CN1325322A - 星形氧化铝挤出物及载于其上的催化剂 - Google Patents
星形氧化铝挤出物及载于其上的催化剂 Download PDFInfo
- Publication number
- CN1325322A CN1325322A CN99812972.0A CN99812972A CN1325322A CN 1325322 A CN1325322 A CN 1325322A CN 99812972 A CN99812972 A CN 99812972A CN 1325322 A CN1325322 A CN 1325322A
- Authority
- CN
- China
- Prior art keywords
- extrudate
- catalyst
- aluminium oxide
- crushing strength
- star shaped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims description 18
- 239000011148 porous material Substances 0.000 claims abstract description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 3
- 238000002459 porosimetry Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052976 metal sulfide Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002196 fatty nitriles Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- -1 this Chemical compound 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/34—Mechanical properties
- B01J35/37—Crush or impact strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/34—Mechanical properties
- B01J35/38—Abrasion or attrition resistance
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
- C04B38/0054—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity the pores being microsized or nanosized
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Nanotechnology (AREA)
- Structural Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及星形氧化铝挤出物,该挤出物由水银孔率测试法所确定的、超过1000nm直径的孔的孔容积至少为0.05ml/g,并且总孔容积在0.5－0.75ml/g之间。挤出物长度在2－8mm之间,长度与直径的比在1－3之间,侧面抗碎强度至少为50N,本体抗碎强度至少为1MPa。
Description
本发明涉及适合用作催化剂或催化剂载体的过渡氧化铝(transitionalumina)挤出物，以及这种挤出物在化学反应中的用途。
在催化作用中，氧化铝起重要作用，既作为催化剂载体，又作为催化活性物质。如Kirk-Othmer第三版第二卷第230-232页中所述，氧化铝可用作克劳斯法(Clause Process)的催化剂，用于醇类脱水，诸如由醇制备烯烃，及其逆反应，以及烯烃异构化。作为相互作用的催化剂载体，氧化铝可在加氢精制催化剂中起作用，例如在氧化铝上的钴或镍-钼氧化物催化剂中。
作为载体，氧化铝常用于诸如废气处理催化剂中的贵金属催化剂，或用于(脱)氢化反应。作为用于镍催化剂的载体，它可用于诸如脂肪和油类氢化、脂肪腈类或硝基芳烃化合物的氢化反应或烯烃低聚的(脱)氢化反应。
载体的结构，即BET表面积、孔径和孔容分布，构成了氧化铝或基于氧化铝的催化剂的一个重要方面。由活性和选择性考虑，最好是有一种一方面高孔隙度的即有大量大孔的、并且具有好的机械强度和稳定性的氧化铝产品。不幸地，这些要求是难以相互兼容的。
在固定床方法中，常常使用氧化铝的成形体。其中一个重要方面是压降的形状相关性。片剂和挤出物是通常用在固定床中的物料。为了使压降达到最小，星形挤出物的使用将是最适合的。但是，由于星形上有尖儿，星形体挤出物易于磨损。
本发明的目的是调和过渡氧化铝挤出物的不同要求，这些形式具有精细平衡的一组特性。另外的目的和优点将在本发明后面的描述及其优选实施方式中越来越清楚。
本发明是基于发明人现在已经能够提供一方面具有如上所述的最佳结构，而且另一方面具有好的强度的星形氧化铝挤出物。
因此本发明涉及星形氧化铝挤出物，该挤出物具有由水银孔率测试法所确定的、超过1000nm直径的孔中的孔容积积至少为0.05ml/g，侧面抗碎强度(side crushing strength)至少为50N，本体抗碎强度(bulkcrushing strength)至少为1MPa。
令人惊讶地，这组特性可在一种物料上得到，由此提供一种可使由其进行的化学反应更高效的物料，结果形成更高的活性和/或选择性。而且，当用在固定床反应器中时，与圆筒形常规挤出物相比，本发明的物料提供一种降低了的压降。
使用BET方程式(例如由G.Sandstede等人在Chem.Ing.Tech.32(1960),413中所述)，由单点吸附确定的BET表面积，至少为10m2/g氧化铝。这一点与使用过渡氧化铝，即，不是α氧化铝的要求相符合。合适的氧化铝是包括γ-氧化铝、δ-氧化铝、ε-氧化铝、κ-氧化铝、ξ-氧化铝、θ-氧化铝和τ-氧化铝在内的不同的过渡氧化铝。这些氧化铝具有大的、通常在25至超过100m2/g范围内的BET表面积。
孔容积积是另一个重要的要求，由此重要的是：一方面由压汞法确定的总孔容积足够高，并且另一方面超过1000nm的孔中的孔容积构成了总孔容积的重要部分。以绝对值而言，总孔容积应当至少为0.50ml/g，而超过1000nm的孔中的孔容积与总孔容积的比率应当优选超过0.04。就反应物易于到达(reactant accessibility)而论，具有那些特性的氧化铝有好的性能，这样使其非常适合于要求反应物和产物在氧化铝上有好的扩散性的各种催化反应，由此，尽可能地消除扩散限制问题。
孔容积和孔径分布是由如J.Rouquerol等人在纯&应用化学(Pure &Applied Chem.),66(8),1994第1752-1753页中所述的水银孔率测量法、用瓦什伯恩(Washburn)方程式确定的。
如上所述，就与氧化铝内表面的易于到达性有关的压降而论，星形挤出物的使用是重要的。这也在消除扩散问题中起作用。星形挤出物可定义为具有某种中心部位或核心的、在其周围带有三个或多个三角形伸长部分的物体。最优选的是有五个伸长部分的星形挤出物，因为这提供了强度、多孔性、压降和易于到达性之间的最佳平衡。星形挤出物的另一个有利特性是：外表面与容积的比率，比常规的圆筒形或片形的情况更有利。
挤出物的长度与直径的比率，优选是在1-3之间，由此作为直径，该距离表示挤出物任一侧面上的两个平行平面之间的距离。
本发明的物料的重要方面还有强度特性。如上所述，其中必要的是：至少为50N的侧面抗碎强度和至少为1MPa的本体抗碎强度。这些参数构成了在象石油工业中的大型反应器中使用的挤出物的适宜性的基础。当该挤出物满足这些要求时，它们可以用在需要高强度物料的、大型固定床反应器中。侧面抗碎强度和本体抗碎强度定义如下：
挤出物的侧面抗碎强度(SCS)定义为：在两个平板之间用AIKOH9500系列检测器在压力下处理时，将4.5-5.00mm长度的挤出物压碎的压力(牛顿)。
催化剂的本体抗碎强度(BCS)定义为：在管道中活塞的作用下，形成0.5％细粒(即小于0.425mm的颗粒)的压力(兆帕)。为此，将预先在0.425mm的筛子上筛分的17ml催化剂颗粒，装填到圆柱形样品管(直径27.3mm)中，并将8ml钢珠装填到顶部。随后将催化剂在不同压力(渐增的)下处理3分钟，然后回收细粒并确定它们的百分比。重复进行这个过程，直到达到0.5％重量细粒的程度。
物料强度的另一方面是磨损，即挤出物在使用时可能折断的物料的量。这种依照ASTM D4058-87所确定的磨损率，应当优选小于5重量％，尤其是更优选小于3重量％。
具有上述特性的氧化铝挤出物，可通过下述方法制备：将过渡氧化铝粉末与适当的粘合剂，在有通常为水或诸如盐酸、磺酸或硝酸的无机酸的水溶液的液体存在的情况下混合，形成浆糊，随后使用适当的模头将该浆糊按所需的星形挤出，将挤出的条形物料切成所需的长度。任选地，在干燥后焙烧挤出物。
可使用各种类型的、诸如那些基于氧化硅或氧化铝的粘合剂材料。实例为胶态氧化硅、水玻璃或粘土。优选使用基于氧化铝的粘合剂或在焙烧过程中被除去的粘合剂，而同时提供并保持所需的强度。适当的粘合剂体系的一个实例，是在例如通过使用有机或无机酸进行酸处理的情况下形成胶体的氧化铝粘合剂。在制备待挤出的浆糊时所使用的粘合剂材料的量，将随物料的类型和所需的强度而变化。通常，基于粘合剂和氧化铝的总的干重，它不会超过30重量％。
现在，以实施例为基础说明本发明。
实施例
将含65重量％Al2O3、平均粒径为30-50μm的1.5kg三水合铝，与0.4kg氧化铝粘合剂混合。充分混合粉末，同时缓慢加入稀释的、以全部氧化铝的重量计为2重量％的硝酸水溶液。
由此，氧化铝粘合剂成胶体溶液。继续混合，直到获得较干的产品。中间产品用配备具有星形孔和切割装置的模头的单螺杆挤出机挤出。
将得到的挤出物在105℃下干燥16小时，并随后在850℃下焙烧1小时。所附的是两个从两个不同角度展示的挤出物的照片的图形。
现已分析了最终产物的物理特性，结果如下：
N2-BET表面积106m/g2
总Hg孔容积0.56ml/g
超过1000nm的孔中的孔容积0.07ml/g
侧面抗碎强度65N
本体抗碎强度1.08MPa
Claims (9)
1．星形氧化铝挤出物，由水银孔率测试法所确定的、超过1000nm直径的孔的孔容积至少为0.05ml/g，侧面抗碎强度至少为50N，本体抗碎强度至少为1MPa。
2．根据权利要求1的挤出物，长度在2-8mm之间。
3．根据权利要求1或2的挤出物，长度与直径的比在1-3之间。
4．根据权利要求1-3的挤出物，其中，由水银孔率测试法所确定的总孔容积在0.5-0.75ml/g之间。
5．根据权利要求1-4的挤出物，其中，BET表面积至少为75m2/g。
6．根据权利要求1-5的挤出物，其中，依照ASTM D4058-87，磨损率小于5重量％，优选小于3重量％。
7．催化剂，含有至少一种担载在权利要求1-6的挤出物上的催化活性物质。
8．根据权利要求7的催化剂，其中，催化活性物质选自金属、金属氧化物、金属硫化物及它们的组合。
9．权利要求1-6的挤出物或权利要求7或8的催化剂在化学反应中的应用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP98203719A EP0998976A1 (en) | 1998-11-04 | 1998-11-04 | Star shaped alumina extrudates and catalyst based thereon |
| EP98203719.4 | 1998-11-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1325322A true CN1325322A (zh) | 2001-12-05 |
| CN1213808C CN1213808C (zh) | 2005-08-10 |
Family
ID=8234295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99812972.0A Expired - Lifetime CN1213808C (zh) | 1998-11-04 | 1999-11-04 | 星形氧化铝挤出物及载于其上的催化剂 |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US7351393B1 (zh) |
| EP (2) | EP0998976A1 (zh) |
| JP (1) | JP4689831B2 (zh) |
| CN (1) | CN1213808C (zh) |
| AT (1) | ATE287763T1 (zh) |
| AU (1) | AU1189600A (zh) |
| DE (1) | DE69923474T2 (zh) |
| DK (1) | DK1137487T3 (zh) |
| ES (1) | ES2237211T3 (zh) |
| WO (1) | WO2000025918A1 (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149466A (zh) * | 2008-09-12 | 2011-08-10 | 约翰森·马瑟公开有限公司 | 成型异相催化剂 |
| CN115052847A (zh) * | 2020-02-07 | 2022-09-13 | 巴斯夫欧洲公司 | 用作催化剂的星形陶瓷体 |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0226514D0 (en) * | 2002-11-13 | 2002-12-18 | Statoil Asa | Fischer-tropsch catalysts |
| GB2410449B (en) * | 2004-01-28 | 2008-05-21 | Statoil Asa | Fischer-Tropsch catalysts |
| US8414778B2 (en) * | 2005-05-17 | 2013-04-09 | Universal Bio Research Co., Ltd. | Filtration method, filter-incorporated tip, and filtration device |
| US7700005B2 (en) * | 2006-12-26 | 2010-04-20 | Saudi Arabian Oil Company | Oil-based thermo-neutral reforming with a multi-component catalyst |
| GB2446127A (en) * | 2007-01-30 | 2008-08-06 | Gtl F1 Ag | Preparation of Fischer-Tropsch Catalysts |
| GB0816703D0 (en) | 2008-09-12 | 2008-10-22 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
| GB0816705D0 (en) | 2008-09-12 | 2008-10-22 | Johnson Matthey Plc | Shaped heterogeneous catalysts |
| JP2010179267A (ja) * | 2009-02-07 | 2010-08-19 | Kosei:Kk | 担体およびその製造方法 |
| US8586813B2 (en) | 2009-07-21 | 2013-11-19 | Lummus Technology Inc. | Catalyst for metathesis of ethylene and 2-butene and/or double bond isomerization |
| GB2473071B (en) | 2009-09-01 | 2013-09-11 | Gtl F1 Ag | Fischer-tropsch catalysts |
| GB2475492B (en) | 2009-11-18 | 2014-12-31 | Gtl F1 Ag | Fischer-Tropsch synthesis |
| WO2012020210A2 (en) | 2010-08-09 | 2012-02-16 | Gtl.F1 Ag | Fischer-tropsch catalysts |
| USD697676S1 (en) * | 2010-10-18 | 2014-01-14 | Kyle Hansen | Star-shaped pet treat dispensing puzzle |
| DE102016219114A1 (de) | 2016-09-30 | 2018-04-05 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Partikel aus einem feuerfesten keramischen Werkstoff zur Beeinflussung der Schadenstoleranz von Hochtemperaturwerkstoffen, und Verfahren zu ihrer Herstellung |
| EP3574993A1 (en) | 2018-05-29 | 2019-12-04 | Basf Se | Method for producing transition alumina catalyst monoliths |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673079A (en) * | 1970-01-21 | 1972-06-27 | Chevron Res | Catalyst manufacture |
| DE2811115A1 (de) * | 1978-03-15 | 1979-09-27 | Hoechst Ag | Traeger-katalysator fuer die herstellung von vinylacetat aus ethylen, essigsaeure und sauerstoff in der gasphase |
| DE2837018A1 (de) * | 1978-08-24 | 1980-03-06 | Basf Ag | Verwendung von kobalt- und/oder nickelmolybdaenoxid-katalysatoren zur hydrierenden raffination von erdoel- kohlenwasserstoffen |
| DE2922116A1 (de) * | 1979-05-31 | 1980-12-11 | Basf Ag | Verfahren zur oxidation von schwefeldioxid |
| DD218736A3 (de) * | 1982-05-12 | 1985-02-13 | Leuna Werke Veb | Formspezifische katalysatorteilchen fuer kohlenwasserstoffumwandlungsreaktionen |
| FR2553302B1 (fr) * | 1983-10-14 | 1986-04-18 | Shell Int Research | Procede pour la preparation d'oxydes refractaires modifies et leur utilisation dans des procedes d'hydroconversion |
| US5633081A (en) * | 1986-03-24 | 1997-05-27 | Ensci Inc. | Coated porous substrates |
| GB8811817D0 (en) * | 1988-05-19 | 1988-06-22 | Shell Int Research | Process for preparation of catalyst particles & catalyst particles thus prepared |
| KR930702069A (ko) * | 1990-10-04 | 1993-09-08 | 제임스 클리프튼 보울딩 | 말레산 무수물 제조를 위한 특수한 형상으로 된 산화촉매 구조물 |
| US5372620A (en) * | 1993-12-13 | 1994-12-13 | Saint Gobain/Norton Industrial Ceramics Corporation | Modified sol-gel alumina abrasive filaments |
| DE19739746A1 (de) * | 1997-09-10 | 1999-03-11 | Basf Ag | Katalysator in Tablettenform |
| CN1160286C (zh) * | 1998-05-11 | 2004-08-04 | 国际壳牌研究有限公司 | 苯乙烯的制法 |
-
1998
- 1998-11-04 EP EP98203719A patent/EP0998976A1/en not_active Withdrawn
-
1999
- 1999-11-04 EP EP99971351A patent/EP1137487B1/en not_active Expired - Lifetime
- 1999-11-04 CN CN99812972.0A patent/CN1213808C/zh not_active Expired - Lifetime
- 1999-11-04 WO PCT/NL1999/000676 patent/WO2000025918A1/en active IP Right Grant
- 1999-11-04 DE DE69923474T patent/DE69923474T2/de not_active Expired - Lifetime
- 1999-11-04 JP JP2000579348A patent/JP4689831B2/ja not_active Expired - Lifetime
- 1999-11-04 AU AU11896/00A patent/AU1189600A/en not_active Abandoned
- 1999-11-04 US US09/830,907 patent/US7351393B1/en not_active Expired - Lifetime
- 1999-11-04 DK DK99971351T patent/DK1137487T3/da active
- 1999-11-04 AT AT99971351T patent/ATE287763T1/de not_active IP Right Cessation
- 1999-11-04 ES ES99971351T patent/ES2237211T3/es not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149466A (zh) * | 2008-09-12 | 2011-08-10 | 约翰森·马瑟公开有限公司 | 成型异相催化剂 |
| CN102149466B (zh) * | 2008-09-12 | 2014-01-15 | 约翰森·马瑟公开有限公司 | 成型异相催化剂 |
| CN115052847A (zh) * | 2020-02-07 | 2022-09-13 | 巴斯夫欧洲公司 | 用作催化剂的星形陶瓷体 |
| CN115052847B (zh) * | 2020-02-07 | 2024-05-28 | 巴斯夫欧洲公司 | 用作催化剂的星形陶瓷体 |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2237211T3 (es) | 2005-07-16 |
| ATE287763T1 (de) | 2005-02-15 |
| DE69923474D1 (de) | 2005-03-03 |
| DE69923474T2 (de) | 2005-07-07 |
| US7351393B1 (en) | 2008-04-01 |
| EP1137487B1 (en) | 2005-01-26 |
| DK1137487T3 (da) | 2005-04-25 |
| JP4689831B2 (ja) | 2011-05-25 |
| AU1189600A (en) | 2000-05-22 |
| WO2000025918A1 (en) | 2000-05-11 |
| CN1213808C (zh) | 2005-08-10 |
| JP2002528262A (ja) | 2002-09-03 |
| EP0998976A1 (en) | 2000-05-10 |
| EP1137487A1 (en) | 2001-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1213808C (zh) | 星形氧化铝挤出物及载于其上的催化剂 | |
| RU2386477C2 (ru) | Слоистая композиция и способы приготовления и применения композиции | |
| EP1900713B1 (de) | Verfahren zur Spaltung von Methyl-tertiär-butylether | |
| RU2008138887A (ru) | Катализатор гидролиза целлюлозы и/или восстановления продуктов гидролиза целлюлозы и способ получения из целлюлозы сахарных спиртов | |
| US4713363A (en) | High surface area supported noble metal catalysts and process for their preparation | |
| CN1502409A (zh) | 一种适用作选择性放热反应的催化剂载体的中空颗粒 | |
| KR20000006466A (ko) | 실리카를기재로한성형품 | |
| MXPA97001681A (en) | Catalysts for the dehydrogenation of ethylbenzene to stretch | |
| HU220090B (hu) | Meghatározott geometriai alakú granulátumok formájában lévő katalizátorok és katalizátorhordozók és előállítási eljárásuk | |
| KR20080020523A (ko) | Ｍｔｂｅ의 해리 방법 | |
| EP1077916B1 (en) | Process for the preparation of styrenes | |
| WO2019229061A1 (en) | Method for producing transition alumina catalyst monoliths | |
| CN1145687C (zh) | 选择加氢催化剂载体及其制备方法和用途 | |
| JPH11514291A (ja) | ハニカム触媒担体 | |
| RU2469999C2 (ru) | Способ получения стирола и/или замещенного стирола | |
| JP2008132488A (ja) | 酸活性化層状ケイ酸塩系吸着剤ペレットの製造方法、およびこれを触媒として用いる方法 | |
| CN109092298B (zh) | 用于裂解碳四选择加氢催化剂 | |
| US2973330A (en) | Hydroforming catalyst | |
| US4253990A (en) | Preparation method for catalyst supports and materials produced thereby | |
| KR100833635B1 (ko) | 미정제 테레프탈산의 정제 방법 및 이에 적당하며 탄소섬유를 포함하는 촉매 | |
| RU2318868C1 (ru) | Способ гидрирования растительных масел и дистиллированных жирных кислот | |
| RU2323046C1 (ru) | Катализатор для переработки растительных масел и дистиллированных жирных кислот и способ его приготовления | |
| EP4100380B1 (en) | Star-shaped ceramic body for use as catalyst | |
| CN112403531A (zh) | 一种耐水型催化剂载体 | |
| JP6624634B2 (ja) | 脂肪酸エステルの製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20050810 |
|
| CX01 | Expiry of patent term |