的方法,包括将一种具有下表所示基面间距及相对强度数值的前体层状氧化物材料转化成所述材料,
d:弱,0-20%相对强度 m: 中等,20-40%相对强度
f:强,40-60%相对强度 mf:很强,60-100%相对强度其中所述方法包括通过机械搅拌或超声波处理方法,对所述前体层状氧化物材料的溶胀产物进行至少部分分层,其中该前体层状氧化物材料是通过一种合成混合物的结晶而获得的,该合成混合物包括二氧化硅源、氟化物盐及氟化氢以及4-氨基-2,2,6,6-四甲基哌啶及水。
12.按照权利要求11的方法,其中所述溶胀产物已通过将所述前体层状氧化物材料悬浮在一种含有如下两种化合物(a)和(b)的溶胀溶液中获得:其中(a)是长链烃胺、含1-4个8-30个碳原子的长链的季烷基铵化合物或链中具有至少8个碳原子的醇,并且其中(b)是碱金属氢氧化物或具有1-4个少于8个碳原子的烷基的季烷基铵氢氧化物。
13.按照权利要求12的方法,其中该前体层状氧化物材料是被分散在包括十六烷基三甲基氢氧化铵及四丙基氢氧化铵的溶胀溶液中的。
14.按照权利要求11的方法,其中至少部分分层后接着进行酸处理。
15.一种催化组合物,其包括按照权利要求1的氧化物材料及至少任何一种催化活性的过渡金属。
16.按照权利要求15的一种组合物,它也包括一种载体。
17.按照权利要求16的一种组合物,其中的载体为氧化铝、二氧化硅、或二氧化硅和氧化铝。
18.按照权利要求15的组合物,其中的金属具有加氢效应。
19.按照权利要求15的组合物,其中的金属为Pt、Pd、Ru、Ni、Co、Mo、V、W、Rh或任意这些金属的混合物。
20.按照权利要求19的组合物,其中的金属是Pt。
21.按照权利要求19的组合物,其中的金属是Ni及Mo。
22.一种催化组合物,其包括按照权利要求1的氧化物材料及一种基质。
23.按照权利要求22的一种组合物,其中基质为耐热氧化物。
24.一种将正链烯烃催化异构化为分支链烯烃的方法,包括将所述正链烯烃与权利要求15或22的催化组合物在200-500℃的温度以及0.1-1MPa的压力下进行接触。
25.一种使烃类加氢裂化的方法,包括将所述烃类与权利要求15或22的催化组合物,在有水蒸气或无水蒸气的存在下,在300-450℃的温度以及1-20MPa的压力下进行接触。
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JP6741410B2 (ja) | 2015-09-25 | 2020-08-19 | 株式会社フジミインコーポレーテッド | 溶射用スラリー、溶射皮膜および溶射皮膜の形成方法 |
WO2017074898A1 (en) | 2015-10-28 | 2017-05-04 | Exxonmobil Research And Engineering Company | Methods and apparatus for converting oxygenate-containing feedstocks to gasoline and distillates |
CN110911699B (zh) * | 2019-12-06 | 2021-04-23 | 中国科学院宁波材料技术与工程研究所 | 一种双功能催化剂及其制备方法及其在锌空气电池中的应用 |
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CA1272999A (en) * | 1985-11-12 | 1990-08-21 | Guenter H. Kuehl | Crystalline layered and large pore catalytic material |
US4761391A (en) * | 1986-06-30 | 1988-08-02 | Union Oil Company Of California | Delaminated clays and their use in hydrocarbon conversion processes |
US5114895A (en) * | 1990-02-22 | 1992-05-19 | Uop | Alumina clay compositions |
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DE69229132T2 (de) * | 1991-07-09 | 1999-11-04 | Mitsubishi Heavy Ind Ltd | Katalysator und Verfahren zur Reinigung von Abgasen |
US5266541A (en) * | 1991-12-20 | 1993-11-30 | Mobil Oil Corp. | Crystalline oxide material |
ES2124154B1 (es) * | 1995-11-08 | 1999-12-01 | Univ Politecnica De Valencia C | Metodo de preparaciion y propiedades cataliticas de un solido microporoso con alta superficie externa. |
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1999
- 1999-08-04 DK DK99936880T patent/DK1102630T3/da active
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- 1999-08-04 EA EA200100178A patent/EA004799B1/ru not_active IP Right Cessation
- 1999-08-04 PT PT99936880T patent/PT1102630E/pt unknown
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- 1999-08-04 AU AU51850/99A patent/AU742902B2/en not_active Ceased
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- 1999-08-04 CN CNB998117501A patent/CN100374202C/zh not_active Expired - Fee Related
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- 1999-08-04 BR BRPI9912641-9A patent/BR9912641B1/pt not_active IP Right Cessation
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CN85106482A (zh) * | 1984-09-10 | 1987-03-18 | 米德雷克斯鹿特丹国际公司苏黎世分公司 | 高级烃类的重整 |
US4844790A (en) * | 1986-06-30 | 1989-07-04 | Union Oil Company Of California | Hydrocarbon conversion processes using delaminated clay catalysts |
Also Published As
Publication number | Publication date |
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DE69903562D1 (de) | 2002-11-21 |
PT1102630E (pt) | 2003-03-31 |
DK1102630T3 (da) | 2003-02-17 |
EA004799B1 (ru) | 2004-08-26 |
BR9912641B1 (pt) | 2010-07-13 |
AU5185099A (en) | 2000-02-28 |
ATE226110T1 (de) | 2002-11-15 |
JP2002522329A (ja) | 2002-07-23 |
EP1102630B1 (en) | 2002-10-16 |
EP1102630A1 (en) | 2001-05-30 |
DE69903562T2 (de) | 2003-02-20 |
BR9912641A (pt) | 2001-05-02 |
ID27427A (id) | 2001-04-05 |
NZ509624A (en) | 2003-03-28 |
WO2000007722A1 (en) | 2000-02-17 |
ES2186391T3 (es) | 2003-05-01 |
EA200100178A1 (ru) | 2001-08-27 |
US6469226B1 (en) | 2002-10-22 |
AU742902B2 (en) | 2002-01-17 |
CN1322150A (zh) | 2001-11-14 |
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