CN1228032A - 催化蒸馏法 - Google Patents
催化蒸馏法 Download PDFInfo
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- CN1228032A CN1228032A CN97197363A CN97197363A CN1228032A CN 1228032 A CN1228032 A CN 1228032A CN 97197363 A CN97197363 A CN 97197363A CN 97197363 A CN97197363 A CN 97197363A CN 1228032 A CN1228032 A CN 1228032A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/002—Apparatus for fixed bed hydrotreatment processes
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- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D59/28—Separation by chemical exchange
- B01D59/32—Separation by chemical exchange by exchange between fluids
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
- B01J19/2495—Net-type reactors
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/32—Packing elements in the form of grids or built-up elements for forming a unit or module inside the apparatus for mass or heat transfer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2219/32408—Metal
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/32—Details relating to packing elements in the form of grids or built-up elements for forming a unit of module inside the apparatus for mass or heat transfer
- B01J2219/324—Composition or microstructure of the elements
- B01J2219/32466—Composition or microstructure of the elements comprising catalytically active material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
在催化蒸馏工艺中使用一种催化剂填料，它是将至少一种作为催化剂和/或促进剂的活性物质通过汽相沉积和/或喷射到作为基体的纺织物、针织品或薄片填料上制成。其中一种多相催化反应是与催化剂填料上同时进行的蒸馏或精馏相结合。
Description
本发明涉及一种催化加氢方法，其中多相催化加氢反应与一种在催化剂填料上同时进行的蒸馏或精馏相结合。本发明还涉及在催化蒸馏方法中催化剂填料的应用。
物料进行催化反应同时将反应产物进行蒸馏分离是精炼范畴广泛使用的操作法。例如将裂化气流选择性加氢及分离。
EP-A1-0556025涉及C5-气流的选择性加氢。其中描述了将C5-气流的选择性加氢制成叔戊基甲基醚(TAN)的方法。加氢过程几乎没有发生将单烯烃饱和。气流中的单烯烃一部分被异构化。双烯烃则加氢成单烯烃，也就是将由轻质石脑油及氢组成的气流通过含沉积在氧化铝上的氧化钯作为催化剂的蒸馏装置。催化剂装在若干由编织物制成的袋内，它们按照螺旋形排列在钢丝结成的网状框架中。作为编织物的材料最好用玻璃纤维或特氟隆。
USA 4443559提出了一种催化蒸馏设备。这种结构既可作为催化剂又可作为蒸馏填料。结构中的催化剂是0.25到1mm粒度范围装在例如编织物、钢丝或塑料制的网袋之类的多孔容器中。这种装有催化剂的网袋排列在基床上留出至少70体积％的空隙使催化剂网袋有扩张收缩的余地。专利中还列举了一些催化反应实例。
US 4242530中提出了一种从C4-气流中分离异丁烯的方法。这里是将异丁烯催化二聚或多聚后从蒸馏塔的釜中分离出来。蒸馏塔从载体上的一种酸性催化剂产生作用。催化剂装在编织成的网袋内，而网袋又安排在钢丝结成的网架。钢丝网形成催化剂的支撑而它可让蒸汽自由通过催化剂的网袋。特别是使用一种酸性阳离子交换固定催化床。
EP-A1-0631813提出了一种催化固定床反应器。固定床反应器由堆叠成的填充单元构成，长条形的填充物形成的壁面可让蒸馏介质自由通过。长条形填充物内部为颗粒状的催化材料，这种颗粒状材料可通过例如振动器从填充物上端装到填充料单元的内部。
EP-B1-0201614提出了一种进行多相催化化学反应的反应器。催化剂由按流体主流轴方向平行排列的瓦楞状平板构成，平板壁面与流体主流轴方向相对稍倾斜，相邻近的平板的倾斜方向正好相反。相邻近的平板之间有一条带形，至少有一部分呈瓦楞状的催化剂块可以随意更换。催化剂块可由例如玻璃金属、钢丝编织或弯曲的物料构成。催化剂块可以是全部为催化活性物质或只是表面催化活化。
EP-B1-0068862提出了一种按一定方式排列的反应床上的催化剂填充模型。催化剂床由交替重叠的平面及波纹形的轨道构成并卷成卷筒。流体可以从平面及波纹形轨道之间通过。在所进行的气液转化反应中平面轨道所包裹的是亲水性的由纺织用的灯芯状材料制成的一种纺织品，卷曲的或制成毡状的布料。波纹形轨道所包裹的则是对反应中的液体为疏水性构成大网眼的材料，催化剂晶粒中含至少一种周期表的VIII族元素。晶粒分布在多孔性基体中部分被包裹起来，这样晶粒与液体的接触基本上被多孔性基体隔离开，但液体内蒸汽状态的气体则可与晶粒接触。所描述的这种基体是用聚四氟乙烯与作为催化剂的铂晶粒构成而以具有较大表面积的碳粒为载体。催化活性Pt/C颗粒是以在水中悬浮的状态加在疏水性聚合物上面，然后在60℃到200℃干燥后接着在365℃烧结加以固定。作为气液转化反应的实例列举了氢同位素在氢气与液态水之间的转换。
EP-B1-0433223提出了催化剂实体与进行多相反应的反应器。这里的催化剂实体是一种静态混合元件作为载体，它可以用金属骨架制成也可由一层陶瓷层作为载体和在它上面加上涂层，涂层表面才是催化剂本身。载体也可以由一个整体构成。材料中没有介绍特定的多相催化反应。
带涂层的催化剂实体在机械力的作用下被液体浸渍的涂层由于附着强度不够可能脱落而被破坏。
散装在填充料单元如纺织物袋中的颗粒状催化剂可能被磨损，特别是装进催化蒸馏装置时以及在操作中受到冲击时。外加在散装填充物料中产生的气压损失较周围要大些造成反应器中的径向混合不均而出现不均一的浓度分布和经常会出现不希望有的死角。
本发明的一个目的是提供一种催化剂供催化蒸馏使用，在这种操作中多相催化反应是与在一种催化剂填料上进行的蒸馏或精馏相结合的。
本发明的另一目的是提供一种适合的催化剂体系供这种催化蒸馏使用，而避免前面所提到的那些缺点。
本发明的再一目的是提供一种反应器用来进行催化蒸馏，反应器中的催化剂填料易于进行更换。
本发明的又一目的是提供一种催化加氢的方法。
按照本发明可实现这些目的，其方法是通过在一种催化蒸馏工艺中使用一种催化剂填料，其制法是通过在作为载体的纺织物、针织物或薄膜上汽相沉积和/或喷射至少一种作为催化剂和/或促进剂的活性物质，此工艺中一种多相催化反应是与在这种催化剂填料上同时进行蒸馏或精馏相结合。在后面的从属权利要求中列举了一些优选的实施方案。这些目的可以采用催化蒸馏反应器来实现，该反应器包括填充有上述催化剂填料的蒸馏塔。此外，这些目的可通过使用这种催化剂填料进行催化加氢方法来实现。
载体材料
作为本发明使用的催化剂所用的载体物料可以是各种各样的薄片、针织品及纺织物，也可以是绕制成的物料。作为丝网按照本发明不同实施方案可用能进行纺织的金属丝织成，如铁、弹性钢、黄铜、磷青铜、钝镍、蒙乃尔镍铜合金、铝、银、锌白铜、镍合金、镍铬、铬钢、不锈钢、耐酸钢以及高耐热的镍铬合金钢等，还有钛等制成的金属丝。
还可用一些无机材料如Al2O3和/或SiO2制成的织物。
按照本发明的另一种实施方案还可用合成材料如塑料制成的丝或纺织品，例如聚酰胺、聚酯、聚乙烯、聚烯烃如聚乙烯、聚丙烯、聚四氟乙烯以及其他可以加工成织物的塑料。
优选的载体材料为金属薄片或金属纺织品，例如由材料号码为1.4767、l.4401、2.4610、1.4765、1.4847、1.4301等的优质钢制造的材料。这些材料的标号是按照德国钢铁员工协会出版的“Stahleisenliste”(钢铁产品目录)第8版87，89，106页，VerlagStahleisen mbH，Düsseldorf，1990摘录的。材料号1.4767又有”Kanthal”(康泰尔)的名称。
金属薄片及金属织品的使用性能特别好，因为它们在涂敷催化活性物质或促进剂之前可以进行表面热处理。例如将金属载体在温度400到1100℃，优选用800到1000℃处理0.5到24小时，优选用1到10小时，也就是在含氧的气氛如空气中加热。按照本发明的一种实施方案可以通过这种热处理调节催化剂的活性或提高其活性。
催化剂载体的涂覆
按照本发明可使用的催化剂载体，特别是纺织物、针织品及薄片可以用真空汽相沉积技术在其上面涂覆催化剂活性物质及促进剂的“薄层”。所谓“薄层”是指厚度为几个埃(A)到最厚为0.5μm之间的涂层。作为真空汽相沉积技术按照本发明可采用的方法是多种多样的，例如热蒸汽化、闪蒸汽化、阴极雾化喷射(喷溅)以及热蒸汽化与阴极喷射相结合的方法。热蒸汽化可以采用直接或间接电加热。
按照本发明也可用电子射线进行汽化。这里是将可汽化的物质放在用水冷却的坩锅内并在物料表面用电子射线强烈加热，即使是高熔点的金属及介电体也可以被汽化。按照本发明的一种实施方案在气流中有目的地加入适当份量的活性气体就可在用汽相沉积技术涂层过程中产生某些化学反应。通过适当的化学反应可在载体上形成氧化物、氮化物或碳化物。
载体，特别是纺织物、针织品及薄片可用本发明提供的方法在一种真空汽相喷镀装置中进行连续的或间歇式的汽相喷镀。例如在此过程中加入的催化活性组分或化合物，例如一种贵重金属在10-2到1010Torr(モ，相当1mm汞柱的压强)优选用10-4到10-8Torr的真空中用电子射线强烈加热使在水冷却的坩锅中的金属汽化并凝结在载体上。比较恰当的安排是尽可能使绝大部分的蒸汽流在载体上冷凝。通过在设备中安装的卷绕机使纺织物、针织品及薄片物连续进行涂布。按照本发明可优选一种由空气到空气的连续喷溅装置。
真空喷镀技术的适当参数及操作条件可参阅例如“Handbook ofthin Film Technology(薄膜技术手册)，Verlag Maissel及Glang，McGraw Hill，New York 1970，“Thin Film Processes”(薄膜制造)由J.L.Voss及B.Kern，Academie Press，New York出版以及EP-A2-0198435。EP-A2-0198435中还提到在优质钢织物上汽相喷镀铂或铂及铑制成的催化剂网状填料。
按照本发明采用真空汽相喷技术制造的催化剂要求在载体上形成的颗粒尽可能是无序的分裂的多晶体并且原子的绝大部分是在薄层的表面。也就是它与光学及电子工业使用的熟知的汽相喷镀技术不同之处。那里要求保证载体及涂层的高纯度还要求载体保持预定的凝结温度以及规定的汽相喷镀速率。
按照本发明的方法可以在载体上汽相喷镀一种或几种催化活性化合物或促进剂。
按照本发明的一种实施方案优选用的涂层厚度在0.2nm到10nm范围，特别优选是在0.5nm到20nm范围。
按照本发明的一种实施方案作为催化活性化合物采用元素周期表中第1族及/或第VII及/或第VIII副族元素。促进剂按照本发明可以选择元素周期表中第IV、V、VI主族以及第II、III、VI、VII副族元素。
作为促进剂按照本发明的一种实施方案可采用稀土金属。
按照本发明作为催化活性元素的例子是：铜、银、金、铼、钌、钴、铑、镍、钯和/或铂以及这些元素的混合物。促进剂的例子是：铅、饧、硅、锌、镉、钛、锆，以及它们的混合物。
带涂层的载体材料可以在涂层后进行热处理，例如用钯涂布的载体材料可以在温度200到800℃，优选300到700℃处理0.5到2小时。
催化物制成后可以按要求或在需要时用氢在温度20到250℃，优选在100到200℃还原。还原过程也可以直接在反应器中进行比较有利。
如果对某种催化蒸馏需要时也可用抑制剂代替促进剂进行汽相喷镀。
按照本发明的一种实施方案，催化剂也可系统地进行组合，例如在一个汽相喷镀装置中设置若干个不同的发生蒸汽的来源。这样就可以在载体上镀一层氧化物层或通过活性蒸汽镀一层粘着层在载体上。在这个底层上可以交替汽相喷镀上若干具有催化活性的组分及促进剂。在配料中引入一些反应活性气体可以从氧化物及其他化合物汽相喷镀成促进剂层。热处理步骤也可在中间插入或安排在最后。
按照本发明用汽相喷镀制成的催化剂，特别是催化织物、催化针织品，催化薄片上的催化活性化合物或促进剂的附着强度很好。因此可以制成各种形状，通过剪裁加工成整体的催化元件、催化活性化合物或促进剂不会从上面剥落。按本发明制造的催化剂织物、针织品及薄片，可以用来制成填料反应器或蒸馏塔的各种几何形状的填料，如在蒸馏技术及萃取技术中熟知的那些填料品种。本发明优选用的催化剂填料的几何形状为在方法中压力损失最小的品种例如Montz A3及Sulzer BX，DX及EX型。按照本发明用催化薄片或催化压延金属薄片的一个几何形状例子为Montz BSH型。
按照单位体积所使用的催化剂量，特别是按催化剂织物量、针织品量或薄片量(带催化剂)可以在一个较大范围内控制，从而制成不同大小的孔隙或通道宽度在催化剂织物、针织品或薄片内。通过适当选择催化剂织物、针织品或薄片按单位体积计算的使用量可以调节蒸馏反应器中最大的压力损失以适合催化剂的实验所规定的要求。
本发明优选用的催化剂具有一种整体的形状如在EP-A2-0564830中所描述的例子。EP-A1-0218124及EP-A1-0412415中还描述了别的适用的催化剂例子。
催化蒸馏
按照本发明制成的催化剂填料可以在催化蒸馏反应中使用。通过适当的催化剂填料形状的选择可以调整按单位体积计算的催化剂密度，例如采用整体形状的填料可以将催化蒸馏设备中的压力分布按要求进行调整。通过控制催化活性化合物或促进剂或抑制剂的汽相喷镀量可以调整催化剂元件的反应活性以适应所进行的反应过程的要求强度。如前所述，在催化填料的参与下进行的催化反应与反应混合物的蒸馏或精馏同时进行。
“催化蒸馏”的含意是在适当的设备中化学反应与一种蒸馏或精馏过程结合进行。反应过程与蒸馏或精馏过程的基本上同时在一种多相催化剂填料上进行，当然主要作用是催化化学反应。化学反应是一种化合物与催化剂填料接触后转化成另一种化合物，例如吸收了另一些化学成分，如在加氢中吸收氢。在催化剂填料上的化学反应是多相的，也就是在进行转化的反应混合物中至少有一个组分直接或转化后立即从反应混合物中蒸馏分离出去。结果是化学反应与物质分离同时进行，在化学反应中生成的产品可以被蒸馏出去或残留在蒸馏釜中。
如在本发明的一种实施方案中，两种不同的化合物通过催化剂填料后，至少是其中之一转化成另一种化合物。加氢的情况就是一个例子。
催化加氢
本发明还涉及一种加氢的工艺。如上述加氢过程中在催化剂填料内还同时出现将加氢混合物的一个组分蒸馏或精馏出去。
反应器
本发明还涉及进行催化蒸馏的反应器，它包含一个蒸馏塔，如前述塔中用催化填料填充。这种反应器可用来进行前述的化学反应，其优点为在反应器操作以及装催化填料时对填料不产生磨损现象，因为催化填料可以简单用置换法更新而具反应器操作中的压力损失可以降低到最小。
结合下列实例将本发明作进一步说明：
实例1：
用1.4767号材料与亚麻结合制成丝网，网眼宽0.18mm，网丝直径为0.112mm，在空气中加热到900℃，5小时后接着将处理后的丝网载体在电子射线汽相喷镀装置中正反两面汽相喷镀上6nm厚的钯。钯层厚度用振荡石英测量，汽相喷镀速率也是用振荡石英控制。汽相喷镀的钯量为138mg/m2。用这种催化剂丝网加成整体元件并用一种滚动齿轮将一部分丝网加工成波纹状。波纹状的丝网与平面丝网重叠在一起卷起来和用点焊固定形成整体。
将20cm长及20cm直径由0.112m2催化剂丝网制成的催化剂整体元件2个装在一个催化蒸馏设备中，丝网密度为1.79m2/l相当于0.247g Pa/l。
实例2：
不锈钢丝(材料号1.4767)制成的平面丝网，网眼宽180μ，网丝直径为110μ放在超声波浴中洗净后在900℃的空气中热处理7小时。20cm宽的丝网带卷在一个超高真空汽相喷镀装置中的卷筒上，接着在10-6mbar的压力下连续汽相喷镀上2nm的Pd层。将丝网往回卷时作第二次汽相喷镀上0.7nm Bi层。喷镀后的催化剂半成品放在隔焰电炉中在600℃经30分钟成型。
热处理过程中先将炉温在40分钟内加热到600℃，并在此温度保持30分钟然后关断电源。冷却后将催化制品从炉中取出加工成一个整体元件。这里是将41.5cm平面丝网用滚动齿轮压成波纹状然后与38cm平丝网重叠卷起来。制成的整体催化剂元件的体积为67cm3。
Claims (8)
1.一种催化剂填料在催化蒸馏工艺中的应用，该催化剂填料是通过汽相喷镀和/或喷射至少一种作为催化剂和/或促进剂的活性物质在作为载体物料的纺织物、针织品或薄片上制成，在此催化蒸馏工艺中一种多相催化反应是与在催化剂填料上同时进行的蒸馏或精馏相结合。
2.如权利要求1的应用，其特征在于催化剂填料至少为从带状的纺织物、针织品或薄片形成的一个整体元件。
3.如权利要求1或2的应用，其特征在于所用的纺织物、针织品或薄片由金属组成，优选用不锈钢。
4.如权利要求3的应用，其特征在于所用的纺织物、针织品或薄片在进行汽相喷镀和/或喷射之前在含氧的气氛中0.5到24小时，优选用1到10小时加热到400到1100℃范围，优选加热到800到1000℃范围的温度进行热处理。
5.如权利要求1或2的应用，其特征在于所用的纺织物、针织品或薄片由无机物或由塑料组成。
6.如上述权利要求中之一的应用，其特征在于作为催化剂活性物质选用元素周期表所列的第I副族元素和/或第VII副族和/或第VIII副族元素，和/或作为促进剂选用第IV、第V、第VII主族元素及第II、III、VI、VII副族元素。
7.进行催化蒸馏使用的反应器，其中一种多相催化反应是与在催化剂填料上进行的蒸馏或精馏相结合，包括一个蒸馏塔，该塔用前面的权利要求中所述一种催化剂填料进行填充。
8.如权利要求7的反应器在如权利要求1到5所提出的催化蒸馏中的应用。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19624130A DE19624130A1 (de) | 1996-06-17 | 1996-06-17 | Verfahren zur katalytischen Destillation |
| DE19624130.8 | 1996-06-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1228032A true CN1228032A (zh) | 1999-09-08 |
| CN1149122C CN1149122C (zh) | 2004-05-12 |
Family
ID=7797165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971973636A Expired - Fee Related CN1149122C (zh) | 1996-06-17 | 1997-06-16 | 催化蒸馏法 |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US6297415B1 (zh) |
| EP (1) | EP0909204B1 (zh) |
| JP (1) | JP2000512207A (zh) |
| CN (1) | CN1149122C (zh) |
| AT (1) | ATE224225T1 (zh) |
| AU (1) | AU736817B2 (zh) |
| BR (1) | BR9709801A (zh) |
| CA (1) | CA2258797C (zh) |
| DE (2) | DE19624130A1 (zh) |
| DK (1) | DK0909204T3 (zh) |
| ES (1) | ES2184102T3 (zh) |
| MY (1) | MY117371A (zh) |
| PT (1) | PT909204E (zh) |
| RU (1) | RU2192299C2 (zh) |
| TW (1) | TW418113B (zh) |
| WO (1) | WO1997048466A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549121A (zh) * | 2014-12-23 | 2015-04-29 | 天津大学 | 用于反歧化反应精馏塔制备三氯氢硅的结构催化填料 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19748468A1 (de) * | 1997-11-03 | 1999-05-06 | Hoechst Ag | Beschichtete Gestricke als katalytische Füllungen für Destillationskolonnen |
| US6039865A (en) * | 1997-12-19 | 2000-03-21 | Trisol Inc. | Removal of phosphates from hydrocarbon streams |
| CA2288312C (en) * | 1998-12-22 | 2004-01-06 | Willem Wiekert Levering | Reactive distillation |
| DE19936276A1 (de) * | 1999-08-02 | 2001-02-08 | Basf Ag | Vorrichtung und Verfahren zur isothermen Durchführung von heterogen katalysierten Dreiphasenreaktionen |
| US20030012711A1 (en) * | 1999-11-17 | 2003-01-16 | Conoco Inc. | Honeycomb monolith catalyst support for catalytic distillation reactor |
| DE10005663A1 (de) * | 2000-02-09 | 2001-08-23 | Basf Ag | Herstellungsverfahren für eine Katalysatorpackung, Reaktor mit Katalysatorpackung sowie deren Verwendung |
| DE10022465A1 (de) * | 2000-05-09 | 2001-11-15 | Basf Ag | Verfahren und Vorrichtung zur Aufarbeitung eines C4-Schnitts aus der Fraktionierung von Erdöl |
| US6773580B2 (en) * | 2001-12-11 | 2004-08-10 | Corning Incorporated | Catalytic reforming system and process |
| US7302812B2 (en) * | 2003-09-02 | 2007-12-04 | Air Products And Chemicals, Inc. | Process for production of isotopes |
| RU2697465C2 (ru) * | 2017-10-25 | 2019-08-14 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" (ФГБОУ ВО "ТГТУ") | Конструкция реакционно-ректификационного аппарата периодического действия для осуществления термокаталитических процессов |
| RU2709089C2 (ru) * | 2018-05-07 | 2019-12-13 | Государственное бюджетное образовательное учреждение высшего образования Нижегородский государственный инженерно-экономический университет (НГИЭУ) | Установка для гранулирования измельченного сырья с зубчатыми кольцевыми матрицами в процессе диэлектрического нагрева |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4242530A (en) | 1978-07-27 | 1980-12-30 | Chemical Research & Licensing Company | Process for separating isobutene from C4 streams |
| CA1146148A (en) | 1981-06-30 | 1983-05-10 | James Den Hartog | Ordered bed packing module |
| US4443559A (en) | 1981-09-30 | 1984-04-17 | Chemical Research & Licensing Company | Catalytic distillation structure |
| DE3574937D1 (de) | 1985-05-14 | 1990-02-01 | Sulzer Ag | Reaktor zum durchfuehren von heterogenen, katalysierten chemischen reaktionen. |
| DE3926561A1 (de) * | 1989-08-11 | 1991-02-14 | Basf Ag | Palladiumkatalysatoren |
| JPH03181338A (ja) | 1989-12-11 | 1991-08-07 | Gebr Sulzer Ag | 触媒エレメントおよび触媒反応用反応器 |
| AU654757B2 (en) * | 1992-02-10 | 1994-11-17 | Chemical Research & Licensing Company | Selective hydrogenation of C5 streams |
| DE4209631A1 (de) * | 1992-03-25 | 1993-09-30 | Basf Ag | Monolithischer Trägerkatalysator, Verfahren zu seiner Herstellung und seine Verwendung |
| DE59307946D1 (de) | 1993-06-30 | 1998-02-12 | Sulzer Chemtech Ag | Katalysierender Festbettreaktor |
| DE19636064A1 (de) * | 1996-09-05 | 1998-03-12 | Basf Ag | Verfahren zur Hydrierung |
-
1996
- 1996-06-17 DE DE19624130A patent/DE19624130A1/de not_active Withdrawn
-
1997
- 1997-06-06 MY MYPI97002534A patent/MY117371A/en unknown
- 1997-06-16 TW TW086108316A patent/TW418113B/zh not_active IP Right Cessation
- 1997-06-16 WO PCT/EP1997/003122 patent/WO1997048466A1/de active IP Right Grant
- 1997-06-16 AU AU33388/97A patent/AU736817B2/en not_active Ceased
- 1997-06-16 ES ES97929190T patent/ES2184102T3/es not_active Expired - Lifetime
- 1997-06-16 PT PT97929190T patent/PT909204E/pt unknown
- 1997-06-16 AT AT97929190T patent/ATE224225T1/de not_active IP Right Cessation
- 1997-06-16 BR BR9709801A patent/BR9709801A/pt not_active IP Right Cessation
- 1997-06-16 EP EP97929190A patent/EP0909204B1/de not_active Expired - Lifetime
- 1997-06-16 JP JP10502238A patent/JP2000512207A/ja active Pending
- 1997-06-16 DK DK97929190T patent/DK0909204T3/da active
- 1997-06-16 RU RU99101046/12A patent/RU2192299C2/ru not_active IP Right Cessation
- 1997-06-16 CA CA002258797A patent/CA2258797C/en not_active Expired - Fee Related
- 1997-06-16 CN CNB971973636A patent/CN1149122C/zh not_active Expired - Fee Related
- 1997-06-16 US US09/202,474 patent/US6297415B1/en not_active Expired - Fee Related
- 1997-06-16 DE DE59708272T patent/DE59708272D1/de not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549121A (zh) * | 2014-12-23 | 2015-04-29 | 天津大学 | 用于反歧化反应精馏塔制备三氯氢硅的结构催化填料 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2258797C (en) | 2005-04-05 |
| BR9709801A (pt) | 1999-08-10 |
| CA2258797A1 (en) | 1997-12-24 |
| CN1149122C (zh) | 2004-05-12 |
| MY117371A (en) | 2004-06-30 |
| PT909204E (pt) | 2003-01-31 |
| RU2192299C2 (ru) | 2002-11-10 |
| US6297415B1 (en) | 2001-10-02 |
| JP2000512207A (ja) | 2000-09-19 |
| AU736817B2 (en) | 2001-08-02 |
| TW418113B (en) | 2001-01-11 |
| DE59708272D1 (de) | 2002-10-24 |
| EP0909204A1 (de) | 1999-04-21 |
| ATE224225T1 (de) | 2002-10-15 |
| AU3338897A (en) | 1998-01-07 |
| WO1997048466A1 (de) | 1997-12-24 |
| EP0909204B1 (de) | 2002-09-18 |
| ES2184102T3 (es) | 2003-04-01 |
| DE19624130A1 (de) | 1997-12-18 |
| DK0909204T3 (da) | 2002-10-14 |
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