CN1370131A - 结晶态沸石固体的制备 - Google Patents
结晶态沸石固体的制备 Download PDFInfo
- Publication number
- CN1370131A CN1370131A CN00811846A CN00811846A CN1370131A CN 1370131 A CN1370131 A CN 1370131A CN 00811846 A CN00811846 A CN 00811846A CN 00811846 A CN00811846 A CN 00811846A CN 1370131 A CN1370131 A CN 1370131A
- Authority
- CN
- China
- Prior art keywords
- solid
- crystal form
- zeolite
- drying
- template compound
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
- C01B33/181—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process
- C01B33/185—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof by a dry process of crystalline silica-polymorphs having molecular sieve properties, e.g. silicalites
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/005—Silicates, i.e. so-called metallosilicalites or metallozeosilites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/22—MFI, e.g. ZSM-5. silicalite, LZ-241
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
含有至少一种沸石材料的结晶态固体的制备方法,其中所述固体自至少一种前体化合物中结晶出来,而且结晶的反应生成物直接输到干燥步骤。
Description
本发明涉及一种制备含有至少一种沸石材料的结晶态固体的改进方法,自结晶过程得到的反应生成物未经除去任何成分而直接输到连续干燥步骤,涉及用该方法制备的固体本身和其作为催化剂、催化剂的载体材料、吸着剂、颜料或塑料填充剂的用途,尤其涉及由烯烃制备环氧化物,并由此用氢过氧化物,尤其是H2O2,由丙烯制备氧化丙烯。
众所周知,沸石是具有有序孔道和笼形结构的结晶态的硅铝酸盐,其开孔是在小于0.9nm的微孔范围之内。这类沸石的网状结构由经共用的氧桥连接的SiO4-和AlO4-四面体结构组成。对已知结构的综述可以参见例如M.W.Meier、D.H.Olson、Ch.Baerlocher所著的《沸石结构类型的概貌》(Atlas of Zeolite Structure Types),第四版,Elsevier,伦敦1996年,第9至229页。
为补偿由于Al(III)嵌入到Si(IV)硅酸盐晶格中而产生的负电价,沸石中存在可交换的阳离子。具体来说,依制备方法的不同,这些阳离子可以是钠、钾、锂或铯的阳离子。如果这些阳离子例如经离子交换而与质子交换,则得到相应的有沸石结构的酸性(即H型)固体。
不含铝且其中硅酸盐晶格中的部分Si(IV)已被钛以Ti(IV)置换的沸石也是众所周知的。在例如EP-A 0 311 983和EP-A 405 978中介绍了这类钛沸石,尤其是有MFI型晶体结构的钛沸石,及其可能的制备方法。除硅和钛外,这类材料还可以含有其它元素,例如铝、锆、锡、铁、钴、镍、镓、硼或少量的氟。在本发明新的方法中所用的沸石催化剂中,沸石的部分或全部的钛可被钒、锆、铬或铌或者两种或多种这些金属所置换。一般来讲,钛和/或钒、锆、铬或铌与硅和钛和/或钒和/或锆和/或铬和/或铌的总和的摩尔比为0.01∶1到0.1∶1。
已知钛沸石可以自X射线衍射图谱的特殊图案判断出来,还可以自其在约960cm-1的红外范围内的骨架振动谱带来判断出来。这样也就可以将其与碱金属钛酸盐或者结晶态或非晶态TiO2相区分开来。
已知具有MFI结构的钛沸石适合作为氧化反应的催化剂。这样,例如EP-A 0 100 118和EP-A 0 100 119介绍了一种方法,其中用钛沸石可使丙烯在水相中与过氧化氢进行环氧化,得到氧化丙烯。EP-A 0 208 311介绍了用环己酮与氨和过氧化氢反应制备环己酮肟。在GB-A 2 116 974和EP-A 0 376 453中分别介绍了用这类催化剂的其它反应,例如芳烃的羟基化和饱和C2-C18烃类的H2O2氧化等。
通常,上文所述的钛沸石的制备方法是使SiO2源、二氧化钛和一种含氮的有机碱(例如氢氧化四丙基铵)的含水混合物在有或没有碱性溶液存在的条件下、在耐压容器中、在升高的温度下反应数小时或数日,得到结晶态产物。原则上,产物要经过过滤、洗涤和干燥并在升高的温度下焙烧以除去含氮的有机相。在由此得到的粉末中,至少一部分钛以不同比例的四倍、五倍或六倍配位存在于沸石的框架中[见Behrens等,《化学会志-化学通报》(J.Chem.Soc.,Chem.Commun.),1991年第678-680页]。正如例如EP-A 0 276 362所介绍的,为改善其催化性能,在上述过程之后用过氧化氢的硫酸溶液洗涤而反复处理,然后必须再次对钛沸石进行干燥和焙烧。为了使其以能够被处置的形式用作催化剂,必须最后在成型阶段向由此得到的钛沸石粉末中加入合适的粘结剂进行成型加工。EP-A 0 200 260介绍了能实现此目的一种方法。
上文所述的自合适原料经水热反应结晶钛沸石的过程通常在50℃到250℃的温度下进行足够长的时间,并且反应过程中随温度的变化存在自生压力。
结晶后,将所需要的通常粒径显著小于1μm的结晶态固体与仍然含有有机模板的强碱性母液分离是一个难题。为实现这一目的,EP-A 0 893158在其实施例中介绍的是要么用传统方法离心分离,再洗涤固体,要么先加入絮凝剂,再离心分离。根据这份公开文件,后续的干燥是经喷雾干燥,或经流化床喷雾造粒干燥。将沸石自结晶过程得到的悬浮液中分离出来以及加入凝絮剂二者构成费时和增加花费的额外工艺步骤。
本发明的目的是提供一种制备含有至少一种沸石材料的结晶态固体的方法,该方法不存在上文所述的缺点,尤其是做到了在结晶和干燥之间不用额外的中间步骤。
我们发现一种制备含有至少一种沸石材料的结晶态固体的方法实现了该目的,该方法中所述固体自至少一种前体化合物中结晶出来,而且结晶的反应生成物直接输到干燥步骤。这里,“直接”一词是指在结晶和干燥之间没有除去任何成分,而且结晶产物最好不经其他中间步骤而输到干燥步骤。
本发明的干燥宜采用喷雾干燥或借助流化床喷雾造粒的干燥进行。这两种方法都可以连续或间歇进行。干燥过程中温度维持在100到350℃、优选100到250℃的范围内,并同时维持该方法所需的安全条件,直到得到自由流动的粉末。干燥宜在含有氧和至少一种惰性气体的气氛中进行。该气氛宜作为载气流循环使用。作为惰性气体,可以采用传统的惰性气体,例如氮、一氧化碳、二氧化碳、氦和氩或者两种或多种这些气体的混合物。该气氛的氧含量宜少于10%(体积),少于5%(体积)更好。此外,为保证不发生爆炸问题,作为惰性气体也可采用含COx的烟道气混合物。可以通过燃烧用于生产烟道气的天然气来得到这种烟道气混合物,而且这样也可以同时为本方法的耗能步骤提供能量。
在本发明的干燥步骤中,调节所用的气氛(尤其是氧含量),以使该过程安全地在爆炸极限之外进行是必要的。
如果上文所述的结晶过程是在一种模板化合物存在的条件下进行,则可以以干物质形式附着在结晶态固体上的该模板化合物可以在后续的步骤中通过用优选含水的洗涤溶液除掉,并可循环到结晶步骤。然而,大部分模板化合物在反应生成物干燥的过程中被除掉。存在于载气流中的可冷凝模板化合物被冷凝出来。
这样,本发明还涉及一种制备含有至少一种沸石材料的结晶态固体的联合方法,其中
(1)所述固体在至少一种模板化合物的存在下自至少一种前体化合物中连续结晶出来;
(2)结晶过程的反应生成物被连续地喷雾干燥,在干燥之前未自结晶的反应生成物中分离出任何成分;
(3)干燥在含有氧(优选少于10%(体积)的氧)和至少一种惰性气体的气氛中进行,该气氛被循环用作载气流;
(4)可以从载气流中冷凝的模板化合物在该气流与待干燥的反应生成物接触后冷凝出来并被循环到步骤(1);
(5)自步骤(2)得到的经喷雾干燥的结晶态固体经连续洗涤过程,使结晶态固体中所含的模板化合物分离出来并被循环到步骤(1);并且
(6)焙烧自步骤(5)得到的结晶态固体,剩余量的模板化合物燃烧所释放的能量被送回到步骤(1)。
此外,当然还可以在干燥前向反应生成物中加入能够使喷雾干燥的材料粘结(即能使所述材料具有机械稳定性)的添加剂,或能够给喷雾干燥的材料掺杂催化活性成分的添加剂。在此应提及德国专利申请DE-A44 25 672,其中介绍了在得到的作为氧化催化剂的固体中使用金属。
按本发明的方法干燥的或制备的含有至少一种沸石材料的结晶态固体没有任何限制。下列的沸石可逐一提及。
宜采用的沸石有Ti、Ge、Te、Ta、V、Cr、Nb和Zr沸石,其中Ti沸石更可取。
宜采用的沸石具体地包括下列结构类型的Ti、Ge、Te、Ta、V、Cr、Nb和Zr沸石:ABW、ACO、AEI、AEL、AEN、AET、AFG、AFI、AFN、AFO、AFR、AFS、AFT、AFX、AFY、AHT、ANA、APC、APD、AST、ATN、ATO、ATS、ATT、ATV、AWO、AWW、BEA、BIK、BOG、BPH、BRE、CAN、CAS、CFI、CGF、CGS、CHA、CHI、CLO、CON、CZP、DAC、DDR、DFO、DFT、DOH、DON、EAB、EDI、EMT、EPI、ERI、ESV、EUO、FAU、FER、GIS、GME、GOO、HEU、IFR、ISV、ITE、JBW、KFI、LAU、LEV、LIO、LOS、LOV、LTA、LTL、LTN、MAZ、MEI、MEL、MEP、MER、MFI、MFS、MON、MOR、MSO、MTF、MTN、MTT、MTW、MWW、NAT、NES、NON、OFF、OSI、PAR、PAU 、PHI、RHO、RON、RSN、RTE、RTH、RUT、SAO、SAT、SBE、SBS、SBT、SFF、SGT、SOD、STF、STI、STT、TER、THO、TON、TSC、VET、VFI、VNI、VSV、WEI、WEN、YUG、ZON和ITQ-4或者含有两个或多个上述结构的混合结构,或者两种或多种上述沸石的混合物,其中具有MFI结构、BEA结构、MEL结构、ITQ-4结构或MFI/MEL混合结构的沸石应被视为是尤其适用的。此类沸石由例如W.M.Meier等人在上文所述的出版物中做了描述。
尤其适用的催化剂具体的是含钛沸石催化剂,通常被称为“TS-1”、“TS-2”、“TS-3”、“ZSM-48”和“ZSM-12”(均含有钛)、TTM-1、Ti-RUT、Ti-MCM-35,“UTD-1”、“CIT-5”、“CIT-1”和“SSZ-24”型含钛沸石,以及其骨架结构与β-沸石同晶的钛沸石。
例如在US 3 329 481中介绍的钛沸石可以使用。在这种钛沸石中,原先在硅酸盐晶格中存在的一些Si(IV)被钛以Ti(IV)所置换。
US4 410 501、EP-A0 311 983、US4 666 692、DE-A 3 047 798和BE1 001 038尤其介绍了其它钛沸石,尤其是具有MFI型晶体结构的钛沸石及其可能的制备方法。这些文献的这部分内容在此完全引入本申请中作为参考。其它具有与MFI结构不相同的结构的并易于用于本发明的含钛沸石例如在EP-A 0 405 978中做了介绍。除硅和钛以外,这些沸石还可含有其它元素,例如铝(例如尤其如DE-A 31 41 283所介绍的)、镓(见EP-A0 266 825)、硼(见US4 666 692)或少量的氟(见EP-A0 292 363)。这些文献中有关介绍沸石的内容在此也完全引入本申请中作为参考。
本发明的方法中可用的其它沸石催化剂尤其在US-A5 430 000和WO94/29408中做了介绍。这些文献的这部分内容在此引入本申请中作为参考。
含钛沸石的其它例子是有铁素沸石(ferrierite)或β-沸石或丝光沸石结构的沸石。
此外,本发明的方法中可以用下列沸石催化剂:
例如DE-A196 23 611.8中介绍的有沸石结构的催化剂,该文献有关催化剂的内容在此完全引入本申请中作为参考。
这些催化剂是基于有沸石结构的硅酸钛或硅酸钒的氧化催化剂,对于该沸石结构,上文所述的结构为优选。正如上述申请所详细介绍的,这些催化剂的特征是它们是经过可提高其强度的成型过程而成形的。
此外,也可以使用基于有沸石结构且含有0.01-30%(重量)一种或多种选自钌、铑、钯、锇、铱、铂、铼、金和银的贵金属的硅酸钛或硅酸钒的氧化催化剂,其特征同样在于经过可提高其强度的成型过程而成形。这类催化剂在DE-A196 23 609.6中有介绍。该文献有关催化剂的内容在此完全引入本申请中作为参考。
关于可提高催化剂强度的成型过程,以及粘合剂和助剂和氧化催化剂的结构,可以参见DE-A196 23 611.8。
DE-A196 23 609.6中介绍的氧化催化剂含有0.01-30%(重量),更好是0.05-15%(重量),尤其好是0.1-8%(重量)(在每种情况下以钛沸石或钒沸石的量为准)的所述贵金属。在此,尤其适用的是钯。贵金属可以以合适的贵金属组分的形式施于催化剂上,例如在可提高催化剂强度的成型步骤之前、过程中或之后以水溶性盐的形式施于催化剂上。
此外,根据本发明,下列催化剂可以使用:
含有至少一种多孔氧化材料且可由包括有下列步骤的方法得到的模制品:
(I)向含有一种多孔氧化材料或者两种或多种混合的多孔氧化材料的混合物中加入含有至少一种醇和水的混合物,和
(II)捏合、模制、干燥并焙烧由步骤(I)得到的混合物。
这种催化剂的细节可以参见DE-A197 23 751.7。该文献的内容在此完全引入本申请中作为参考。
根据本发明,还可以使用可由包括下列步骤(I)的方法制备的含硅石的固体:
(I)在一种液态介质中使至少一种硅石前体与至少一种结构成形剂接触,其特征是所述结构成形剂是一种聚乙烯亚胺或者两种或多种聚乙烯亚胺的混合物。
这种固体的细节可参见DE-A197 32 865.2。该文献有关这部分的内容在此完全引入本申请中作为参考。
另一种易于使用的催化剂是含有一种惰性载体和在其上施加的至少一种硅酸盐(最好是结晶态硅酸盐)的模制品,其制法可以是向DE-A19754 924.1所介绍的那样将含有至少一种硅酸盐和至少一种金属酸酯或其水解产物或者金属酸酯与其水解产物的混合物的一种混合物施于惰性载体上。该文献有关这部分的内容在此同样引入本申请中作为参考。
根据本发明,还可以使用含有至少一种硅酸盐和至少一种金属氧化物的模制品,其制备方法可以包括如下步骤(i):
(i)将至少一种硅酸盐与至少一种碱金属和碱土金属离子含量低的金属氧化物溶胶混合,见DE-A198 15 879.3。
该文献有关这方面的内容在此同样引入本申请中作为参考。
根据本发明,还可以使用有RUT结构的硅酸钛,其制法包括如下步骤(i)和(ii):
(i)制备含至少一种SiO2源和至少一种钛源的混合物;
(ii)在一个耐压容器中加入至少一种模板化合物,使步骤(i)的混合物结晶,得到一种悬浮液,其特征是使用了适于稳定硅酸盐结构[445462]和[44566581]的笼子的胺或铵盐作为模板化合物。
这些催化剂的细节可参见DE-A198 39 792.5。
根据本发明,还可以使用DE-A198 47 630.2所介绍的含有中孔和微孔的硅石,其中所述的硅石宜具有下列(1)到(3)项特征中的一项或多项:(1)中孔和微孔的比表面积之和至少为200m2/g;(2)中孔和微孔的孔体积之和为至少0.2ml/g;(3)中孔的直径分布的最大值为至少3nm。
这些催化剂的进一步细节可参见上述申请。该文献有关这方面的内容在此完全引入本申请中作为参考。
如上文所述,按本发明的方法制备的含沸石的结晶态固体可按常规方式用作催化剂、催化剂的载体材料、吸着剂,用作塑料的颜料或填料,尤其可提到用于使用氢过氧化物由链烯烃制备烯化氧,尤其是使丙烯与H2O2反应制备氧化丙烯。
下面参照实施例来说明本发明。
实施例
把11.98千克四乙氧基硅烷,240克原钛酸四乙酯和7.06千克氢氧化四丙铵(40%(重量)水溶液)与10.54千克软化水的混合物在一个可搅拌的钢质耐压容器中混合并在室温下均化一小时。蒸除所生成的醇,向残余物中加水至18.1千克,并在搅拌下于175℃结晶24小时。
将结晶产物不经过进一步分离或纯化步骤直接通过管道输往一个喷雾干燥器(购自Niro)中,并通过一个喷嘴以3升/小时的速率喷雾。入口温度为230℃,出口温度为110到120℃。所用载气是含2%(体积)氧气的氮气。干燥气的通量为70m3(标准温度压力(S.T.P.))/小时,且干燥气用出去气预热到110℃。
以所用的SiO2为基准,结晶和喷雾干燥联合过程后钛沸石中SiO2的收率为94%。
Claims (10)
1.一种制备含有至少一种沸石材料的结晶态固体的方法,其中所述固体自至少一种前体化合物中结晶出来,而且结晶的反应生成物直接输到干燥步骤。
2.根据权利要求1的方法,其特征在于所述干燥是喷雾干燥。
3.根据权利要求1或2的方法,其特征在于所述干燥在含有氧,优选少于10%(体积)的氧,和至少一种惰性气体的气氛中进行。
4.根据权利要求1-3中任意一项的方法,其特征在于结晶是在至少一种模板化合物的存在下进行的。
5.根据权利要求4的方法,其特征在于在载气流形式的气氛与待干燥的反应生成物接触后,该气流中可以冷凝的模板化合物冷凝出来。
6.根据权利要求4或5的方法,其特征在于在干燥的结晶态固体中所含的模板化合物通过至少一次洗涤过程与所述固体分离。
7.一种可按权利要求1-6中任何一项的方法制备的结晶态固体,其特征在于所述的沸石材料是Ti、Ge、Te、Ta、V、Cr、Nb或Zr沸石,其结构类型为ABW、ACO、AEI、AEL、AEN、AET、AFG、AFI、AFN、AFO、AFR、AFS、AFT、AFX、AFY、AHT、ANA、APC、APD、AST、ATN、ATO、ATS、ATT、ATV、AWO、AWW、BEA、BIK、BOG、BPH、BRE、CAN、CAS、CFI、CGF、CGS、CHA、CHI、CLO、CON、CZP、DAC、DDR、DFO、DFT、DOH、DON、EAB、EDI、EMT、EPI、ERI、ESV、EUO、FAU、FER、GIS、GME、GOO、HEU、IFR、ISV、ITE、JBW、KFI、LAU、LEV、LIO、LOS、LOV、LTA、LTL、LTN、MAZ、MEI、MEL、MEP、MER、MFI、MFS、MON、MOR、MSO、MTF、MTN、MTT、MTW、MWW、NAT、NES、NON、OFF、OSI、PAR、PAU、PHI、RHO、RON、RSN、RTE、RTH、RUT、SAO、SAT、SBE、SBS、SBT、SFF、SGT、SOD、STF、STI、STT、TER、THO、TON、TSC、VET、VFI、VNI、VSV、WEI、WEN、YUG、ZON和ITQ-4或者含有两个或多个上述结构的混合结构,或者是两种或多种上述沸石的混合物。
8.根据权利要求7的固体,其特征在于所述沸石材料含有选自铝、钛、硼、铁、镓、钒、锆、锌、锡、碲、锗、稀土金属和两种或多种这些元素混合物中的至少一种,和/或选自钠、钾、镁、钙、Ib族、IIb族和VIIIa族金属和两种或多种这些元素混合物中的至少一种。
9.可按权利要求1-6中任意一项制备的固体或权利要求7或8的固体作为催化剂、催化剂的载体材料、吸着剂、颜料或塑料填料的用途。
10.一种制备含有至少一种沸石材料的结晶态固体的联合方法,其中
(1)所述固体在至少一种模板化合物的存在下自至少一种前体化合物中连续结晶出来;
(2)结晶过程的反应生成物被连续地喷雾干燥,在干燥之前自结晶的反应生成物中未分离出任何成分;
(3)干燥在含有氧,优选少于10%(体积)的氧,和至少一种惰性气体的气氛中进行,该气氛被循环用作载气流;
(4)可以从载气流中冷凝的模板化合物在该气流与待干燥的反应生成物接触后冷凝出来并被循环到步骤(1);
(5)自步骤(2)得到的经喷雾干燥的结晶态固体经连续洗涤过程,使结晶态固体中所含的模板化合物分离出来并被循环到步骤(1);并且
(6)焙烧自步骤(5)得到的结晶态固体,剩余量的模板化合物燃烧所释放的能量被送回到步骤(1)。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19939416A DE19939416A1 (de) | 1999-08-20 | 1999-08-20 | Verfahren zur Herstellung eines kristallinen, zeolithischen Feststoffs |
DE19939416.4 | 1999-08-20 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005100088390A Division CN100460323C (zh) | 1999-08-20 | 2000-08-08 | 结晶态沸石固体 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1370131A true CN1370131A (zh) | 2002-09-18 |
CN1197768C CN1197768C (zh) | 2005-04-20 |
Family
ID=7918951
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB008118469A Expired - Lifetime CN1197768C (zh) | 1999-08-20 | 2000-08-08 | 结晶态沸石固体的制备 |
CNB2005100088390A Expired - Lifetime CN100460323C (zh) | 1999-08-20 | 2000-08-08 | 结晶态沸石固体 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2005100088390A Expired - Lifetime CN100460323C (zh) | 1999-08-20 | 2000-08-08 | 结晶态沸石固体 |
Country Status (14)
Country | Link |
---|---|
US (2) | US6805851B1 (zh) |
EP (2) | EP2347997A3 (zh) |
JP (2) | JP4782962B2 (zh) |
KR (2) | KR100961445B1 (zh) |
CN (2) | CN1197768C (zh) |
AT (1) | ATE510798T1 (zh) |
AU (1) | AU7408300A (zh) |
CA (1) | CA2382297A1 (zh) |
DE (1) | DE19939416A1 (zh) |
ES (1) | ES2365320T3 (zh) |
IN (1) | IN2002CH00261A (zh) |
MX (1) | MXPA02001784A (zh) |
WO (1) | WO2001014251A1 (zh) |
ZA (1) | ZA200201375B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101489648B (zh) * | 2006-06-26 | 2013-11-20 | 艾尼股份公司 | 用于气体分离的方法和沸石材料 |
CN109890757A (zh) * | 2016-11-17 | 2019-06-14 | 雪佛龙美国公司 | 通过沸石间转变合成mtw骨架型分子筛 |
CN112805272A (zh) * | 2018-10-09 | 2021-05-14 | 巴斯夫欧洲公司 | 包含具有mfi型骨架的沸石材料的模制品 |
Families Citing this family (75)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4241068B2 (ja) | 2002-03-07 | 2009-03-18 | 昭和電工株式会社 | Mww型ゼオライト物質の製造方法 |
DE10320635A1 (de) | 2003-05-08 | 2004-11-18 | Basf Ag | Verfahren zur Herstellung von Propylenoxid |
US7309355B2 (en) | 2003-06-27 | 2007-12-18 | Depuy Mitek, Inc. | Flexible tibial sheath |
US7182932B2 (en) * | 2004-01-30 | 2007-02-27 | Lyondell Chemical Technology, L.P. | Catalyst preparation |
US8109965B2 (en) | 2004-06-09 | 2012-02-07 | Biomet Sports Medicine, LLP | Method and apparatus for soft tissue fixation |
JP2006069864A (ja) * | 2004-09-03 | 2006-03-16 | National Institute Of Advanced Industrial & Technology | ナノポーラス体及びその製造方法 |
US8118836B2 (en) | 2004-11-05 | 2012-02-21 | Biomet Sports Medicine, Llc | Method and apparatus for coupling soft tissue to a bone |
US8303604B2 (en) | 2004-11-05 | 2012-11-06 | Biomet Sports Medicine, Llc | Soft tissue repair device and method |
US7905904B2 (en) | 2006-02-03 | 2011-03-15 | Biomet Sports Medicine, Llc | Soft tissue repair device and associated methods |
US7749250B2 (en) | 2006-02-03 | 2010-07-06 | Biomet Sports Medicine, Llc | Soft tissue repair assembly and associated method |
US8840645B2 (en) | 2004-11-05 | 2014-09-23 | Biomet Sports Medicine, Llc | Method and apparatus for coupling soft tissue to a bone |
US7658751B2 (en) | 2006-09-29 | 2010-02-09 | Biomet Sports Medicine, Llc | Method for implanting soft tissue |
US7909851B2 (en) | 2006-02-03 | 2011-03-22 | Biomet Sports Medicine, Llc | Soft tissue repair device and associated methods |
US9017381B2 (en) | 2007-04-10 | 2015-04-28 | Biomet Sports Medicine, Llc | Adjustable knotless loops |
US8298262B2 (en) | 2006-02-03 | 2012-10-30 | Biomet Sports Medicine, Llc | Method for tissue fixation |
US8137382B2 (en) | 2004-11-05 | 2012-03-20 | Biomet Sports Medicine, Llc | Method and apparatus for coupling anatomical features |
US8361113B2 (en) | 2006-02-03 | 2013-01-29 | Biomet Sports Medicine, Llc | Method and apparatus for coupling soft tissue to a bone |
US8088130B2 (en) | 2006-02-03 | 2012-01-03 | Biomet Sports Medicine, Llc | Method and apparatus for coupling soft tissue to a bone |
US8128658B2 (en) | 2004-11-05 | 2012-03-06 | Biomet Sports Medicine, Llc | Method and apparatus for coupling soft tissue to bone |
US9801708B2 (en) | 2004-11-05 | 2017-10-31 | Biomet Sports Medicine, Llc | Method and apparatus for coupling soft tissue to a bone |
US8998949B2 (en) | 2004-11-09 | 2015-04-07 | Biomet Sports Medicine, Llc | Soft tissue conduit device |
US8652171B2 (en) | 2006-02-03 | 2014-02-18 | Biomet Sports Medicine, Llc | Method and apparatus for soft tissue fixation |
US11259792B2 (en) | 2006-02-03 | 2022-03-01 | Biomet Sports Medicine, Llc | Method and apparatus for coupling anatomical features |
US8652172B2 (en) | 2006-02-03 | 2014-02-18 | Biomet Sports Medicine, Llc | Flexible anchors for tissue fixation |
US8562647B2 (en) | 2006-09-29 | 2013-10-22 | Biomet Sports Medicine, Llc | Method and apparatus for securing soft tissue to bone |
US8574235B2 (en) | 2006-02-03 | 2013-11-05 | Biomet Sports Medicine, Llc | Method for trochanteric reattachment |
US8597327B2 (en) | 2006-02-03 | 2013-12-03 | Biomet Manufacturing, Llc | Method and apparatus for sternal closure |
US11311287B2 (en) | 2006-02-03 | 2022-04-26 | Biomet Sports Medicine, Llc | Method for tissue fixation |
US9271713B2 (en) | 2006-02-03 | 2016-03-01 | Biomet Sports Medicine, Llc | Method and apparatus for tensioning a suture |
US8801783B2 (en) | 2006-09-29 | 2014-08-12 | Biomet Sports Medicine, Llc | Prosthetic ligament system for knee joint |
US8771352B2 (en) | 2011-05-17 | 2014-07-08 | Biomet Sports Medicine, Llc | Method and apparatus for tibial fixation of an ACL graft |
US9078644B2 (en) | 2006-09-29 | 2015-07-14 | Biomet Sports Medicine, Llc | Fracture fixation device |
US8251998B2 (en) | 2006-08-16 | 2012-08-28 | Biomet Sports Medicine, Llc | Chondral defect repair |
US9149267B2 (en) | 2006-02-03 | 2015-10-06 | Biomet Sports Medicine, Llc | Method and apparatus for coupling soft tissue to a bone |
US8506597B2 (en) | 2011-10-25 | 2013-08-13 | Biomet Sports Medicine, Llc | Method and apparatus for interosseous membrane reconstruction |
US8936621B2 (en) | 2006-02-03 | 2015-01-20 | Biomet Sports Medicine, Llc | Method and apparatus for forming a self-locking adjustable loop |
US9538998B2 (en) | 2006-02-03 | 2017-01-10 | Biomet Sports Medicine, Llc | Method and apparatus for fracture fixation |
US10517587B2 (en) | 2006-02-03 | 2019-12-31 | Biomet Sports Medicine, Llc | Method and apparatus for forming a self-locking adjustable loop |
US8968364B2 (en) | 2006-02-03 | 2015-03-03 | Biomet Sports Medicine, Llc | Method and apparatus for fixation of an ACL graft |
US8562645B2 (en) | 2006-09-29 | 2013-10-22 | Biomet Sports Medicine, Llc | Method and apparatus for forming a self-locking adjustable loop |
US7381674B1 (en) * | 2006-07-28 | 2008-06-03 | Uop Llc | Iridium and germanium-containing catalysis and alkylaromatic transalkylation processes using such catalysts |
US9918826B2 (en) | 2006-09-29 | 2018-03-20 | Biomet Sports Medicine, Llc | Scaffold for spring ligament repair |
US11259794B2 (en) | 2006-09-29 | 2022-03-01 | Biomet Sports Medicine, Llc | Method for implanting soft tissue |
US8500818B2 (en) | 2006-09-29 | 2013-08-06 | Biomet Manufacturing, Llc | Knee prosthesis assembly with ligament link |
US8226714B2 (en) | 2006-09-29 | 2012-07-24 | Depuy Mitek, Inc. | Femoral fixation |
US8672969B2 (en) | 2006-09-29 | 2014-03-18 | Biomet Sports Medicine, Llc | Fracture fixation device |
US20080253959A1 (en) * | 2007-03-30 | 2008-10-16 | Johnson Ivy D | Synthesis crystalline molecular sieves |
US9365430B2 (en) * | 2007-10-26 | 2016-06-14 | Exxonmobil Chemical Patents Inc. | Method of making M41S family molecular sieve |
FR2931708B1 (fr) * | 2008-05-28 | 2014-03-14 | Inst Francais Du Petrole | Catalyseur a base d'un materiau cristallise a porosite hierarchisee et organisee et son utilisation en oligomerisation des olefines legeres |
US8063259B2 (en) * | 2008-08-18 | 2011-11-22 | Fina Technology, Inc. | Toluene disproportionation using Nb/mordenite catalyst |
US20100305710A1 (en) | 2009-05-28 | 2010-12-02 | Biomet Manufacturing Corp. | Knee Prosthesis |
TWI399242B (zh) * | 2009-12-11 | 2013-06-21 | China Petrochemical Dev Corp Taipei Taiwan | Method for preparing large-diameter titanium-silicon molecular sieve and method for producing cyclohexanone oxime using the molecular sieve |
US9357991B2 (en) | 2011-11-03 | 2016-06-07 | Biomet Sports Medicine, Llc | Method and apparatus for stitching tendons |
US9314241B2 (en) | 2011-11-10 | 2016-04-19 | Biomet Sports Medicine, Llc | Apparatus for coupling soft tissue to a bone |
US9370350B2 (en) | 2011-11-10 | 2016-06-21 | Biomet Sports Medicine, Llc | Apparatus for coupling soft tissue to a bone |
US9381013B2 (en) | 2011-11-10 | 2016-07-05 | Biomet Sports Medicine, Llc | Method for coupling soft tissue to a bone |
US9259217B2 (en) | 2012-01-03 | 2016-02-16 | Biomet Manufacturing, Llc | Suture Button |
US9757119B2 (en) | 2013-03-08 | 2017-09-12 | Biomet Sports Medicine, Llc | Visual aid for identifying suture limbs arthroscopically |
US9918827B2 (en) | 2013-03-14 | 2018-03-20 | Biomet Sports Medicine, Llc | Scaffold for spring ligament repair |
JP6545157B2 (ja) * | 2013-06-13 | 2019-07-17 | ビーエーエスエフ ソシエタス・ヨーロピアBasf Se | ブタジエンの製造方法 |
CN105848781B (zh) | 2013-10-23 | 2020-07-17 | 巴斯夫欧洲公司 | 疏水性沸石材料的模制品及其制备方法 |
US10136886B2 (en) | 2013-12-20 | 2018-11-27 | Biomet Sports Medicine, Llc | Knotless soft tissue devices and techniques |
US9615822B2 (en) | 2014-05-30 | 2017-04-11 | Biomet Sports Medicine, Llc | Insertion tools and method for soft anchor |
US9700291B2 (en) | 2014-06-03 | 2017-07-11 | Biomet Sports Medicine, Llc | Capsule retractor |
US10039543B2 (en) | 2014-08-22 | 2018-08-07 | Biomet Sports Medicine, Llc | Non-sliding soft anchor |
US9955980B2 (en) | 2015-02-24 | 2018-05-01 | Biomet Sports Medicine, Llc | Anatomic soft tissue repair |
US9974534B2 (en) | 2015-03-31 | 2018-05-22 | Biomet Sports Medicine, Llc | Suture anchor with soft anchor of electrospun fibers |
EP3205398A1 (en) | 2016-02-12 | 2017-08-16 | Hyundai Motor Company | Method for preparing zeolite catalyst |
US10343925B2 (en) | 2016-02-12 | 2019-07-09 | Hyundai Motor Company | Method for preparing zeolite catalyst |
KR101982040B1 (ko) | 2016-06-21 | 2019-05-24 | 삼성전기주식회사 | 팬-아웃 반도체 패키지 |
AU2017210592A1 (en) | 2016-08-04 | 2018-02-22 | Stryker Corporation | Soft tissue or suture sheath and methods of use in surgery |
JP7068298B2 (ja) * | 2016-12-13 | 2022-05-16 | ビーエーエスエフ ソシエタス・ヨーロピア | チタン含有ゼオライトの製造の方法 |
JP2019056723A (ja) * | 2017-09-19 | 2019-04-11 | シャープ株式会社 | 液晶表示装置 |
US10941342B2 (en) | 2018-07-23 | 2021-03-09 | Samsung Display Co., Ltd. | Etchant composition and method of manufacturing wiring substrate using the same |
JP7085688B2 (ja) * | 2019-03-08 | 2022-06-16 | 日本碍子株式会社 | 結晶性物質および膜複合体 |
Family Cites Families (44)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3329481A (en) | 1963-10-18 | 1967-07-04 | Union Oil Co | Crystalline titano-silicate zeolites |
US3838192A (en) * | 1971-10-28 | 1974-09-24 | Huber Corp J M | Production of alkali metal polysilicates |
GR66589B (zh) | 1978-06-22 | 1981-03-30 | Snam Progetti | |
IT1127311B (it) | 1979-12-21 | 1986-05-21 | Anic Spa | Materiale sintetico,cristallino,poroso costituito da ossidi di silicio e titanio,metodo per la sua preparazione e suoi usi |
DE3141283A1 (de) | 1981-10-17 | 1983-04-28 | Hoechst Ag, 6230 Frankfurt | "titanhaltige zeolithe und verfahren zu ihrer herstellung sowie ihre verwendung" |
IT1150699B (it) | 1982-03-19 | 1986-12-17 | Anic Spa | Procedimento per la ossidrilazione di idrocarburi aromatici |
IT1152299B (it) | 1982-07-28 | 1986-12-31 | Anic Spa | Procedimento per l'espossidazione di composti olefinici |
IT1152296B (it) | 1982-07-28 | 1986-12-31 | Anic Spa | Procedimento per la sintesi di monometileteri dei glicoli |
IT1187661B (it) | 1985-04-23 | 1987-12-23 | Enichem Sintesi | Catalizzatore a base di silicio e titanio ad elevata resistenza meccanica |
IT1214622B (it) | 1985-07-10 | 1990-01-18 | Montedipe Spa | Processo catalitico per laproduzione di cicloesanonossima. |
IT1213363B (it) | 1986-10-22 | 1989-12-20 | Eniricerche Spa | Materiale sintetico cristallino poroso contenente ossidi di silicio titanio e gallio. |
US4794198A (en) | 1986-11-14 | 1988-12-27 | Montedipe S.P.A. | Catalytic process for the manufacture of oximes |
DE3766612D1 (de) | 1987-01-29 | 1991-01-17 | Pilot Precision K K | Mechanischer schreibstift mit automatischem minenvorschub. |
EP0292363B1 (fr) | 1987-05-22 | 1993-04-21 | Rhone-Poulenc Chimie | Zéolites de structures MFI à base de silice et d'oxyde de titane et procédé de synthèse de celles-ci |
IT1222868B (it) | 1987-10-12 | 1990-09-12 | Montedipe Spa | Metodo per la preparazione di titanio silicaliti |
IT1216500B (it) | 1988-03-23 | 1990-03-08 | Eniricerche S P A Milano Enich | Procedimento per la preparazione di materiali sintetici cristallini porosi costituiti da ossidi di silicio e titanio. |
KR0151712B1 (ko) | 1988-11-08 | 1998-10-15 | 피터 챨스 보우덴 | 포화탄화수소 사슬의 산화 |
US5244650A (en) | 1989-06-29 | 1993-09-14 | Engelhard Corporation | Large-pored molecular sieves with charged octahedral titanium and charged tetrahedral aluminum sites |
JP2984317B2 (ja) * | 1990-05-02 | 1999-11-29 | 株式会社トクヤマ | ゼオライト組成物の製造方法 |
SE469080B (sv) * | 1991-10-28 | 1993-05-10 | Eka Nobel Ab | Foerpackningsmaterial, foerfarande foer framstaellning av foerpackningsmaterial, anvaendning av hydrofob zeolit foer framstaellning av foerpackningsmaterial samt anvaendning av foerpackningsmaterial |
JP3023581B2 (ja) * | 1992-06-25 | 2000-03-21 | 住友化学工業株式会社 | ゼオライト成形体の強度向上方法 |
EP0674600B1 (en) * | 1992-12-16 | 2001-10-17 | Chevron U.S.A. Inc. | Preparation of aluminosilicate zeolites |
US5378671A (en) | 1993-06-03 | 1995-01-03 | Mobil Oil Corp. | Method for preparing catalysts comprising zeolites |
US5430000A (en) | 1993-08-25 | 1995-07-04 | Mobil Oil Corporation | Method for preparing titania-bound zeolite catalysts |
CN1070822C (zh) * | 1993-10-21 | 2001-09-12 | 切夫里昂研究和技术公司 | 铝硅酸盐沸石的制备 |
IL108272A (en) * | 1994-01-05 | 1998-02-22 | Super Industry Ltd | Process for production of zeolites |
DE4425672A1 (de) | 1994-07-20 | 1996-01-25 | Basf Ag | Oxidationskatalysator, Verfahren zu seiner Herstellung und Oxidationsverfahren unter Verwendung des Oxidationskatalysators |
CN1049610C (zh) * | 1995-06-02 | 2000-02-23 | 复旦大学 | 不含铝的钛(锆、钒)硅五员环沸石催化剂的制备方法 |
US5637287A (en) * | 1996-02-02 | 1997-06-10 | Exxon Research & Engineering Company | Synthesis process for faujasite family zeolites using mother liquor recycle |
DE19623609A1 (de) | 1996-06-13 | 1997-12-18 | Basf Ag | Oxidationskatalysator und Verfahren zur Herstellung von Epoxiden aus Olefinen, Wasserstoff und Sauerstoff unter Verwendung des Oxidationskatalysators |
DE19623611A1 (de) | 1996-06-13 | 1997-12-18 | Basf Ag | Verfahren zur Herstellung von Epoxiden aus Olefinen und Wasserstoffperoxid |
US5919430A (en) * | 1996-06-19 | 1999-07-06 | Degussa Aktiengesellschaft | Preparation of crystalline microporous and mesoporous metal silicates, products produced thereby and use thereof |
DE59702854D1 (de) * | 1996-12-19 | 2001-02-08 | Ciba Sc Holding Ag | Farbmittelbeladenes Molekularsieb |
US6042807A (en) * | 1997-04-02 | 2000-03-28 | Arco Chemical Technology, L.P. | Tellurium-containing molecular sieves |
DE19723751A1 (de) | 1997-06-06 | 1998-12-10 | Basf Ag | Formkörper und Verfahren zu dessen Herstellung |
DE19731627A1 (de) * | 1997-07-23 | 1999-01-28 | Degussa | Granulate, enthaltend Titansilikalit-l |
DE19732865A1 (de) | 1997-07-30 | 1999-02-04 | Basf Ag | Siliciumdioxid enthaltender Feststoff mit großer Oberfläche |
IT1295267B1 (it) * | 1997-10-03 | 1999-05-04 | Enichem Spa | Processo per preparare zeoliti legate |
DE19754924A1 (de) | 1997-12-10 | 1999-06-17 | Basf Ag | Formkörper umfassend einen inerten Träger und mindestens ein poröses oxidisches Material |
DE19815879A1 (de) | 1998-04-08 | 1999-10-14 | Basf Ag | Verfahren zur Herstellung eines Formkörpers |
AU742902B2 (en) * | 1998-08-04 | 2002-01-17 | Bp Oil International Limited | Delaminated microporous solid |
DE19839792A1 (de) | 1998-09-01 | 2000-03-02 | Basf Ag | Verfahren zur Herstellung eines Titansilikates mit RUT-Struktur |
DE19847630A1 (de) | 1998-10-15 | 2000-04-20 | Basf Ag | Siliciumdioxid mit Meso- und Mikroporen |
IT1314263B1 (it) * | 1999-12-03 | 2002-12-06 | Enichem Spa | Processo per la preparazione di catalizzatori zeolitici. |
-
1999
- 1999-08-20 DE DE19939416A patent/DE19939416A1/de not_active Withdrawn
-
2000
- 2000-08-08 JP JP2001518353A patent/JP4782962B2/ja not_active Expired - Lifetime
- 2000-08-08 AT AT00962299T patent/ATE510798T1/de active
- 2000-08-08 CN CNB008118469A patent/CN1197768C/zh not_active Expired - Lifetime
- 2000-08-08 EP EP10181285A patent/EP2347997A3/de not_active Withdrawn
- 2000-08-08 ES ES00962299T patent/ES2365320T3/es not_active Expired - Lifetime
- 2000-08-08 AU AU74083/00A patent/AU7408300A/en not_active Abandoned
- 2000-08-08 EP EP00962299A patent/EP1230156B1/de not_active Revoked
- 2000-08-08 MX MXPA02001784A patent/MXPA02001784A/es active IP Right Grant
- 2000-08-08 WO PCT/EP2000/007704 patent/WO2001014251A1/de active Application Filing
- 2000-08-08 US US10/049,907 patent/US6805851B1/en not_active Expired - Lifetime
- 2000-08-08 KR KR1020097013088A patent/KR100961445B1/ko active IP Right Grant
- 2000-08-08 CN CNB2005100088390A patent/CN100460323C/zh not_active Expired - Lifetime
- 2000-08-08 CA CA002382297A patent/CA2382297A1/en not_active Abandoned
-
2002
- 2002-02-19 IN IN261CH2002 patent/IN2002CH00261A/en unknown
- 2002-02-19 ZA ZA200201375A patent/ZA200201375B/en unknown
- 2002-02-19 KR KR20027002136A patent/KR100927668B1/ko active IP Right Grant
-
2004
- 2004-08-30 US US10/928,104 patent/US7081237B2/en not_active Expired - Lifetime
-
2011
- 2011-05-20 JP JP2011113862A patent/JP5300917B2/ja not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101489648B (zh) * | 2006-06-26 | 2013-11-20 | 艾尼股份公司 | 用于气体分离的方法和沸石材料 |
CN109890757A (zh) * | 2016-11-17 | 2019-06-14 | 雪佛龙美国公司 | 通过沸石间转变合成mtw骨架型分子筛 |
CN109890757B (zh) * | 2016-11-17 | 2022-05-03 | 雪佛龙美国公司 | 通过沸石间转变合成mtw骨架型分子筛 |
CN112805272A (zh) * | 2018-10-09 | 2021-05-14 | 巴斯夫欧洲公司 | 包含具有mfi型骨架的沸石材料的模制品 |
Also Published As
Publication number | Publication date |
---|---|
WO2001014251A1 (de) | 2001-03-01 |
CN100460323C (zh) | 2009-02-11 |
EP2347997A3 (de) | 2012-11-07 |
KR100927668B1 (ko) | 2009-11-20 |
US6805851B1 (en) | 2004-10-19 |
EP1230156A1 (de) | 2002-08-14 |
KR100961445B1 (ko) | 2010-06-09 |
KR20090074828A (ko) | 2009-07-07 |
DE19939416A1 (de) | 2001-02-22 |
CN1197768C (zh) | 2005-04-20 |
MXPA02001784A (es) | 2002-08-12 |
KR20020047123A (ko) | 2002-06-21 |
CA2382297A1 (en) | 2001-03-01 |
IN2002CH00261A (zh) | 2005-10-28 |
ATE510798T1 (de) | 2011-06-15 |
ES2365320T3 (es) | 2011-09-29 |
EP2347997A2 (de) | 2011-07-27 |
JP5300917B2 (ja) | 2013-09-25 |
US7081237B2 (en) | 2006-07-25 |
US20050031535A1 (en) | 2005-02-10 |
ZA200201375B (en) | 2004-05-26 |
CN1673080A (zh) | 2005-09-28 |
JP4782962B2 (ja) | 2011-09-28 |
EP1230156B1 (de) | 2011-05-25 |
JP2011162441A (ja) | 2011-08-25 |
AU7408300A (en) | 2001-03-19 |
JP2003507306A (ja) | 2003-02-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1197768C (zh) | 结晶态沸石固体的制备 | |
CN1444575A (zh) | 制备氧化丙烯的方法 | |
CN100348485C (zh) | 生产含沸石的固体的方法 | |
CN101607211A (zh) | 成型催化剂体 | |
ZA200203681B (en) | Oxide and method for production thereof. | |
US6867326B1 (en) | Method of producing glyphosate or a salt thereof | |
JP6544118B2 (ja) | ゼオライトの製造方法及びε−カプロラクタムの製造方法 | |
CN112742470B (zh) | 核壳结构钛硅材料及其制备方法和大分子酮类氨肟化反应生产酮肟的方法 | |
CN1226187C (zh) | 一种钛硅分子筛复合材料及其合成方法 | |
CN112742469B (zh) | 核壳结构钛硅材料及其制备方法和大分子酮类氨肟化反应生产酮肟的方法 | |
WO2022196043A1 (ja) | ゼオライトの製造方法 | |
CN1538962A (zh) | 1,2-环氧丙烷的制备 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
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 | ||
CX01 | Expiry of patent term |
Granted publication date: 20050420 |