CN1227770A - 用含有改进的β－沸石的催化剂使芳烃烷基化 - Google Patents
用含有改进的β－沸石的催化剂使芳烃烷基化 Download PDFInfo
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- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
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- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
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- B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明公开了一种新型β－沸石催化剂，其用于芳香化合物的烷基化和烷基转移时表现出明显高的稳定性和更高的催化剂寿命。该新型表面改性的β－沸石的特征在于通过X射线光电子能谱测量其表面铝的2p结合能为至少74.8电子伏特。通过在pH在约0和约2之间和温度最高至约125℃下用酸处理模板化的β－沸石足够长时间以改变表面铝原子的化学环境而不导致β－沸石脱铝制备该表面改性的β－沸石。
Description
本申请涉及一种新型的β-沸石催化剂及其在芳烃烷基化中的应用。更具体地，本申请涉及一种β-沸石，其用于芳烃的烷基化和烷基转移时稳定性和催化剂寿命明显提高。预计本发明催化剂可能在用丙烯使苯烷基化生产枯烯中特别有价值。为便于说明，以下描述将具体参考本发明催化剂在用丙烯使苯烷基化提供枯烯中的应用，但应认识到这样做仅仅是为了清楚和简便之目的。
枯烯是一种主要的工业产品，主要用途之一是利用其空气氧化和中间体过氧化物随后的酸催化分解而成为酚和丙酮的来源，
由于苯酚和丙酮都是重要的商用化学物质，所以一直很注重枯烯的制备，文献中有很多关于其制备方法的报道。最常用或许最直接的枯烯制备方法是用丙烯使苯烷基化，特别是使用酸性催化剂。参见“Encyclopedia of ChemicalProcessing and Design,”J.J.McKetta and W.A.Cunningham,Editors,V.14,pp33-51(1982)。虽然丙烯的转化率高和单烷基化产物的选择性高是任何工业可行方法的两个主要的先决条件，但也必须满足其它约束。
苯与丙烯反应的主要方向对应于马科尼科夫加成产生枯烯。然而，发生少但很明显量的反应通过反马科尼科夫加成而提供正丙基苯(NPB)。生成NPB的重要性是其影响枯烯氧化成苯酚和丙酮，因此用于氧化的枯烯对于NPB的含量必须相当纯。由于枯烯和NPB很难通过常规方法(如蒸馏)分离，所以通过苯的烷基化生产枯烯的一个约束是生成的正丙基苯相对于枯烯最少。关于烷基化的此方面的观察结果是生成NPB的相对量随着温度的增加而增加。因此，从使NPB生成最少的观点出发，希望在尽可能低的温度下进行烷基化。换言之，使NPB最少要求避免高反应温度。
至于芳烃烷基化中所用催化剂，从设计连续法的角度出发，固体酸催化剂是相当理想的。在这里不必列举芳烃烷基化中所用固体酸催化剂；只要说有很多描述而且这些沸石催化剂已受到关注足以。不论使用何种催化剂，失活是不可避免而应尽可能减少的特征。对于沸石催化剂，失活通常是由于多烷基化产物在催化剂表面和沸石通道内积聚所致，已观察到失活速率随反应温度增加而降低。因此，为使催化剂失活最少一般建议在相对高的反应温度下进行烷基化。因此，显然企图通过在高温下进行反应降低催化剂失活与企图通过在低温下进行反应减少NPB的生成相矛盾。
用于例如枯烯生产的所需最佳催化剂是对于在足够低以避免生成不可接受的NPB的温度下以可接受的反应速率进行烷基化有足够的活性同时表现出通常与较高反应温度相联的慢催化剂失活的催化剂。由于β-沸石明显比其它沸石的活性高，已对其在芳烃烷基化中作为催化剂进行了详细的研究；参见US-4891458；US-A-5030786和EP-A-432814。然而，发现所述的β-沸石在使NPB生成最少所需的低温下仍以不可接受的高速率失活。为使基于β-沸石的工业方法变得可行，首先必须增加催化剂活性-即在给定温度下增加枯烯生产速率，或降低催化剂失活-即增加催化剂寿命以增加催化剂再生之前枯烯的生产。本发明的目的是要改进天然β-沸石以提供相对于其它β-沸石失活降低的催化剂。
本发明中所用原理是假设催化剂失活是由芳烃的多烷基化所致，或许有一小部分是由低聚所致，特别是当丙烯浓度相当高时。还假设多烷基化物(和其它失活物质)主要是由于沸石表面上的强酸位而生成。从而得出结论：除去沸石表面上的较强酸位，特别是将强酸位转化成在产生失活物质中无效或作用较小的较弱酸位，可减少失活物质的形成。现在我们已发现用低浓度的强无机酸处理模板β-沸石，然后焙烧，可提供优异的β-沸石催化剂。处理的次序很重要；酸洗焙烧后的β-沸石无效！此外，我们相信我们的处理仅影响表面酸位的性质，由硅：铝表面比不变和X射线光电子能谱测量的表面铝2p结合能改变可见。
本发明的目的是提供一种在用烯烃使芳烃烷基化中有活性且在给定温度下失活速率低于常规β-沸石的改进的β-沸石催化剂。实施方案包括一种焙烧后的、未模板化的表面改性的β-沸石，通过X射线光电子能谱测量其表面铝的2p结合能为至少74.8电子伏特。另一实施方案包括上述表面改性的β-沸石的制备方法，该方法包括在pH为约2和70℃下用硝酸和硝酸铵处理模板化的β-沸石约3小时，然后在550至700℃的温度下焙烧所述酸处理过的β-沸石。本发明的另一方面涉及利用上述表面改性的β-沸石催化用烯烃使芳烃烷基化。在具体的实施方案中，烯烃是丙烯，芳烃是苯。在另一实施方案中，烯烃是洗涤剂用烯烃。在再另一实施方案中，烯烃有8至16个碳原子。
本发明源于必须在尽可能低的温度下催化用丙烯使苯选择性单烷基化同时保持作为催化剂的β-沸石在明显更高的温度下所表现出的低失活速率。产生后发现本发明适用于全体芳烃被烯烃的烷基化。本发明的关键是β-沸石的表面改性以降低多烷基化(它是导致催化剂失活的主要因素)和低聚(它是导致催化剂失活的次要因素)所必需的表面酸性，同时保留催化所要的芳烃的选择性单烷基化所需的酸位。本发明不仅适用于芳烃的选择性单烷基化，而且适用于多烷基化芳烃的烷基转移。
在由本发明表面改性的β-沸石催化的用烯烃使芳烃选择性单烷基化中，所述烯烃可含有2到至少20个碳原子，可以是支链或直链烯烃，端或内烯烃。因此，烯烃的特性不很重要。烷基化作用的共性是在至少部分液相的条件下进行反应，对于低级烯烃通过调节反应压力很容易实现。在低级烯烃中，乙烯和丙烯是最重要的代表。其余烯烃中，洗涤剂用范围的烯烃是特别感兴趣的。该类由内或端不饱和的含有6至约20个碳原子的直链烯烃构成。含有8至16个碳原子的直链烯烃特别适用作洗涤剂范围的烯烃，尤其优选含有10至约14个碳原子的。
苯是可用于实施本发明的可烷基化芳香化合物中最重要的代表。更一般地，所述芳香化合物可选自苯、萘、蒽、菲及其取代衍生物。可烷基化芳香化合物的芳环上发现的最重要的一类取代基是含有1至20个碳原子的烷基部分。另一类重要的取代基是羟基部分及烷氧基部分，其烷基也含1至20个碳原子。当取代基为烷基或烷氧基时，苯基部分也可被取代在石蜡链上。虽然未取代和单取代的苯、萘、蒽和菲最常用于实施本发明，但多取代的芳烃也可使用。除上述之外适合的可烷基化芳香化合物的例子包括联苯、甲苯、二甲苯、乙苯、丙苯、丁苯、戊苯、己苯、庚苯、辛苯等；苯酚、甲酚、茴香醚、乙氧基-、丙氧基-、丁氧基-、戊氧基-、己氧基苯等。
在本发明用表面改性的β-沸石催化可烷基化芳香化合物的选择性单烷基化中，进行反应的具体条件取决于所用的芳香化合物和烯烃。由于反应在至少部分液相的条件下进行，所以调节反压力以保持烯烃至少部分地溶解在液相中。对于高级烯烃，反应可在自生压力下进行。实际上，压力一般在200和1000psig(1480-6996kPa)之间的范围内，但通常在约300-600psig(2171-4241kPa)之间的范围内。但我们再次强调压力不是关键的变量，只需保持至少部分液相的条件足以。代表性的烷基化温度包括：对于用乙烯使苯烷基化在200-250℃之间的范围内，对于用丙烯使苯烷基化在90-200℃的范围内。用C2-C20烯烃使本发明的可烷基化芳香化合物烷基化适合的温度范围在60和400℃之间，最常用的温度范围在90和250℃之间。
本发明方法中所用可烷基化芳香化合物与烯烃之比将取决于所要求的选择性单烷基化度及反应混合物的芳烃和烯烃组分的相对成本。对于用丙烯使苯烷基化，苯与烯烃之比可在约1和约10之间，优选2.5-8。用乙烯使苯烷基化时，苯与烯烃之比优选在约1∶1和8∶1之间。对于洗涤剂用的C6-C20烯烃，苯与烯烃之比在5∶1至30∶1之间一般足以保证所要求的单烷基化选择性，更优选在8∶1和20∶1之间。
本发明表面改性的β-沸石还可用于催化烷基转移及烷基化。“烷基转移”意指芳环上的烷基在分子间被转移至第二芳环的方法。本文特别感兴趣的烷基转移是多烷基化的芳香化合物的一或多个烷基转移至未烷基化的芳香化合物的烷基转移，例如二异丙基苯与苯反应得到两分子枯烯。因此，烷基转移通常用于通过使烷基化期间必然生成的多烷基化物与未烷基化的芳烃反应生成附加的单烷基化产物增加所要选择性单烷基化的选择性。为此，多烷基化芳香化合物是在如上所述的用烯烃使可烷基化芳香化合物烷基化中生成的，未烷基化的芳香化合物是苯、萘、蒽和菲。烷基转移的反应条件与烷基化相似，温度在100至250℃的范围内，压力在100至750psig(791至5276kPa)的范围内，未烷基化芳烃与多烷基化芳烃之摩尔比在1至10的范围内。可与例如作为未烷基化芳烃的苯反应的多烷基化芳烃的例子包括二乙苯、二异丙苯、二丁苯、三乙苯、三异丙苯等。
本发明的催化剂是表面改性的β-沸石，由酸洗模板化的天然β-沸石得到。即形成表面改性的β-沸石始于模板化的β-沸石，其中模板为例如四烷基铵盐，如四乙铵盐。关键是酸洗模板化的β-沸石以保护沸石的内位并防止脱铝。在约0至2之间的pH下用强酸处理模板化的β-沸石，但优选pH低于1。可使用的酸包括硝酸、硫酸、磷酸等。例如，弱的0.01摩尔硝酸可与硝酸铵一起用于进行酸洗，但优选更高浓度、最高至20％(重)的硝酸。硝酸是优选的酸，因为它是非配位的酸，因而不促进脱铝。用强酸处理模板化的β-沸石可在20至125℃的温度下进行。重要的是在不导致脱铝的条件下进行酸洗。
进行酸洗的时间与温度很有关。如上所述，形成本发明表面改性的β-沸石中关键在于沸石没有明显的本体脱铝。因此，一般来说酸洗应进行不足以导致脱铝的时间。例如，在70℃下使用0.01摩尔硝酸和约40％硝酸铵，接触时间为2-3小时足够改变表面铝的环境而不导致明显的本体脱铝。在85℃用约15％的硝酸与硝酸铵处理约25％的浆液，90分钟的处理是有效的。在酸洗中相关变量包括酸浓度、浆液浓度、时间和温度，本领域技术人员很容易确定可制备表面改性的β-沸石而不明显本体脱铝的适合条件。
然后在550-700℃的温度下焙烧除去模板剂。焙烧条件为本领域所公知，在此不需详细说明。还需提仍粉末沸石本身不常用。因此，在更通常的情况下，模板化沸石酸洗后，与常规粘合剂混合，挤出，最后将挤出物焙烧。但应理解本发明制备方法的关键部分是按上述酸洗模板化的β-沸石。正如本文中所见，酸洗焙烧后的(即未模板化的)β-沸石不能提供本发明表面改性的材料。
已发现如上所述处理后，表面的铝原子被化学改性。据信此改性是催化剂表面的强酸位被弱酸位取代。然而，显然这只是假设，本发明的成功不建立在其上。已明确观察到的是通过X射线光电子能谱测量的本发明改性β-沸石的表面铝的2p结合能为至少74.8电子伏特。
本发明用烯烃使可烷基化化合物烷基化可列举用丙烯使苯烷基化。此烷基化可以本领域公知的任何方式进行。例如，该方法一般可通过在搅拌的高压釜中在60和400℃之间的温度下和在足以保持至少部分液相的压力下加热催化剂、芳烃和烯烃以间歇方式进行。压力典型地在200至1000psig(1481至7001kPa)的范围内，但仅用于保证至少部分液相反应。
然而，该方法更利于使用以上流或下流方式操作的固定床反应器或使用并流或逆流催化剂和烃流操作的移动床反应器以连续方式进行。反应器还可含有一或多个催化剂床，可配备有级间添加烯烃和级间冷却装置。级间烯烃添加确保更接近恒温操作，并趋于增加产品质量和催化剂寿命。移动床反应器提供从再生区中连续除去废催化剂和置换新鲜或再生的催化剂的优点。然而，也可用变换床反应器实施本发明。
以用丙烯使苯烷基化为例，用固定床反应器进行连续的烷基化。苯和丙烯可在90和160℃之间的温度下加入反应器中。总的苯与丙烯之比可在2和10之间，但一般在2.5和8之间。原料可上流或下流通入，但下流方式更常用。一般使用200-500psig(1418-3551kPa)的压力，苯的流速在10hr-1LHSV的区域内。
以下实施例仅用于说明而不以任何方式限制。
实施例1
酸洗β-沸石的制备。将工业β-沸石(SiO2 92.2wt％、Al2O3 7.0wt％、LOI24.3wt％和N2 BET 672m2/g)(以下实施例中称为试样A)在650℃下空气中焙烧2小时。向在3224g蒸馏水中的1428g硝酸铵溶液中加入932g 70wt％的硝酸，将混合物加热至85℃。加入焙烧后的β-沸石(干重1416g)，将此混合物在85℃下搅拌90分钟。过滤浆液，用10L蒸馏水洗涤，然后在100℃干燥16小时。分析表明SiO2/Al2O3之摩尔比为137,SiO2 96.8wt％,Al2O3 1.2wt％,N2 BET表面积720m2/g。该试样在以下实施例中称为试样B。
基本上如试样B所述制备试样C，但使用的硝酸少10％(839g 70％的硝酸)。分析表明SiO2 93.6wt％,Al2O3 1.5wt％,SiO2/Al2O3之摩尔比为105，表面积689m2/g。
基本上如试样B所述制备试样D和E，但用未焙烧的β-沸石粉末作为原料。焙烧之前酸处理过的原料对应于试样D；酸处理后焙烧的材料(650℃空气中3小时)对应于试样E。对E分析表明SiO2 91.7wt％,Al2O3 6.1wt％,SiO2/Al2O3之摩尔比为25.5。
用X射线光电子能谱(XPS)测定试样的结合能及表面硅∶铝原子比。结果示于表1中。
表1
| 峰 | 结合能(eV) | ||||
| A | B | C | D | E | |
| Al2p | 74.65 | 74.18 | 74.13 | 74.07 | 75.20 |
| Si2p | 103.30 | 103.30 | 103.30 | 103.30 | 103.30 |
| C1s | 284.48 | 285.18 | |||
| C1s | 286.80 | 286.44 | |||
| C1s | 288.80 | ||||
| O1s | 530.52 | ||||
| O1s | 532.53 | 532.44 | 532.45 | 532.47 | 532.43 |
| 表面浓度(原子％) | |||||
| Al | 1.83 | 0.41 | 0.35 | 1.44 | 1.93 |
| Si | 26.66 | 30.99 | 31.88 | 24.28 | 29.91 |
| Si/Al(本体) | ≈15 | ≈68 | ≈53 | ≈15 | ≈13 |
| Si/Al(XPS) | 15 | 76 | 91 | 17 | 16 |
Si2p和O1s的结合能是高硅沸石的特征。值得注意的是对比试样A的Al2p结合能比所有酸洗试样的高约0.5eV。这表明前一试样中的铝最可能是在骨架中。所有酸洗试样的Al2p结合能约74.1eV是游离氧化铝的特征。还值得注意的是酸洗和焙烧过的试样E的Al2p结合能比对比试样高约0.5eV。还可见表面和本体的Si/Al比在与非常低的Al浓度的测量相关的不可靠性内近似相同。
这些数据表明表面铝浓度不相对于本体铝浓度降低(即没有表面脱铝)，还表明表面铝的性质已经改变。
实施例2
利用各种β-沸石用丙烯使苯烷基化。在所有情况下，用于反应器试验的上述试样均与氧化铝粘合(70/30 沸石/粘合剂)，挤出(1.6mm挤出物)，干燥，然后在650℃焙烧2小时。每次试验中，均将10cc的1.6mm挤出物装入反应器中形成直径12.7mm、长95.3-101.6mm的床。在140℃、500psig(3549kPa)和6hr-1苯LHSV下将苯气流通过催化剂，使催化剂活化。将温度调节至要求的试验温度，进料切换至6wt％丙烯在6LHSV苯中的混合物。记录床中最高温度的位置(由于放热反应)。在试验条件下48小时后记录最高温度的位置确定失活。用这两个位置之差除以床长，再除以时间间隔(天)，计算失活。结果乘以100％得到催化剂床/天的失活率％。
先焙烧β-沸石粉末然后酸洗制备两个催化剂试样(Ⅰ,Ⅱ)在130℃下试验。试样Ⅰ和Ⅱ类似于前一实施例中的试样B和C。两种催化剂均在48小时的试验周期结束之前出现丙烯穿透，导致100％失活或＞50％/天。本发明的催化剂Ⅲ，与前一实施例的试样E相似，在130℃下进行试验，结果示于下表中。催化剂 失活(％/天)Ⅰ ＞50Ⅱ ＞50Ⅲ 10.3
在尽可能相同的实验条件下得到的这些结果明确地证明了本发明催化剂的极大优越性。
Claims (10)
1．一种焙烧后的、未模板化的表面改性的β-沸石，特征在于通过X射线光电子能谱测量其表面铝的2p结合能为至少74.8电子伏特。
2．权利要求1的表面改性的β-沸石的制备方法，包括在pH在约0和约2之间和温度最高至约125℃下用酸处理模板化的β-沸石足够长时间以改变表面铝原子的化学环境而不导致β-沸石脱铝，然后在550至700℃的温度下焙烧所述酸处理过的β-沸石。
3．芳烃的单烷基化方法，包括在权利要求1的焙烧后的、未模板化的表面改性的β-沸石催化剂存在下，使烯烃与1至30摩尔比的可烷基化芳香化合物在烷基化条件下和在至少部分液相条件下反应。
4．权利要求3的方法，其中所述烯烃含有2至20个碳原子。
5．权利要求3的方法，其中所述可烷基化芳香化合物选自苯、萘、蒽、菲、及其取代衍生物。
6．权利要求3的方法，其中所述烷基化条件包括温度60至400℃，反应压力最高至1000psig。
7．烷基转移方法，包括在权利要求1的焙烧后的、未模板化的表面改性的β-沸石催化剂存在下，使多烷基化芳香化合物与未烷基化芳香化合物在烷基转移反应条件下反应，其中至少一个烷基从所述多烷基化芳香化合物转移至所述未烷基化芳香化合物。
8．权利要求7的方法，其中所述多烷基化芳香化合物的烷基含有约2至约20个碳原子。
9．权利要求7的方法，其中所述未烷基化芳香化合物选自苯、萘、蒽、菲、及其取代衍生物。
10．通过用丙烯使苯烷基化制备枯烯的方法，包括在权利要求1的焙烧后的、未模板化的表面改性的β-沸石催化剂存在下，使丙烯与2至10摩尔比的苯在90和200℃之间的温度下在足以保持至少部分液相的压力下反应。
Priority Applications (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/682,862 US5723710A (en) | 1996-07-12 | 1996-07-12 | Zeolite beta and its use in aromatic alkylation |
| EP98301526A EP0940178B1 (en) | 1996-07-12 | 1998-03-02 | Aromatic alkylation with a catalyst containing a surface-modified zeolite beta |
| ES98301526T ES2200273T3 (es) | 1996-07-12 | 1998-03-02 | Alquilacion aromatica con un catalizador que contiene una zeolita beta modificada superficialmente. |
| ZA981716A ZA981716B (en) | 1996-07-12 | 1998-03-02 | Aromatic alkylation with a catalyst containing an improved zeolite beta |
| PT98301526T PT940178E (pt) | 1996-07-12 | 1998-03-02 | Alquilacao arometica com um catalisador contendo um zeolito beta de superficie modificada. |
| DE69814814T DE69814814T2 (de) | 1996-07-12 | 1998-03-02 | Alkylierung von aromatischen Verbindungen mit einem Katalysator, der ein oberflächenmodifiziertes Beta-Zeolith enthält |
| AT98301526T ATE240785T1 (de) | 1996-07-12 | 1998-03-02 | Alkylierung von aromatischen verbindungen mit einem katalysator, der ein oberflächenmodifiziertes beta-zeolith enthält |
| CA002230772A CA2230772A1 (en) | 1996-07-12 | 1998-03-02 | Aromatic alkylation with a catalyst containing an improved zeolite beta |
| DK98301526T DK0940178T3 (da) | 1996-07-12 | 1998-03-02 | Aromatisk alkylering med en katalysator indeholdende en overflademodificeret beta-zeolit |
| CN98106935A CN1227770A (zh) | 1996-07-12 | 1998-03-03 | 用含有改进的β－沸石的催化剂使芳烃烷基化 |
| JP10050882A JPH11267511A (ja) | 1996-07-12 | 1998-03-03 | 改良ゼオライト・ベータを含む触媒による芳香物のアルキル化 |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/682,862 US5723710A (en) | 1996-07-12 | 1996-07-12 | Zeolite beta and its use in aromatic alkylation |
| EP98301526A EP0940178B1 (en) | 1996-07-12 | 1998-03-02 | Aromatic alkylation with a catalyst containing a surface-modified zeolite beta |
| ZA981716A ZA981716B (en) | 1996-07-12 | 1998-03-02 | Aromatic alkylation with a catalyst containing an improved zeolite beta |
| CA002230772A CA2230772A1 (en) | 1996-07-12 | 1998-03-02 | Aromatic alkylation with a catalyst containing an improved zeolite beta |
| CN98106935A CN1227770A (zh) | 1996-07-12 | 1998-03-03 | 用含有改进的β－沸石的催化剂使芳烃烷基化 |
| JP10050882A JPH11267511A (ja) | 1996-07-12 | 1998-03-03 | 改良ゼオライト・ベータを含む触媒による芳香物のアルキル化 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1227770A true CN1227770A (zh) | 1999-09-08 |
Family
ID=31950880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98106935A Pending CN1227770A (zh) | 1996-07-12 | 1998-03-03 | 用含有改进的β－沸石的催化剂使芳烃烷基化 |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US5723710A (zh) |
| EP (1) | EP0940178B1 (zh) |
| JP (1) | JPH11267511A (zh) |
| CN (1) | CN1227770A (zh) |
| AT (1) | ATE240785T1 (zh) |
| CA (1) | CA2230772A1 (zh) |
| DE (1) | DE69814814T2 (zh) |
| DK (1) | DK0940178T3 (zh) |
| ES (1) | ES2200273T3 (zh) |
| PT (1) | PT940178E (zh) |
| ZA (1) | ZA981716B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675613A (zh) * | 2018-12-29 | 2019-04-26 | 浙江工业大学 | 一种选择性去除分子筛催化剂外表面酸中心的方法 |
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| US5962759A (en) * | 1996-02-12 | 1999-10-05 | Uop Llc | Minimizing diphenylethane formation in alkylation of benzene by ethylene catalyzed by zeolite beta |
| US6153806A (en) * | 1996-02-12 | 2000-11-28 | Uop Llc | Minimizing diphenylethane formation in alkylation of benzene by ethylene catalyzed by zeolite beta |
| US6162416A (en) | 1996-07-12 | 2000-12-19 | Uop Llc | Zeolite beta and its use in aromatic alkylation |
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| KR100531066B1 (ko) * | 1999-02-27 | 2005-11-25 | 유오피 엘엘씨 | 제올라이트 베타 촉매를 사용한 올레핀에 의한 방향족의 알킬화에 있어서 디아릴알칸 부산물 형성의 조절 방법 |
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| DE60220322T2 (de) * | 2002-03-21 | 2008-01-17 | Council Of Scientific & Industrial Research | Verfahren zur herstellung von dimethylcumolen |
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| ES2206030B1 (es) * | 2002-07-11 | 2005-08-01 | Universidad Politecnica De Valencia | Un catalizador zeolitico para alquilacion de compuestos aromaticos con olefinas, alcoholes o compuestos aromaticos polialquilados. |
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| EP1780786A4 (en) * | 2004-06-07 | 2009-11-25 | Nikon Corp | STAGE DEVICE, EXPOSURE DEVICE AND EXPOSURE METHOD |
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| US7348465B2 (en) * | 2005-02-08 | 2008-03-25 | Shell Oil Company | Selective alkylation of aromatic hydrocarbons |
| JP5322307B2 (ja) * | 2006-05-08 | 2013-10-23 | エクソンモービル・ケミカル・パテンツ・インク | 改善された触媒組成物 |
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| US7727490B2 (en) * | 2007-08-17 | 2010-06-01 | Uop Llc | Aromatic production apparatus |
| US7686946B2 (en) * | 2007-08-17 | 2010-03-30 | Uop Llc | Method of altering a feed to a reaction zone |
| CN101784507A (zh) * | 2007-08-22 | 2010-07-21 | 埃克森美孚化学专利公司 | 仲丁基苯的制备方法 |
| EP2098498A1 (en) | 2008-03-04 | 2009-09-09 | ExxonMobil Chemical Patents Inc. | Selective oligomerization of isobutene |
| US8865958B2 (en) * | 2008-09-30 | 2014-10-21 | Fina Technology, Inc. | Process for ethylbenzene production |
| WO2010042269A1 (en) | 2008-10-10 | 2010-04-15 | Exxonmobil Chemical Patents Inc. | Process for producing phenol and methyl ethyl ketone |
| US8440864B2 (en) * | 2008-10-10 | 2013-05-14 | Exxonmobil Chemical Patents Inc. | Process for producing sec-butylbenzene |
| US8450232B2 (en) * | 2009-01-14 | 2013-05-28 | Lummus Technology Inc. | Catalysts useful for the alkylation of aromatic hydrocarbons |
| US8455383B2 (en) * | 2009-09-28 | 2013-06-04 | Fina Technology, Inc. | Process for catalyst regeneration and extended use |
| US8350111B2 (en) * | 2010-10-12 | 2013-01-08 | Uop Llc | Method for producing cumene |
| US20140100401A1 (en) | 2011-05-09 | 2014-04-10 | Saudi Basic Industries Corporation | Catalyst for the alkylation of aromatic hydrocarbons |
| US8841500B2 (en) * | 2011-11-08 | 2014-09-23 | Chevron U.S.A. Inc. | Preparation of alkyl aromatic compounds |
| CN104918885B (zh) * | 2012-10-18 | 2016-12-07 | 巴斯夫欧洲公司 | 脱硼β沸石的后处理 |
| RU2639706C2 (ru) * | 2016-05-26 | 2017-12-22 | федеральное государственное бюджетное образовательное учреждение высшего образования "Самарский государственный технический университет" | Способ получения изопропилбензола |
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| US4665255A (en) * | 1983-05-10 | 1987-05-12 | Mobil Oil Corporation | Catalytic conversion of aromatic compounds |
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| US4891458A (en) * | 1987-12-17 | 1990-01-02 | Innes Robert A | Liquid phase alkylation or transalkylation process using zeolite beta |
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| US5522984A (en) * | 1994-08-18 | 1996-06-04 | Uop | Modified zeolite beta, processes for preparation and use thereof |
-
1996
- 1996-07-12 US US08/682,862 patent/US5723710A/en not_active Expired - Lifetime
-
1998
- 1998-03-02 DE DE69814814T patent/DE69814814T2/de not_active Expired - Lifetime
- 1998-03-02 ZA ZA981716A patent/ZA981716B/xx unknown
- 1998-03-02 EP EP98301526A patent/EP0940178B1/en not_active Expired - Lifetime
- 1998-03-02 PT PT98301526T patent/PT940178E/pt unknown
- 1998-03-02 ES ES98301526T patent/ES2200273T3/es not_active Expired - Lifetime
- 1998-03-02 CA CA002230772A patent/CA2230772A1/en not_active Abandoned
- 1998-03-02 DK DK98301526T patent/DK0940178T3/da active
- 1998-03-02 AT AT98301526T patent/ATE240785T1/de not_active IP Right Cessation
- 1998-03-03 JP JP10050882A patent/JPH11267511A/ja active Pending
- 1998-03-03 CN CN98106935A patent/CN1227770A/zh active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675613A (zh) * | 2018-12-29 | 2019-04-26 | 浙江工业大学 | 一种选择性去除分子筛催化剂外表面酸中心的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| PT940178E (pt) | 2003-10-31 |
| DK0940178T3 (da) | 2003-09-22 |
| ES2200273T3 (es) | 2004-03-01 |
| EP0940178B1 (en) | 2003-05-21 |
| ZA981716B (en) | 1998-11-25 |
| CA2230772A1 (en) | 1999-09-02 |
| DE69814814T2 (de) | 2004-02-26 |
| US5723710A (en) | 1998-03-03 |
| JPH11267511A (ja) | 1999-10-05 |
| EP0940178A1 (en) | 1999-09-08 |
| DE69814814D1 (de) | 2003-06-26 |
| ATE240785T1 (de) | 2003-06-15 |
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