CN1077661A - 柴油机氧化控制催化剂 - Google Patents
柴油机氧化控制催化剂 Download PDFInfo
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- 230000001590 oxidative effect Effects 0.000 title claims abstract description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 39
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 20
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- 230000000694 effects Effects 0.000 claims abstract description 7
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
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Abstract
本发明涉及一种柴油机氧化控制催化剂，该催化
剂对烃和一氧化碳的转化率高，并能阻止对氮的氧化
物和二氧化硫的氧化作用，它包含具有陶瓷或金属的
流通通道的整体性催化剂元件，该陶瓷或金属用氧化
铝、氧化钛、氧化硅、沸石各种细颗粒金属氧化物或它
们的混合物的促进活性的分散体涂料涂敷，该分散体
涂料作为催化活性组分的载体，该活性组分为以钒掺
杂或与氧化钒化合物接触的铂、钯、铑和/或铱。
Description
本发明涉及一种柴油机氧化控制催化剂，该催化剂对烃和一氧化碳的转换率高，并能阻止对氮的氧化物和二氧化硫的氧化作用，它包含一个具有陶瓷或金属的流通通道的整体性催化剂元件，该陶瓷或金属用氧化铝、氧化钛、氧化硅、沸石等各种细颗粒金属氧化物或它们的混合物可促进活性的分散体系涂料来涂敷，该分散体涂料作为催化活性组分的载体，该活性组分为用钒掺杂或与氧化钒化合物接触的铂、钯、铑和/或铱。
柴油机废气含有一氧化碳、醛、烃、多芳烃（PAC）、二氧化硫和氮的氧化物等多种污染物质，它们应通过适宜的废气净化来去除。废气中的二氧化硫是因为柴油中存在约0.3%的硫而产生的、并导致在废气中的二氧化硫含量为10-200ppm，这取决于发动机的特定负载和速度。尽管柴油发动机产生的氮的氧化物远远低于火花点火发动机产生的氮的氧化物，但氮的氧化物在柴油机废气中的百分比含量却约三倍于经过三路受控催化剂净化后的火花点火发动机废气中氮的氧化物的百分比含量。
除了这些在225-350℃典型的柴油发动机废气温度下主要呈气态的污染物以外，柴油机还排出相当数量的各种废粉粒，该数量取决于操作方式。上述粉粒包括积炭芯体和被吸附在其上的未燃烧的烃、多芳烃（PAC）以及金属化合物、水和硫酸盐。
由于柴油机废气中的氧含量高达1-15%（体积），因而火花点火发动机所用的三路催化剂不能用于控制柴油机排放。这使得柴油机废气的空气比λ＞1。相反，三路催化剂对于烃和一氧化碳的氧化反应和同时进行的氮的氧化物的还原反应而言，要求废气与空气的配比是化学计量的，即λ＝1。
具有许多相对受阻通道的细孔陶瓷元件（所谓的壁流过滤器）、泡沫陶瓷、丝网填料块、陶瓷管、缠绕陶瓷纤维的过滤器等多种过滤器已被建议用于减少含有硫和氮的各种氧化物的柴油机废气中的粉粒排放量。可以通过上述多种过滤装置从废气流中去除柴油机的废粉粒。然而，仅仅在废气温度足够高的少数几种操作状态下通过燃烧才能清除被过滤下来的粉粒以再生过滤器。
已知通过涂敷能降低点火温度的催化剂物质如五氧化二钒、钒酸盐（例如AgVO3）和高铼酸盐可以改进上述过滤器***的再生行为。可以给上述活性物质掺杂细粒载体材料和通过浸渍来引入贵金属如铂（专利申请DE-OS 3232729，DE-OS 3141713和DE-OS 3407712）。
业已同时发现，即令用上述催化活性物质涂敷过滤器，现在主要用于烃和一氧化碳的壁流过滤器的转换效率并不令人满意，特别是在柴油机废气温度低时尤其如此。此外，使用涂敷了催化剂和载体材料的壁流过滤器还带来废气背压高的缺点，这将降低发动机的效率，特别是当废气含有大量粉粒时尤其如此。增加催化剂数量企图克服上述缺点的尝试并未获得成功。增加几何尺寸以降低背压也由于在大多数机动车中可得到的空间有限而归于失败。
使用DE-OS 3940758的柴油机氧化催化剂可在柴油机废气控制方面获得第一个较大的改进。上述催化剂对于柴油机废气氧化控制是一种可连续工作而没有粉粒沉积也无需周期性清除粉粒的催化剂，在低温下，该催化剂对烃和一氧化碳的转换率高，并能阻止对NO和SO2的氧化作用，该催化剂含有作为活性组分被涂敷于作为促进活性的载体的细颗粒氧化铝、氧化钛、氧化硅、沸石以及它们的混合物之上的各种钡化合物和各种铂族金属。
同壁流过滤器比较，这种结合由燃烧作用有效地清除各种粉粒的已知催化剂可提高气态污染物质的转换率。假定网眼密度相同，上述有益效应可通过以下事实进行解释，通过自由流通元件或蜂巢结构的长通道的微粒或团聚块有效地同涂敷了催化剂的通道表面接触，其接触频率远远超过使用壁流过滤器的接触情况，当使用壁流过滤器时，每种废气成分首先（仅只一次）流过涂敷了催化剂的多孔壁，然后通过流经四个相邻通道进入给定通道的气流进入流出通道的中部而被浓集，并被阻止进入器壁以发生与催化剂同等程度的表面接触。
使用所述柴油机氧化催化剂可净化柴油机废气的程度明显地超过了使用过滤器***所能获得的净化效果。然而，考虑到柴油机排放控制必须满足比较严格的法律要求，则还需要进一步减少粉粒排放和提高对烃、一氧化碳及氮的氧化物等各种气态污染物的相同高转换率的长期稳定性。
由于在废气中存在各种硫酸盐而使排放粉粒的团聚作用发展到非常严重的程度。因而必须采取措施来减少粉粒排放和加强阻止柴油中的硫从SO2被氧化成SO3。
因此，本发明提出的课题是提供一种上述类型对烃和一氧化碳转换率高、并能阻止对氮的氧化物和二氧化硫的氧化作用的柴油机氧化控制催化剂，同先有技术比较，该催化剂应进一步降低对SO2的氧化作用，同时还应出改善了的长期性能。
上述课题已由于使用一种柴油机氧化控制催化剂而得到解决，该催化剂对烃和一氧化碳具有高的转换率，并能阻止对氮的氧化物和二氧化硫的氧化作用，它包含一个具有陶瓷或金属的流通通道的整体性催化剂元件，该陶瓷或金属用氧化铝、氧化钛、氧化硅、沸石等各种细颗粒金属氧化物或它们的混合物可促进活性的分散体系涂料涂敷，该分散体涂料作为催化活性组分的载体，该活性组分为与钒掺杂或与氧化钒化合物接触的铂、钯、铑和/或铱。
该催化剂的特征在于，细颗粒的金属氧化物是表面改性的氧化铝、氧化钛、氧化硅、沸石或它们的混合物，它们可通过以下方法获得，即通过将各种细颗粒金属氧化物或它们的混合物拌入氧化钛和/或氧化硅前体的乙醇溶液内，在降低压力和连续搅拌状态下去除乙醇溶剂，并在升高温度下干燥留下的固体，将该固体研磨0.5-4小时后于300-600℃煅烧磨碎的固体，同时氧化钛和/或氧化硅的前体分解成二氧化钛和二氧化硅。
根据本发明采取的各种措施有利于改进各种金属氧化物的表面性质。业已发现，经过上述处理的各种金属氧化物对减弱SO2变成SO3的氧化作用具有积极效果。同DE-OS3940758所述的物理混合物（例如，带二氧化钛的氧化铝（Degussa P25，金红石/锐钛矿混合物，比表面为51m2/g）〕，被涂敷于剩留的各种表面改性金属氧化物上的氧化钛显示出长期性能有了相当大的改进。
本发明的各种细颗粒表面改性金属氧化物是催化剂领域内已知的各种大面积金属氧化物，例如，过渡系列的氧化铝，但为了提高温度稳定性，可用已知方法往其中掺杂各种稀土金属的氧化物。
为了有效地改进各种金属氧化物，可用一种具有由1-5个单层组成的二氧化钛和/或二氧化硅的层状结构来提供它们的比表面积。根据Tan等人（“Coated Sillica as Support for platinum Catalyst”in Journal of Catalystis 129（1991）447-456）的计算，涂敷100m2的单层比面所需的TiO2数量为0.098g TiO2。一般通式为Ti（OR）4或Si（OR）4（式中R为有机基）的各种有机钛或有机硅化合物被用作氧化钛和/或氧化硅的前体具有十分特别的优点。例如，适宜的氧化钛前体是原钛酸四乙酯（Ti〔OC2H5〕4）、原钛酸四叔丁酯（Ti〔OC（CH3）3〕4）、原钛酸四异丙酯（Ti〔OCH（CH3）2〕4和原钛酸四丙酯（Ti〔OCH2CH2-CH3〕4）。
为了保证它们的有益作用得到最佳发挥，应将上述改性了的各种金属氧化物以分散体涂料形式涂敷在所说元件上，涂敷时上述改性金属氧化物的浓度为30-250、较好为75-180、更好为90-150g/l（催化剂体积）。催化剂中钒（表示为V2O5）的浓度可为0.1-15g/l（催化剂体积），而各种铂族金属的浓度为0.1-7g/l（催化剂体积）。适宜的催化剂元件是具有5-100个网眼/cm2的蜂巢状惰性承载体。在各种铂族金属中，铂和/或钯已成为特别有效的活性组分。
根据DE-OS 3940758用各种铂族金属化合物的溶液和钒化合物的溶液一次或逐次（以任何顺序）浸透促进活性的分散体涂料;干燥并任选地在至少200℃温度下最好在含氢气流中煅烧，即可以得到与钒渗杂或与氧化钒化合物接触的各种铂族金属。可在促进活性的分散体被涂敷于惰性承载体以前或以后，用活性组分两种原料中的至少一种进行浸透。
本发明使用的各种表面改性金属氧化物对最后的分散体涂料的表面粗糙度具有十分意外和惊奇的效果。业已发现，在二者都使用平均粒径相同的各种金属氧化物的条件下相比较，本发明催化剂的表面粗糙度大于先有技术中对比催化剂的表面粗糙度。本发明催化剂转换效率的提高可部分地被认为是较大的表面粗糙度造成的。由于表面粗糙，废气在催化剂元件的通道内要经受更大的扰动，从而更充分地同催化剂涂层接触。
用以下各实施例并结合各附图来说明本发明，其中：
图1表示柴油机氧化催化剂的老化循环（55kw，容积1.6l，静态试验条件）。
图2a图解说明对比催化剂CC1表面涂层的粗糙度测量结果（扫描曲线）。
图2b图解说明本发明催化剂C1表面涂层的粗糙度测量结果（扫描曲线）。
多种堇青石制蜂巢状元件被用于生产本发明的各种催化剂。其网眼密度为62网眼/cm2，壁厚为0.17mm。
对比1 对比催化剂CC1
一种先有技术的对比催化剂按以下方法生产：
制备一种含有30%固体涂料含水分散体。该悬浮液包含60%（重量）γ-氧化铝（比表面为180m2/g）和40%（重量）二氧化钛（Degussa p 25;比表面为50m2/g;金红石/锐钛矿混合物）（以干燥成分为基准）。然后以浸入分散体涂料中的方式用各种金属氧化物涂敷催化剂元件，通过喷吹去除多余悬浮液后于120℃在空气中进行干燥。于400℃煅烧2小时后，用Pt（NH3）4（OH）2水溶液浸渍已涂敷的单体;于150℃在空气中干燥并于300℃进行煅烧。随后用草酸氧钒浸渍;于120℃干燥并于500℃在空气中进行氧钒根分解。上述所得的催化剂中间产物于500℃在混合气体（95%N2、5%H2）流中被还原2小时。
最后的催化剂（在每升体积的催化剂中）包含64g氧化钛、96g氧化铝、5g五氧化二钒和1.77g铂。
对比例2 对比催化剂CC2
按照对比例1相同的方法制备第二种对比催化剂，但用100%锐钛矿变体（比表面95m2/g）代替氧化钛（Degussa P25）。
实施例1 含有TiO2改性γ-氧化铝的本发明催化剂C1
将对比例1的相同γ-氧化铝用于制备本发明的催化剂。为了用氧化钛来提高它的比表面，将γ-氧化铝拌入原钛酸四乙酯（C8H20O4Ti）的酒精溶液（乙醇）内。在搅拌2小时后，在旋转蒸发器（水喷射真空泵，T＝50℃）内去除乙醇，并将所生成的物料于120℃在空气中干燥16小时。在研磨后，将所生成的TiO2/Al2O3粉于400℃在空气中煅烧4小时。
如此生产的TiO2/Al2O3粉末包含60%（重量）氧化铝和40%（重量）氧化钛（以其总重量为基准）。根据Tan等人（“Coated Silica as Support for Platinum Catalyst”in Journal of Catalysis129，（1991）447-456）计算，该氧化钛的数量相当于用约三个单层的二氧化钛涂敷氧化铝的表面。
用TiO2/Al2O3粉制备含有30%固体成分的涂料含水分散体。用上述涂料分散体涂敷催化剂元件。然后按照对比1完全相同的方法进一步进行处理。最后的催化剂（在每升体积的催化剂中）包含160g TiO2/Al2O3、5g V2O5和1.77g Pt。
实施2 含有TiO2改性二氧化硅的本发明催化剂C2
按照实施例1完全相同的方法制备本发明的催化剂C2，但用二氧化硅（比表面为260m2/g）代替氧化铝。最后的催化剂（在每升体积的催化剂中）包含由40%（重量）TiO2和60%（重量）SiO2（以TiO2/SiO2的总重量为基准）组成的TiO2/SiO2160g。所选择的TiO2的数量相当于用约二个单层的二氧化钛涂敷二氧化硅的表面。
实施例3 含有SiO2改性γ-氧化铝的本发明催化剂C3
按照实施例1完全相同的方法制备本发明的催化剂C3，但用四乙氧基硅烷（C8H20O4Si）代替原钛酸四乙酯（C8H20O4Ti），最后的催化剂（在每升体积的催化剂中）包含由40%（重量）SiO2和60%（重量）Al2O3（以SiO2/Al2O3的总重量为基准）组成的SiO2/Al2O3160g。所选择的SiO2的数量相当于用约二个单层的二氧化硅涂敷氧化铝表面。
实施例4 含有SiO2改性氧化钛的本发明催化剂C4
按照实施例3完全相同的方法制备本发明的催化剂C4，但用二氧化钛（比表面为95m2/g）代替氧化铝。最后的催化剂（在每升体积的催化剂中）包含20%（重量）SiO2和80%（重量）TiO2（以SiO2/TiO2的总重量为基准）。所选择的SiO2的数量相当于用约二个单层的二氧化硅涂敷二氧化钛的表面。
实施例5 点火和活性试验
在固定台式测力计上对对比例1和2以及实施例1到4的各种柴油机氧化催化剂进行试验。该测力计配备一个四汽缸柴油发动机（55KW，1.6升容积）和一个水涡流断路器（Schenck AG230型）。试验燃料是含有0.2%硫的商用柴油。
在各种点火试验中，测量了一氧化碳、烃、氧化氮和二氧化硫的转化率同催化剂达到120，000h-1空间速度以前的废气的关系曲线。
在试验新鲜状态的催化剂以后，发动机内各种催化剂进行50小时老化。图1示出了所用老化循环。一个循环持续60分钟并被重复50次以对催化剂进行老化试验。
各种点火试验的结果被列在表1和2内。它们显示出，相对于对比催化剂、催化剂C1-C4在高温时SO2的转化率呈降低趋势，而其它对CO，HC和NOx的转化率来说是相近的。
实施例6
对对比例1和2以及实施例1到4所述的各种催化剂进行x-射线衍射、光学显微镜和表面粗糙度测量分析。
对预制的TiO2/Al2O3、TiO2/SiO2和SiO2/TiO2粉进行衍射分析。新鲜状态的催化剂CC1的氧化样品显示出锐钛矿和红金石变体的比例为78∶22。于650℃在空气中进行7小时老化后，催化作用最佳的锐钛矿变体的百分比含量降到38%。对比催化剂CC2的氧化样品显示出类似的状况。在新鲜状态时100%的锐钛矿变体于650℃经过老化后其65%转换成金红石。相反，本发明的氧化样品在新鲜状态及于650℃在空气中进行7小时老化后显示出仍存在100%的锐钛矿变体（表3）。
在使用对比催化剂CC1和CC2的情况中，用光学显微镜检查已涂敷催化剂的通道壁，发现表面涂层光滑而致密。相反，本发明的催化剂1到4却具有粗糙而多孔的表面涂层。使用Mahr-perthen 58p Perthometer（一种粗糙度测量仪器）测量粗糙度定量地证实了上述事实。图2a和2b示出了测量长度超过0.88mm的对比催化剂CC1（图2a）和本发明催化剂C1（图2b）表面涂层的扫描曲线。对比催化剂的均方粗糙度（RA）仅为0.58μm，而本发明催化剂的均方粗糙度却为4.55μm，也就是，后者的表面粗糙度是前者表面粗糙度的9倍。
本发明催化剂C1到C4的粗糙表面涂层促进废气流中的局部扰动，该扰动使物质和热量加速从气相迁移到表面层。
表3
各种催化剂CC1、CC2、C1、C2、C3、C4的分散体氧化涂料（TiO2/Al2O3，TiO2/SiO2和SiO2/TiO2）样品的X-射线衍射分析结果
| 催化剂 | 新鲜状态锐钛矿：金红石 | 7h，650℃，空气，加热炉锐钛矿：金红石 |
| CC1CC2C1C2C3C4 | 78:22100:0100:0100:0-100:0 | 38:6235:65100:0100:0-100:0 |
Claims (7)
1、一种柴油机氧化控制催化剂，该催化剂对烃和一氧化碳的转换率高，并能阻止对氮的氧化物和二氧化硫的氧化作用，它包含具有陶瓷或金属的流通通道的整体性催化剂元件，该陶瓷或金属用氧化铝、氧化钛、氧化硅、沸石各种细颗粒金属氧化物或它们的混合物的促进活性的分散体涂料涂敷，该分散体涂料作为催化活性组分的载体，该活性组分为以钒掺杂或与氧化钒化合物接触的铂、钯、铑和/或铱；该催化剂的特征在于，通过将各种细颗粒金属氧化物或它们的混合物拌入氧化钛和/或氧化硅前体的乙醇溶液内，在降低压力和连续搅拌的条件下去除乙醇溶剂，并在升高温度下干燥剩留的固体，将该固体研磨0.5-4小时后于300-600℃煅烧磨碎的固体，同时氧化钛和/或氧化硅前体分解成二氧化钛和二氧化硅，可使各种细颗粒金属氧化物成为表面改性了的氧化铝、氧化钛、氧化硅、沸石或它们的混合物。
2、权利要求1所述的方法，其特征在于，在各种改性金属氧化物的生产中，测量溶解的钛和/或硅氧化物前体的数量，在各种金属氧化物煅烧后，使各种金属氧化物的比表面由一层包含1-5个单层的二氧化钛和/或二氧化硅层来提供。
3、权利要求1或2所述的催化剂，其特征在于，氧化钛和/或氧化硅前体是通式为Ti（OR）4或Si（OR）4（式中R为有机基团）的有机钛或者有机硅化合物。
4、权利要求1到3所述的催化剂，其特征在于，促进活性的分散体涂料的浓度为30-250，较好为75-180，更好为90-150g/dm3（催化剂体积）表达式为V2O5的钒浓度为0.1-15g/dm3（催化剂体积），而各种铂族金属的浓度为0.1-7g/dm3（催化剂体积）。
5、权利要求1到4所述的催化剂，其特征在于，一种陶瓷或单体载体（最好呈整体的峰巢状形式（承载催化剂））被用作结构加强体。
6、权利要求1到5所述的催化剂，其特征在于，整体或蜂巢状惰性载体的网眼密度为5-100个网眼/cm2。
7、权利要求1到6所述的催化剂，其特征在于，铂和/或钯作为铂族金属存在。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4213018A DE4213018C1 (de) | 1992-04-21 | 1992-04-21 | Katalysator zur oxidativen Reinigung der Abgase von Dieselmotoren |
| DEP4213018.2 | 1992-04-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1077661A true CN1077661A (zh) | 1993-10-27 |
Family
ID=6457105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93104608A Pending CN1077661A (zh) | 1992-04-21 | 1993-04-20 | 柴油机氧化控制催化剂 |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US5371056A (zh) |
| EP (1) | EP0566878A1 (zh) |
| JP (1) | JPH067677A (zh) |
| KR (1) | KR930021260A (zh) |
| CN (1) | CN1077661A (zh) |
| AU (1) | AU655724B2 (zh) |
| BR (1) | BR9301613A (zh) |
| CA (1) | CA2094429A1 (zh) |
| CZ (1) | CZ379892A3 (zh) |
| DE (1) | DE4213018C1 (zh) |
| HU (1) | HUT69735A (zh) |
| MX (1) | MX9302276A (zh) |
| PL (1) | PL298569A1 (zh) |
| RO (1) | RO111740B1 (zh) |
| SK (1) | SK379892A3 (zh) |
| TR (1) | TR28120A (zh) |
| TW (1) | TW263448B (zh) |
| ZA (1) | ZA932806B (zh) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091002C (zh) * | 1996-04-12 | 2002-09-18 | 德古萨－于尔斯股份公司 | 柴油催化剂 |
| CN1305562C (zh) * | 2004-11-26 | 2007-03-21 | 南京大学 | 甲醇选择氧化生产甲缩醛的催化剂及其制法和用途 |
| CN103256101A (zh) * | 2012-02-21 | 2013-08-21 | 通用电气公司 | 立方相晶体结构物质的使用和制备方法 |
| CN104661729A (zh) * | 2012-10-25 | 2015-05-27 | 托普索公司 | 选择性氧化进一步包含二氧化硫的尾气中的一氧化碳与挥发性有机化合物的方法 |
| CN108463435A (zh) * | 2015-11-20 | 2018-08-28 | 克里斯特尔美国有限公司 | 二氧化钛组合物和其作为防止污染剂的用途 |
| CN110821616A (zh) * | 2018-08-07 | 2020-02-21 | 通用汽车环球科技运作有限责任公司 | 用于制备催化剂体系的方法 |
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-
1992
- 1992-04-21 DE DE4213018A patent/DE4213018C1/de not_active Expired - Fee Related
- 1992-12-21 SK SK3798-92A patent/SK379892A3/sk unknown
- 1992-12-21 CZ CS923798A patent/CZ379892A3/cs unknown
-
1993
- 1993-03-22 EP EP93104685A patent/EP0566878A1/de not_active Withdrawn
- 1993-03-25 TW TW082102260A patent/TW263448B/zh active
- 1993-04-15 RO RO93-00535A patent/RO111740B1/ro unknown
- 1993-04-15 PL PL29856993A patent/PL298569A1/xx unknown
- 1993-04-19 TR TR00326/93A patent/TR28120A/xx unknown
- 1993-04-20 CN CN93104608A patent/CN1077661A/zh active Pending
- 1993-04-20 BR BR9301613A patent/BR9301613A/pt not_active Application Discontinuation
- 1993-04-20 HU HU9301170A patent/HUT69735A/hu unknown
- 1993-04-20 AU AU37026/93A patent/AU655724B2/en not_active Ceased
- 1993-04-20 JP JP5092830A patent/JPH067677A/ja active Pending
- 1993-04-20 KR KR1019930006609A patent/KR930021260A/ko not_active Application Discontinuation
- 1993-04-20 MX MX9302276A patent/MX9302276A/es unknown
- 1993-04-20 CA CA002094429A patent/CA2094429A1/en not_active Abandoned
- 1993-04-20 US US08/049,224 patent/US5371056A/en not_active Expired - Fee Related
- 1993-04-21 ZA ZA932806A patent/ZA932806B/xx unknown
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091002C (zh) * | 1996-04-12 | 2002-09-18 | 德古萨－于尔斯股份公司 | 柴油催化剂 |
| CN1305562C (zh) * | 2004-11-26 | 2007-03-21 | 南京大学 | 甲醇选择氧化生产甲缩醛的催化剂及其制法和用途 |
| CN103256101A (zh) * | 2012-02-21 | 2013-08-21 | 通用电气公司 | 立方相晶体结构物质的使用和制备方法 |
| CN104661729A (zh) * | 2012-10-25 | 2015-05-27 | 托普索公司 | 选择性氧化进一步包含二氧化硫的尾气中的一氧化碳与挥发性有机化合物的方法 |
| CN108452670A (zh) * | 2012-10-25 | 2018-08-28 | 托普索公司 | 选择性氧化进一步包含二氧化硫的尾气中的一氧化碳与挥发性有机化合物的方法 |
| CN108463435A (zh) * | 2015-11-20 | 2018-08-28 | 克里斯特尔美国有限公司 | 二氧化钛组合物和其作为防止污染剂的用途 |
| CN110821616A (zh) * | 2018-08-07 | 2020-02-21 | 通用汽车环球科技运作有限责任公司 | 用于制备催化剂体系的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| MX9302276A (es) | 1994-02-28 |
| JPH067677A (ja) | 1994-01-18 |
| TW263448B (zh) | 1995-11-21 |
| SK379892A3 (en) | 1996-04-03 |
| RO111740B1 (ro) | 1997-01-30 |
| DE4213018C1 (de) | 1993-12-09 |
| TR28120A (tr) | 1996-01-08 |
| CZ379892A3 (en) | 1993-12-15 |
| PL298569A1 (en) | 1993-11-02 |
| HU9301170D0 (en) | 1993-08-30 |
| BR9301613A (pt) | 1993-10-26 |
| AU3702693A (en) | 1993-10-28 |
| HUT69735A (en) | 1995-09-28 |
| ZA932806B (en) | 1993-11-16 |
| KR930021260A (ko) | 1993-11-22 |
| CA2094429A1 (en) | 1993-10-22 |
| EP0566878A1 (de) | 1993-10-27 |
| US5371056A (en) | 1994-12-06 |
| AU655724B2 (en) | 1995-01-05 |
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