A charging system has: a number of connections for connecting at least one electric energy store to be charged; a number n of at least three inverter bridges, each of which has a center tap; a number n of electric filters, wherein the input of each filter of the number n of filters is electrically connected to a respective corresponding center tap of an inverter bridge of the number of inverter bridges; a controllable assigning unit which is inserted between a respective output of a filter of the number n of filters and the number of connections and which is designed to electrically assign the output of each filter of the number n of filters to a respective corresponding connection of the number of connections depending on at least one actuation signal; and a control unit which is designed to generate the at least one actuation signal depending on a desired charge mode of the charging system.

The invention relates to a charging system.
The object of the invention is the provision of a charging system, by means of which different types of electrical energy accumulators can be charged in the most flexible manner possible.
The invention fulfils this object by means of a charging system according to the independent claims.
The charging system comprises a whole number m of connections for connecting at least one electric energy receiving accumulator (hereinafter "electric energy accumulator") to be charged which, for example, for the purposes of charging, can draw electrical energy from an electrical energy supply accumulator. The number m, for example, can lie between 2 and 20. The electric energy accumulator can be a constituent element of an "IT system" ("Isolé Terre"="Isolated ground"). A single connection can constitute a single electric pole. Three connections or poles of this type can be combined, for example, to constitute a three-phase connection or a three-phase AC connection. Additionally to the three connections, for example, a neutral conductor connection and a PE connection can be further constituent elements of a three-phase AC connection of this type, wherein the neutral conductor connection and the PE connection can be executed separately from the remaining connections.
The charging system further comprises a number n of at least three two-level or multi-level inverter bridges, i.e. n≥3. The charging system preferably comprises a number n of at least six two-level or multi-level inverter bridges, i.e. n≥6. Each of the inverter bridges conventionally comprises a center tap. Conventionally, the inverter bridges can further comprise at least two series-connected and actuatable switching devices, wherein the respective center tap, depending upon a circuit state of the switching devices, is electrically connected to either one or the other outer end of a respective inverter bridge. In this respect, reference may also be made to the relevant specialized literature concerning inverters and their inverter bridges.
The charging system further comprises a number n of single- or multi-phase electric filters, wherein one input of a respective filter of the number n of filters is electrically connected to a respectively associated center tap of an associated inverter bridge of the number of inverter bridges.
The charging system further comprises a controllable assigning unit or switching matrix, which is interpolated between a respective output of one filter of the number n of filters and the number m of connections and is designed, depending upon at least one actuation signal, i.e. one or more actuation signals, to electrically assign a respective output of one filter of the number n of filters to a respectively associated connection of the number m of connections, or to electrically connect a respective output of one filter of the number n of filters to a respectively associated connection of the number m of connections. In this assignment, exactly one connection of the number m of connections can be assigned to exactly one associated output of one filter. In this assignment, one connection of the number m of connections can also be assigned to a plurality of associated outputs of a plurality of filters, i.e. a plurality of filter outputs can be assigned to the same connection, or can be electrically connected to the same connection.
The terms input and output of a respective filter are employed solely for the purposes of distinction between different connections of the filters. A signal flux and/or an energy flux can proceed either from the input of the respective filter in the direction of the output of the respective filter, or from the output of the respective filter in the direction of the input of the respective filter.
The charging system further comprises a control unit, for example in the form of a microprocessor, which is designed to generate the actuation signal(s) in accordance with a desired charging mode of the charging system. The function of the control unit can be divided, for example, between one or more control units.
According to one embodiment, the charging system comprises one or more electrical energy supply accumulators. The energy supply accumulator(s) can be embodied, for example, in the form of rechargeable electrochemical energy accumulators or batteries.
In this case, each of the inverter bridges is supplied by the energy supply accumulator, i.e., for example, a voltage can be applied to their outer ends which is generated by electrical energy of the energy supply accumulator, or which constitutes a voltage which is output or delivered by the electrical energy accumulator. The supply voltage can also be described as an intermediate circuit voltage. A positive intermediate circuit potential, for example, can be applied to one of the outer ends of a respective inverter bridge, and a negative intermediate circuit potential, for example, can be applied to the other outer end of a respective inverter bridge, wherein the potential difference between the positive intermediate circuit potential and the negative intermediate circuit potential constitutes the intermediate circuit voltage which corresponds to the voltage output which is delivered by the electrical energy accumulator.
Additionally or alternatively to the energy supply accumulator, a supply voltage and/or a supply current for the inverter bridges can also be generated by means of an electric generator, which is driven, for example, by means of a combustion engine.
According to one embodiment, a respective filter of the number n of filters comprises at least one reactance coil and at least one capacitor. The filters or reactance coil(s) and the capacitor or capacitors can be interconnected, for example, in an L, T or PI topology.
According to one embodiment, the desired charging mode is selected from the following series of charging modes:
a) simultaneous charging of a plurality of electric energy accumulators with alternating current (for example, single-phase or three-phase),
b) charging of at least one electric energy accumulator with alternating current (for example, single-phase or three-phase), wherein a charging current in charging mode b) is higher than a charging current in charging mode a),
c) simultaneous charging of a plurality of electric energy accumulators with direct current,
d) charging of at least one electric energy accumulator with direct current, wherein a charging current in charging mode d) is higher than a charging current in charging mode c).
According to one embodiment, the control unit is designed to generate the at least one actuation signal for the controllable assigning unit and further actuation signals for switching devices of the inverter bridges, such that the energy supply accumulator is charged by means of electrical energy which is made available on one or more connections of the number m of connections.
According to one embodiment, the control unit is designed to generate the at least one actuation signal for the controllable assigning unit and further actuation signals for switching devices of the inverter bridges, such that electrical energy which is stored in the energy supply accumulator is injected into an electricity supply grid, which is connected to one connection or to a plurality of connections of the number m of connections. The electricity supply grid can be, for example, a conventional single-phase or three-phase AC voltage grid.
According to one embodiment, the energy supply accumulator supplies a voltage at a level which is higher than the level of a voltage which is typically delivered by a charging energy accumulator. For example, a typical level which is delivered by the energy supply accumulator can be greater than 600 V, particularly greater than 750 V, and particularly equal to or greater than 800 V. The level which is delivered by the energy supply accumulator can be greater than √2 times an r.m.s. value of an AC voltage of an electricity supply grid which is connected to a connection or to a plurality of connections of the number m of connections.
On the grounds that, in principle, each inverter can function as a step-down converter, any voltages can be generated from the voltage which is supplied by means of the energy supply accumulator (described hereinafter as the battery voltage) which are lower than the battery voltage. During the charging of the energy supply accumulator, in turn, an inverter bridge can function as a step-up converter wherein, for example, electrical energy from a grid with a lower voltage rating of 400 V or 480 V is converted into a higher battery voltage.
According to one embodiment, the controllable assigning unit comprises a number of actuatable switching devices. The number of actuatable switching devices can be dependent upon the number n and the number m. In a maximum stage of development, with a maximum number of degrees of freedom in assignment, an n×m switching matrix can be constituted, in which each output of a filter can be connected to any desired output of the charging system. In order to reduce the number of actuatable switching devices, the degrees of freedom in assignment can be reduced.
According to one embodiment, the actuatable switching devices are contactors.
The invention is described in detail hereinafter, with reference to the drawings.


An exhaust gas aftertreatment component includes a ceramic carrier body with a plurality of axial flow channels, wherein the carrier body has an inner region and an outer region, which radially surrounds the inner region. A cell density of the carrier body is smaller in the inner region than a cell density in the outer region. At least the outer region of the carrier body has a coaling, wherein the coating of the outer region has an HC adsorber function for a reversible adsorption of unburnt hydrocarbons. An exhaust gas system, which is equipped with such an exhaust gas aftertreatment component, and a vehicle, which has such an exhaust gas system are also provided.

Field of the Invention
The invention relates to an exhaust gas aftertreatment component with an HC adsorber function. The invention further relates to an exhaust gas system having such an exhaust gas purification system and to a vehicle which has such an exhaust gas system.
The use of catalytic converters in the exhaust gas systems of internal combustion engines is nowadays common practice. For example, in particular in the case of diesel engines, oxidation catalytic converters are used, which convert unburnt hydrocarbons (HC) as well as carbon monoxide (CO), and, in the case of diesel engines and Otto cycle engines, reduction catalytic converters are used, which convert nitrogen oxides (NOX). Furthermore, three-way catalytic converters are known that combine the function of oxidation catalytic converters and reduction catalytic converters, and thus catalytically convert all three components and are mainly used in Otto cycle engine. In principle, all catalytic converters require a specific minimum temperature in order to provide a sufficient conversion performance. As a criterion for this, the so-called light-off temperature or start-up temperature is used, at which the catalytic converter converts 50% of the limited exhaust gas components. After a cold start of the engine, this temperature has usually not yet been reached, so that, unless further measures are taken, the emissions, which are referred to as start emissions, leave the exhaust gas system unconverted.
The desire for a further reduction of emissions as well as the progressive lowering of exhaust gas limit values also require the reduction of the start emissions and thus require that the operating temperatures of the catalytic converter system are reached sooner. Current and even more so future exhaust gas emission control legislation therefore requires that also the start emissions are measured for determining the total emissions of a vehicle in standardized driving cycles.
A common measure for reducing the start emissions is to dispose relatively small volume precatalytic converters, which are also referred to as primary catalytic converters, close to the engine,
Due to their small volume and their placement close to the engine, precatalytic converters reach their light-off temperature relatively quickly and then take over the conversion of a large part of the emissions until a main catalytic converter, which is provided downstream, also reaches its operating temperature.
From German Patent Application No. DE 102 01 042 A1 an exhaust gas catalytic converter having a monolithic ceramic carrier body is known, which has an inner region and an outer region, wherein the inner region has a higher cell density than the outer region. The flow channels of the inner and outer regions that pass axially through the carrier body have a catalytic coating (washcoat). Due to the higher cell density of the inner region, this region has a higher catalytic converter activity than the outer region. A swirl generator is disposed upstream of the catalytic converter carrier, wherein the swirl generator, at low flow velocities of the exhaust gas, that is, in case of low engine load ranges, directs the exhaust gas flow essentially into the inner region and, at higher flow velocities, that is in case of higher loads, into the outer region. This arrangement achieves that, after a cold start, initially the exhaust gas flow in the inner region is catalytically treated, wherein, due to the exothermic heat release, the inner region is heated relatively quickly and thus also hears the surrounding outer region.
U.S. Patent Application Publication No. 2002/0132726 A1 describes an exhaust gas system which includes a main catalytic converter and, downstream therefrom, Iwo parallel exhaust gas lines which can be selectively closed or, respectively, opened through the use of a switchover valve. The two parallel exhaust gas lines have a concentric configuration with an inner main line surrounded concentrically by a side line in which a ring-shaped HC adsorber is disposed. A return line branches off from the side line upstream from the HG adsorber, wherein the return line which feeds hydrocarbons, which are unburnt and desorbed from the adsorber, to the internal combustion engine. After a cold start the inner main line is closed and the exhaust gas flow is guided over the HG adsorber, which adsorbs and/or chemisorbs the unburnt hydrocarbons HG and hydrocarbons not converted by the not yet operational main catalytic converter. Once the main catalytic converter has reached its operating temperature, and thus ensures a sufficient HC conversion, the exhaust gas flow is directed into the main line. Due to the heating now taking place, the hydrocarbons desorb from the HG adsorber and are delivered to the engine combustion via the return line.
Furthermore, a similar concept is known that also uses the concentric structure of an HC adsorber provided outside and a main line provided inside, wherein in this concept the main catalytic converter is however not connected upstream but downstream from the HC adsorber. In this configuration, the return line described in U.S. Patent Application Publication No, 2002/0132726 A1 is omitted. Instead, the desorbed hydrocarbons are converted by the main catalytic converter connected downstream.
For the HC adsorber concepts discussed above, it would be desirable to equip them with an additional particulate filter function. Filter functions can however only be achieved through the use of ceramic carrier bodies (monoliths). However, if such monoliths are provided with a central bore, in order to realize the bypass function which bypasses the HC adsorber, the mechanical stability of the carrier body and thus its service life decreases. For this reason and also because of the difficulty of producing ring-shaped ceramic carrier bodies, metal carrier bodies are used in the conventional concepts. Just like ceramic monoliths, metal carrier bodies too have a plurality of longitudinally extending flow channels, which are, however, produced by the combination of a corrugated sheet metal and a flat sheet metal, which are wound in the form of a spiral. A particulate filter function, which is based on partly closed flow channels, is not possible with metal carrier bodies.

Exhaust gas aftertreatment component with an HC adsorber function and exhaust gas system including such an exhaust gas aftertreatment component


Vehicle handle, which comprises a lever (2) which can rotate around a first axis (4) and is mechanically connected to a first rocker (9) which can rotate around a second axis (10) when the lever (2) rotates around the first axis (4) for pulling a cable (11) which can slide in a duct (12) mechanically connected to the lever (2), so that the duct (12) moves in the direction opposite to the direction (32) of the cable (11) when the lever (2) rotates around the first axis (4).

The present invention relates to a vehicle handle, and in particular to a handle with an improved unlocking mechanism which is driven when the lever of the handle is pulled for opening the door of a motor vehicle.
EP 1556569 discloses a vehicle handle, which comprises a lever mechanically connected to a rocker which rotates together with the lever for pulling a cable which drives the unlocking mechanism of the door of a motor vehicle.
The stroke of the cable depends on its distance from the rotation axis of the rocker, so that the size of the rocker cannot be reduced without reducing the stroke of the cable, which however depends in turn on the unlocking mechanism.
It is therefore an object of the present invention to provide a handle, which is free from said disadvantages.
Thanks to the mechanical connection between the lever and the duct containing the cable, the duct moves in the direction opposite to the direction of the cable when the lever rotates around the first axis, so as to increase the stroke of the cable in the duct without changing the size of the rocker.
Said mechanical connection is preferably carried out with a particular second rocker which rotates in the direction opposite to the first, so as to obtain a handle compact and reliable, especially when the rockers rotate around substantially parallel axes.

Vehicle handle with improved unlocking mechanism


A method for preparing a material for medical or veterinary use by uniformly mixing a thermoplastic polymer, preferably polyether etherketone (PEEK), at least with tricalcium phosphate (Ca.sub.3 (PO.sub.4).sub.2), and injection or extrusion moulding the resulting mixture under conditions suitable for converting the tricalcium phosphate into calcium hydroxyapatite. tite. The basic mixture preferably comprises a biocompatible metal oxide such as titanium dioxide (TiO.sub.2). The resulting material is useful for making endosseous implants or bone prostheses.

Numerous types of materials, either metallic or plastic, are used in the medical or veterinary field, for the replacement of biological structures (bones especially) or the fixation of functional organs (dental implants or others, . . .).
The selection of the material is made in relation to its structural intrinsic characteristics and also in relation to its biocompatibility, in terms of integration or, what is better, in terms of biological tolerance.
For informative purposes, the document EP-A-0378102 describes an implantation material obtained by extrusion moulding of a thermoplastic polymer mixture with calcium hydroxyapatite and additional charging constitutive elements.
The document US-A-4645503 suggests a bone reparation material comprising a biocompatible and biodegradable thermoplastic polymer, mouldable at ordinary temperature and mixed with a filler, preferably calcium hydroxyapatite, tricalcium phosphate or glass granules, used alone or in combination.

Method for preparing a material for medical or veterinary use, resulting material, and uses thereof


An improved vehicle chassis for motor homes and busses is provided. According to the invention, the chassis has a front frame chassis subcomponent, a rear chassis subcomponent and a center floor rail system. Each subcomponent has contained within it the appropriate subcomponents associated with the chassis; the front subcomponent, for example, has a suspension unit and steering apparatus while the rear subcomponent has transmission, motor and suspension.. The front and rear frame chassis subcomponents have longitudinally extending frame rails which connect to one another via a plurality of longitudinally extending floor rails and perpendicular steel plates found in the center floor rail system.. The inventive device integrates the chassis and superstructure. Incorporating the superstructure into the chassis lowers vehicle height, and therefore, the center of gravity. This results in better handling and ride characteristics for the finished vehicle. Underbelly storage capacity of a particular vehicle is increased by approximately five inches without increasing vehicle height or lowering ground clearance.

The known construction of a motor home includes a chassis, a superstructure, and a body. The chassis houses the mechanical workings of the vehicle such as suspension, motor and drivetrain. The superstructure is affixed to the top of the chassis and provides the mounting base for the body. While this results in a solid and relatively safe vehicle, there are several shortcomings associated with this construction technique.
First, the resulting vehicle has a relatively high center of gravity. High center of gravity negatively affects vehicle handling and ride. Attempts have been made to lower the center of gravity; however, until now these attempts have resulted in a lowering of the ground clearance of the vehicle. This in turn diminishes the underbelly storage storage capabilities of the vehicle.
Another shortcoming of the present construction technique is that it is expensive and time consuming as it requires three manufacturing "processes": chassis, superstructure and body. A further shortcoming of the present construction technique is that by fitting the superstructure to the chassis, the wheel base is fixed, thereby decreasing body construction flexibility, absent costly customization.
Thus, there is need for an improved motor home and bus chassis which lowers the vehicle's center of gravity without decreasing underbelly storage space, improves the handling and ride of the vehicle, offers flexibility in sizing without costly customization, and is economical to produce.


A stabilizer composition comprising a) an amine and b) a compound selected from aliphatic, non-cyclic monomeric polyunsaturated hydrocarbons and terpenes is useful for stabilizing an organic solvent against degradation.

Organic solvents, such as hydrocarbons, halogenated hydrocarbons, glycol ethers, esters or ketones, are used in several applications, such as dry-cleaning of textiles or degreasing of metals. However, it is well known that halogenated hydrocarbons, glycol ethers, esters or ketones tend to decompose when they are exposed to heat, oxygen, light or water, particularly if metals or metal salts are present. Acidic products, such as hydrochloric acid, are produced during decomposition of halogenated hydrocarbons. Therefore, it is common in the industry to add a stabilizer to halogenated hydrocarbons.
The published Patent Application WO 0236531 discloses a stabilizer composition comprising an olefinic amine with a boiling point of 5 to 80° C., an aliphatic, acyclic ester or formate of 2 to 6 carbon atoms, optionally a saturated aliphatic amine with a boiling point of 5 to 80° C. and optionally an antioxidant, such as a cyclic alkane or a pentene.
U.S. Pat. No. 3,424,805 suggests stabilization of chlorinated hydrocarbons by addition of an aliphatic diamine, triamine or polyamine. It is taught that the stabilizing effect can be increased by the addition of an aliphatic monoamine, such as diisopropylamine or pyrrole or N-alkyl pyrrole, such as N-methyl pyrrole.
European Patent No. 1 042 257 discloses a stabilizer composition for halogenated hydrocarbons which comprises an N-alkyl morpholine and a straight-chain or cyclic aliphatic amine containing no heteroatoms other than nitrogen with a boiling point of at least 150° C.
European Patent No. 0 059 251 discloses a composition for stabilizing trichloroethylene. The composition comprises an amine with a boiling point of 50 to 150° C., ethyl acetate, N-methylpyrrol and/or an alkylphenol and further diisobutylene and/or cycloheptatriene and an ether comprising no hydroxyl groups.
Typically stabilizer compositions are not added to hydrocarbons due to their well-known stability against decomposition. However it has been observed that the lack of a stabilizer often leads to an undesirable concentration of acidic compounds in the hydrocarbon which originates from the decomposition of contaminants present in the dry-cleaning of textiles or degreasing of metals and which increases over time as the hydrocarbon is recycled. The same observation has been made when using glycol ethers, esters or ketones as a solvent. The produced acidic compounds can cause corrosion problems in the cleaning operations.
Unfortunately, the stabilizer compositions suggested in the prior art often do not meet the requirements of the industry for many applications. Often the capacity of the stabilizer is reduced over time too fast which is made apparent by an increase in acidity of the organic solvent. Many stabilizers suffer in that they are not suitable for solvents of low polarity, such as hydrocarbons. Yet other stabilizers have a very high boiling point and do not stabilize the solvent when it is in the vapor phase.
Accordingly, one object of the present invention is to provide a new stabilizer composition for organic solvents. A preferred object of the present invention is to provide a stabilizer or stabilizer composition which is suitable for stabilizing an organic solvent against an undue increase in acidity over an extended period of time. Yet another preferred object of the present invention is to provide a stabilizer or stabilizer composition which is sufficiently volatile to stabilize organic solvents in the vapor phase. Yet another preferred object of the present invention is to provide a stabilizer or stabilizer composition which can not only be used in halogenated hydrocarbons but also in solvents of medium or low polarity, such as glycol ethers, esters, ketones or hydrocarbons.


A serial communications architecture for communicating between hosts and data store devices. The Storage Link architecture is specially adapted to support communications between multiple hosts and storage devices via a switching network, such as a storage area network. The Storage Link architecture specifies various communications techniques that can be combined to reduce the overall cost and increase the overall performance of communications. The Storage Link architecture may provide packet ordering based on packet type, dynamic segmentation of packets, asymmetric packet ordering, packet nesting, variable-sized packet headers, and use of out-of-band symbols to transmit control information as described below in more detail. The Storage Link architecture may also specify encoding techniques to optimize transitions and to ensure DC-balance.

The described technology relates generally to communications techniques and particularly to communications between hosts and data store devices.
The speed and capacity of the data store devices, such as disk drives and memories, have increased significantly over the past several years. As a result of their improved performance, these data store devices are being used in many new applications, such as database servers, Web servers, personal video recorders, and digital displays. These applications often require large amounts of data to be communicated between data store accessing devices ("hosts") and data store devices. (Hosts may include computers, CPUs, or any logic for accessing a data store device.) Moreover, as host speed increases, the speed in communicating between hosts and data store devices can have a significant impact on the overall performance of the application. In particular, even though the speed of hosts and data store devices has increased significantly, the speed of communications between hosts and data store devices has not increased as significantly, especially for communications over long distances (e.g., greater than one meter). Thus, the communications speed presents a bottleneck in many new applications.
Current communications techniques typically communicate between hosts and certain types of data store devices, such as disk drives, using a bus with many parallel lines or using a single serial communications link. The Integrated Disk Electronics ("IDE") bus and the Small Computer Systems Interface ("SCSI") bus are examples of bus-based parallel communications techniques. These communications techniques, however, present many problems. Performance of bus-based communications techniques is generally improved by increasing the number of lines in the bus, which may significantly increase the cost of such techniques. In addition, bus-based communications techniques generally provide arbitration so that multiple hosts and data store devices can share the same bus. The use of arbitration can significantly increase the cost of such a bus. The cost of such bus-based communication techniques is further increased because their design needs to address additional problems such as cross-talk and clock skew. In particular, as the communications speed increases, the solution to cross-talk and clock skew become much more complex.
Some serial communications techniques have been developed to address some of the problems of bus-based communications techniques. Current serial communications techniques, however, have problems of their own. Serial AT, Attachment, which is intended to replace IDE, does not scale well and only operates in a half duplex mode. Fibre Channel, currently used to support storage area networks ("SANs"), is very generic and therefore, not optimized for any particular application. In particular, Fibre Channel has a relatively small packet size with a large header. As a result, use of Fibre Channel often results in an unacceptably large overhead. For example, data transmitted to disk drives is typically sent in very large blocks (e.g., 216 bytes). With Fibre Channel, such large blocks need to be divided in many (e.g., 32) packets, which results in a high overhead in the amount of redundant header information and in the redundant processing performed as a packet is routed to its destination. Thus, Fibre Channel may not be appropriate for many applications.
Current memory devices, such as SDRAM and RDRAM, are typically designed to be synchronous with the accessing processing unit. The hosts and the memory devices are synchronous in that they share the same clock signal. These memory devices are typically optimized for access patterns that are both temporally and spatially related. In particular, these memory devices are optimized to read and write arrays (or streams) of data. There is a setup overhead (e.g., 5 clock cycles) when accessing the first word of an array in memory, but access of subsequent words in the array occurs at the synchronized clock rate (e.g., 1 access per clock cycle). Since the access patterns of central processing units and graphics processors are typically temporally and spatially related, they can access such memory devices efficiently.
Existing memory devices that are designed to support access patterns with a high temporal and spatial relationship may not be appropriate for uses having access patterns with a lower spatial relationship. The setup overhead for each access may be too high. There are, indeed, many uses for memory devices with access patterns that are not as spatially or temporally related as those of a central processing unit or a graphics processor. For example, a switch may have a memory device in which packets of data received via an input port are stored before they are transmitted via an output port. Traditionally, switches used crossbars to provide the switching function and FIFOs to provide a buffering function. When a memory device is used on a switch in place of a crossbar, then all the input and output ports need access to the memory device. The accesses by the different ports are, however, not particularly spatially related. Moreover, when the packet size is small (e.g., 53 bytes in the case of an ATM switch), the spatial relationship of accesses by a single port may not be significant. Other uses in which there may not be a significant spatial relationship of accesses include network processors and caches for storage area networks. In such uses, the data is received from disparate sources at disparate times and may not be spatially related.
Many existing memory devices are not particularly suitable for many uses because the memory devices typically allow access by only one accessing device at a time and because the memory devices typically operate at different clock rates than the accessing devices. Because such memory devices can only be accessed by one device at a time, the accessing devices may need to enter a wait state because the memory device is busy or a memory controller may need to have a buffering component. Of course, the use of a wait state may result in unacceptable performance. Also, the addition of a buffering component may increase complexity and cost. In addition, when multiple accessing devices access the same memory device through a single bus (e.g., one writing to the memory device and the other reading from the memory device), then all the devices that access the memory device need to be synchronized with the memory device. Because the accessing devices may have different underlying clock rates, complex and costly logic is needed to support the mapping to the bus clock rate.
Existing communications protocols, such as Fibre Channel, may have an unacceptable overhead for communicating with memory devices. The communications from a host to a memory device may occur in relatively short blocks (e.g., 32 bytes). Each block needs to be transmitted in a separate packet with a relatively large header. In some packets, the header may be larger than the data itself, which can significantly reduce the overall bandwidth and speed of transmission. More generally, communications between devices typically occurs in a synchronous or an asynchronous mode. In a synchronous mode, the transmitting and receiving devices use the same clock signal. The transmitting device can send the clock signal to the receiving device either as a separate signal or as a signal that can be derived from the data signals. When the clock is sent as a separate signal, problems arise resulting from the different delays in the data signals and the clock signal. These delays and resulting problems are increased as the transmission speed and distance are increased. It is very difficult and costly to account for these delays. In addition, the receiving device will have an asynchronous clock boundary. That is, a portion of the receiving device will operate at the clock frequency based on the transmitting device's clock frequency (i.e., the transmitter's clock domain) and another portion will operate at the receiving device's local clock frequency (i.e., the receiver's clock domain). As a result of the asynchronous boundary, the receiving device typically needs to buffer control and data signals sent between the clock domains using elastic buffers, which adds to the complexity and cost of the receiving devices. These elastic buffers require substantial space (e.g., chip area), and when a single chip has multiple communications ports, the design is complicated because each port needs its own elastic buffer. When the clock is derived from the data signal, the problems of the delay are reduced somewhat, but there are still the problems associated with an asynchronous clock boundary.
A plesiosynchronous clocking technique can be used to avoid the need to transmit a separate clock signal or derive the clock signal from the data signal. With plesiosynchronous clocking (also known as "plesiochronous" clocking), the transmitting and receiving devices have clocks with nominally the same clock frequency. If the clock frequencies were exactly the same, then transmitting and receiving devices would be synchronized and the receiving device could accurately identify the transmitted data (in the case of serial transmission). Also, since the receiving device operates only at its local clock frequency, there is no asynchronous clock boundary. In practice, however, clock frequencies are not exactly the same but vary, for example, by 100 ppm. The receiving device can use techniques as described in U.S. Pat. No. 6,229,859, entitled "System and Method for High-Speed, Synchronized Data Communication," which is hereby incorporated by reference, to account for clock variations. Those techniques use an oversampling of the data by the receiving device to detect edge boundaries of the transmitted data. The receiving device can vary the number of bits of data detected during an interval to compensate for the variations in frequency.
It would be desirable to have a communications architecture that provides high-performance for applications (e.g., data storage-based applications and memory-based applications) at a low cost. Such a communications architecture would allow for communications techniques to be tailored to particular applications.

Method and system for communicating control information via out-of-band symbols


A process for the utilization of the methane produced by enteric fermentation, specifically to a process that utilizes methane produced by ruminant animals through enteric fermentation as a source of carbon and/or energy for the directed production of methane-based goods or processes is provided.

1. Field of Invention
This invention relates generally to processes for the reduction of ruminant animal methane emissions, specifically to a process for the utilization of ruminant animal methane emissions as a source of energy.
2. Description of the Related Art
Methane emissions from ruminant animals account for about twenty percent of total global methane emissions, and atmospheric methane accounts for about twenty percent of planetary warming. In addition to the environmentally destructive effects of ruminant animal methane emissions, such emissions represent wasted energy, as a significant percentage of the food ruminant animals eat is lost as methane. Accordingly, there have been significant efforts in the past to reduce ruminant animal methane emissions.
Ruminant animal methane emissions, or, more specifically, enteric fermentation methane emissions, originate in the four-stomach digestive tract common to all ruminant animals, which includes the rumen, a large forestomach connected to the four-stomach digestive tract. The rumen contains a host of digestive enzymes, fungi, bacterium, and protozoa, and the bulk of digestion, as well as methane production via enteric fermentation, takes place here. Not surprisingly, all prior efforts to reduce enteric fermentation methane emissions from ruminant animals, which include dairy cows, beef cattle, sheep, goats, water buffalo, and camels, have focused on modifications associated with the rumen or digestive tract.
Past modification efforts have included: vaccines designed to limit methanogenic, or methane-producing, microorganisms in the rumen or digestive tract; feed reformulations designed to alter the chemical or microbial environment of the rumen or digestive tract to limit methane production; feed reformulations designed to decrease the amount of methane-producing foods entering the rumen or digestive tract; and selective breeding aimed at encouraging the reproductive success of ruminant animals which produce relatively low amounts of methane, presumably as a result of factors associated with the rumen or digestive tract.
While most of these prior efforts have had some success in reducing enteric fermentation emissions, none has been shown to completely, or even significantly, eliminate ruminant animal methane production. Since limited success in reducing methane production concurrently limits the economic benefits of using methane-reducing vaccines, feed formulations, or selective breeding, ruminant animal owners have generally been averse or reluctant to employ these methods. Thus, as the ruminant animal population continues to grow in accord with ever-increasing worldwide demand and methane reduction efforts fail to reduce emissions in any significant way, enteric fermentation methane emissions remain a significant source of both environmental degradation and wasted energy.
Prior to the applicants' discovery, no methods were known to reduce ruminant animal methane emissions by using such methane as a source of energy in energy consumption systems maintained outside of the digestive tracts of ruminant animals. In the past, all ruminant animal methane reduction processes have focused on limiting ruminant animal methane production rather than reducing overall atmospheric emissions through a system of methane utilization. Thus, it is one feature of several embodiments of the present invention that ruminant methane emissions are reduced through the utilization of ruminant animal methane as a source of energy.
Methane-utilizing, or methanotrophic, microorganisms are well known in the microbiology art for their capacity to grow and reproduce using methane as a source of carbon and/or energy. Methanotrophic microorganisms, specifically bacteria, have even been employed to reduce ruminant animal methane emissions by being placed directly in the rumen or digestive tract of ruminant animals and subsequently limiting production at its source. They have never, though, been employed in a microbiological growth system. They have also never been employed in a microbiological growth and harvest system that reduces ruminant animal enteric fermentation methane emissions while concurrently providing a means for harvesting products of microorganism growth, such as microorganism biomass. Methods for the utilization or consumption of methane gas as a source of feedstock fuel, including fuel used for the production heat, electricity, liquid natural gas, compressed natural gas, chemicals, industrial feedstock, and a range of other goods, are well known for their capacity to use methane as a source of energy. However, none of these methods has ever been employed to reduce enteric fermentation methane by using such methane as a source of energy for the induction of methane-based processes or for the production of electricity, heat, and/or other methane-based products.
Prior to the applicants' discovery, no methods were known to utilize ruminant animal methane emissions as a source of energy. More specifically, the connection between enteric fermentation methane emissions from ruminant animals and the directed production of methane-based goods or methane-driven processes through the utilization of enteric fermentation methane as a source of carbon and/or energy had ever been made. At least two major factors likely inhibited such a connection. First, it is not a well-known fact that, under certain conditions, certain ruminant animals produce enough methane to make methane-consumption systems such as electricity, heat, or microorganism production platforms technically and/or economically feasible. Second, ruminant animal methane emissions are not considered a viable source of carbon or energy because they are considered low-volume, non-concentrated, and, thus, unusable methane emissions. While up to ninety-five percent of enteric fermentation methane emissions exit the digestive tracts of ruminant animals as exhalation, most continue to regard such emissions as components of low-volume, diffuse, unusable flatulence. No methods are known to capture and/or consolidate enteric fermentation methane emissions in a way that would convert them into a state suitable for use as a fuel stream for the production of methane-based goods or processes. Enteric fermentation methane originates as diffuse emissions, and no methods are known to convert such emissions into a usable form. For these and other reasons, ruminant animal methane emissions have never been considered as a viable source energy, and the connection between enteric fermentation methane emissions and methane-driven process and goods production has never occurred.
Mechanical ventilation systems are well known in the livestock and agricultural science art for their capacity to draw, push, or pull air through a fully or partially enclosed ruminant animal holding, feeding, or enclosure area. The main function of mechanical ventilation systems, including tunnel ventilation systems and other ventilation systems, is to provide air flow or air exchange in order to maintain or improve the health of ruminant animals in a fully or partially enclosed holding or feeding area. It is also well known in the livestock and agricultural science art that some mechanical ventilation systems, particularly tunnel ventilation systems, have the capacity to force all or some of the air inside a fully or partially enclosed ruminant animal holding or feeding area through specific vents or fans. The outflow air coming out of ventilation fans have even been forced, directed, or led into mulch, compost, and/or other platforms designed to limit or reduce outflow air odor or dust emissions. Prior to the applicants' discovery, though, such ventilation systems used in conjunction with enclosure structures had never been considered as means to enable the capture, consolidation, and utilization of ruminant animal methane emissions as a source of energy. It is one feature of several embodiments of the present invention that animal enclosure structures and/or ventilation systems are applied as means to capture, consolidate, direct, and/or convey ruminant animal methane emissions to enable the use of such emissions as a source of energy. Prior to the applicants' discovery, ventilation systems and/or enclosure structures had never been used to capture ruminant animal enteric fermentation methane emissions, nor had such emissions ever been used to grow bacteria in a bioreactor optionally equipped with means to harvest any of the microbial products associated with bioreactor activity, particularly microbial biomass. Similarly, prior to the applicants' discovery, ventilation systems and/or enclosure structures had never been used to capture enteric fermentation methane for utilization by a methane-consumption system such as a reverse-flow reactor or microturbine. The utilization of air conveyance systems to capture enteric fermentation methane for use as a source of carbon and/or energy overcomes a range of practical problems associated with a system for capturing methane emissions from the nose and/or mouth of a ruminant animal using on-animal apparatuses such as bioreactors or microturbines, including animal mobility problems and reactor size requirements for optimal methane conversion. The straightforward utilization of structures, means, and systems that are well known and/or commonly used also overcomes a range of prior emissions capture problems, including practicability, palatability, and viability. One of skill in the art will understand that currently available and other ventilation systems can be used in accordance with embodiments of the invention.
No previous methods were known to reduce ruminant animal methane emissions by using such methane as a source of energy. Consequently, ruminant animal methane emissions remain a significant source of environmental degradation.
Several embodiments of the present invention relate to a process for the utilization of the methane produced by ruminant animals through enteric fermentation as a novel source of energy.
Embodiments of the invention have several surprising and unexpected advantages over the prior art, some of which are surprising and unexpected. One or more of these advantages are present in certain preferred embodiments of the present invention. Further objects and advantages will become apparent from the ensuing description.

Process for the utilization of ruminant animal methane emissions


A decoding device and a decoding method in a digital broadcast receiver are provided, in which received packet data is demultiplexed into video data and audio data, and decoding control signals of the respective data are extracted. An Estimated Program Clock Reference (EPCR) is generated from the decoding control signal of the audio data, and the EPCR is compared with the decoding control signal of the video data to generate a video decoding control signal. The demultiplexed video data is decoded in synchronous with the video decoding control signal, and then the decoded video data is outputted. The demultiplexed audio data is decoded in synchronous with the audio decoding control signal, and then the decoded audio data is outputted. Finally, the decoded video data and the decoded audio data are displayed and reproduced.

1. Field of the Invention:
The present invention relates to a synchronization device and a synchronization method in a digital broadcast receiver. More particularly, the present invention relates to a device and a method capable of synchronizing decoding timing of a digital broadcast receiver.
2. Description of the Related Art:
In general, a digital broadcast receiver refers to a device for receiving and displaying a broadcast signal transmitted from a digital broadcast center. Standardization for digital broadcasting is now actively being discussed throughout the world. Digital broadcasting is largely divided into a Digital Multimedia Broadcasting (DMB) scheme in the USA and a Digital Video Broadcasting (DVB) scheme in Europe. In such digital broadcast systems, a digital broadcast center is provided with an encoder, a modulator and a transmitter for digital broadcasting transmission, and a digital broadcast receiver is provided with a tuner, a demodulator and a decoder for digital broadcasting reception.
A portable terminal with a built-in digital broadcast receiver is also being developed. Such a portable terminal with a digital broadcasting reception function must be able to process data received from respective units of the digital broadcast receiver to reproduce an image. At this time, it is preferred that a structure for performing a multimedia function of the portable terminal is constructed as compact as possible and its power consumption is small. Since a user carrying the portable terminal is mobile, the size of the portable terminal is advantageously if it is as small as possible. Therefore, research is vigorously being pursued to develop a portable terminal with a multimedia function, which has small volume and yet satisfactorily performs the corresponding multimedia function.
FIG. 1 is a bock diagram for explaining clock systems of a transmitting side for encoding and transmitting a broadcast signal and a receiving side for decoding and displaying the encoded broadcast signal in a digital broadcast system. The following description will be given on the assumption that a broadcast signal standard is Moving Picture Experts group 2 (MPEG2). However, the same principle can be applied to digital broadcasting standards other than MPEG2, such as MPEG4, H.264 and the like.
Referring to FIG. 1, reference numerals 11, 13, 15 and 17 designate a structure on a transmitting side of the digital broadcast system, and reference numerals 21, 23, 25, 27 and 29 designate a structure on a receiving side of the digital broadcast system. First, the transmitting side's operation will be described. A clock generated in a clock generator 11 is applied to an encoder 17, the encoder 17 encodes an image, and audio and data by using the clock are outputted from the clock generator 11. The transmitting side transmits transmitting side-clock information to the receiving side. A counter 13, which audio and data are inputted from the clock generator 11, counts the clock by a predetermined division ratio, stores the counted clock as a Program Clock Reference (hereinafter referred to as "PCR") in a register 15, and then transmits the PCR to the receiving side.
Next, the receiving side's operation will be described. The receiving side stores a PCR sample in a register 27 before decoding a broadcast signal transmitted from the transmitting side. A clock generator 21 generates a decoding clock for a decoder 29. Accordingly, a clock frequency is similar to the clock generator 11 on the transmitting side, and the division ratio of a counter 23 also has the same value as that of the counter 13 on the transmitting side. A comparator 25 compares a count value outputted from the counter 23 with the PCR value stored in the register 27 on the transmitting side, and controls the clock generator 21 to supply the decoding clock to the decoder 29 when both the values are the same.
The MPEG2 system as described above uses a system clock of 27 MHz, and uses a clock corresponding to 27 MHz/N (N is an integer) during encoding and decoding. The system clock of 27 MHz outputted from the clock generator 11 is applied to the counter 13, and an output of the counter 13 is stored in the register 15 and is transmitted together with other data at an appropriate time over a transmission channel. The decoder 29 extracts PCR information from an adaptation field of each packet to store the PCR information in the PCR register 27. Then, at a point of time when the PCR stored in the register 27 is the same as the PCR received from the transmitting side (that is, at a point of time when the PCR on the receiving side is synchronized with the PCR on the transmitting side), the comparator 25 drives the clock generator 21 to supply the decoding clock to the decoder 29.
In the above-mentioned operations, the MPEG2 system does not transmit the PCR information from packet to packet, but transmits the PCR information at intervals of 100 ms. Usually, the clock generator may makes an error due to temperature, external impacts and product properties, which becomes an error source when the decoder 29 generates an internal system clock based on the PCR information. In other words, there may occur points of time when the receiving side system is not synchronized with a system clock on the transmitting side because the PCR information is transmitted at intervals. The receiving side is the closest to the transmitting side when the PCR information is received, and the error is the greatest just before the PCR information is received.
If the receiving side is loaded with the PCR value, then a 27 MHz clock source of the clock generator 21 begins to increase a local time reference value of the decoder 29. As stated above, the clock generator 21 make an error due to temperature, external impacts and product properties, which is caused by an error in the local time reference value. Thus, the local time reference value of the decoder 29 becomes different from the PCR count value of the encoder 17. However, if the clock frequency is finely corrected by a different component between the PCR value decoded within the transmission interval of 100 ms and the local time reference value, the local time reference value can consequently correspond to the PCR value of the encoder 17. This finely corrected local time reference value is called a LPCR (Local Program Clock Reference). FIG. 2 is a block diagram illustrating a structure for generating an LPCR to be supplied to the decoder 29 on the receiving side, and simultaneously is a view for explaining a method of reproducing a system PCR. The LPCR generation method using the structure as illustrated in FIG. 2 corresponds to a common PCR generation method used in a MPEG decoding system, such as a settop-box.
Referring to FIG. 2, if a received PCR value is applied to the comparator 25, the comparator 25 compares the received PCR value with the LPCR value of the counter 23 to generate an error signal according to a difference between the two input values. The received PCR value is initially different from the LPCR value, so the clock generator 21 finely corrects a generated erroneous clock (27 MHz). Thus, if a certain time elapses, the received PCR value becomes identical to the LPCR value. Through such a procedure, a LPCR for use in the receiving side can be reproduced. Also, when the LPCR value is identical to the PCR value, a divider 31 divides the clock by a predetermined division ratio to apply the divided clocks as audio, video and data decoding clocks to the decoder 29.
The digital broadcast receiver may use two time stamps in order to control the decoder. In the digital broadcast receiver, there are two types of time stamps, that is, a Decoding Timing Stamp (hereinafter referred to as "DTS") and a Presentation Timing Stamp (hereinafter referred to as "PTS"). Here, the DTS has a PCR value at a point of time when the decoder begins to perform decoding, and the PTS has a PCR value at a point of time when a decoding result is outputted from the decoder. Thus, the digital broadcast receiver controls the decoder such that the decoder begins to decode received data when the DTS is generated, and outputs a decoded broadcast signal when the PTS is generated. Accordingly, the digital broadcast receiver may not use the PTS in a case where the DTS is used, or may not use the DTS in a case where the PTS is used.
FIG. 3 is a block diagram for explaining a synchronization procedure of a digital broadcast receiver using a DTS, and FIG. 4 is a timing chart illustrating timing for controlling a decoding operation in a synchronization structure as shown in FIG. 3.
Referring to FIGS. 3 and 4, the digital broadcast receiver begins to perform decoding of audio, video and/or data in coincident with DTS information. That is, the synchronization of a decoder (audio, video and/or data decoder) is implemented by a DTS. First, if a digital broadcast signal is received, a PCR/DTS extractor 41 extracts a PCR and a DTS from the received digital broadcast signal to output a video DTS (hereinafter referred to as "VDTS") and an audio DTS (hereinafter referred to as "ADTS") to a decoder 45, respectively, as indicated by reference numerals 53 and 55 in FIG. 4. Here, the decoder 45 may be an audio and video decoder. Also, a LPCR generator 43 having a structure as shown in FIG. 2 generates a LPCR synchronized with the PCR, as indicated by reference numeral 51 in FIG. 4. Then, the decoder 45 decodes and outputs the digital broadcast signal at a point of time when the DTS becomes identical to the LPCR value. That is, the LPCR value continually increases by an internal counter of the decoder 45, as indicated by reference numeral 51 in FIG. 4. The corresponding decoder decodes and outputs data stored in an input buffer with reference to the DTS information outputted from the PCR/DTS extractor at a point of time when the LPCR value becomes identical to the DTS, as indicated by reference numerals 53 and 55 in FIG. 4. At this time, an outputting time of the decoder 45 is delayed by a decoding time of the decoder 45.
FIG. 5 is a block diagram for explaining a synchronization procedure of a digital broadcast receiver using a PTS, and FIG. 6 is a timing chart illustrating timing for controlling a decoding operation in a synchronization structure as shown in FIG. 5.
Referring to FIGS. 5 and 6, outputs of a video decoder 65 and an audio decoder 69 are synchronized with each other by using a LPCR and a PTS in FIG. 5. That is, a PCR/PTS extractor 61 extracts PCR information and PTS information from a received digital broadcast signal. Here, the PTS information may be APTS and VPTS information. Then, a LPCR generator 63 generates a LPCR from the PCR, as indicated by reference numeral 81 in FIG. 6, and the video decoder 65 and the audio decoder 69 decode encoded video data and encoded audio data from the received digital broadcast signal, respectively. Also, a video output buffer 67 buffers the video data decoded in the video decoder 65, and outputs the buffered video data at a point of time when the LPCR becomes identical to the VPTS, as indicated by reference numeral 83 in FIG. 6. An audio output buffer 71 buffers the audio data decoded in the audio decoder 69, and outputs the buffered audio data at a point of time when the LPCR becomes identical to the APTS, as indicated by reference numeral 85 in FIG. 6.
However, the decoder synchronization method as stated above must include the LPCR generator for generating the LPCR based on the PCR after the PCR is received. That is, the LPCR generator functions to generate the LPCR corresponding to the PCR transmitted from the transmitting side, and the LPCR is used as a PCR for controlling decoding timing of the audio, video and data decoder. Since a clock generator is included inside the LPCR generator, and the clock generator must generate a clock at high frequency, the LPCR generator requires high precision. Also, the above-mentioned decoding synchronization method of the digital broadcast receiver must make use of the LPCR. In this case, a counter capable of maintaining a preset level (for example, in FIG. 2, 90 KHz) must be designed, and such counter design is difficult to be supported by an Operating System (OS) of a portable terminal with the digital broadcast receiver.
As stated above, the DTS and the PTS are generally used as a synchronization signal for controlling decoding timing of the digital broadcast receiver. At this time, the intermittence of an audio signal is more sensitively perceived as compared with a video signal, so the audio signal is continuously reproduced. Thus, a decoding control signal (ADTS or APTS) of the audio signal can be used if the audio signal becomes identical to the PCR value. That is, decoding timing of audio and video can be controlled with reference to the ADTS or APTS. Since the audio signal has the very short necessary time for decoding, the ADTS and the APTS substantially have the same value. Therefore, after a PCR on a receiving side is set by estimating the PCR value from the ADTS or APTS value, audio decoding timing can be controlled using the ADTS or APTS, and video decoding timing can be controlled by synchronizing a VDTS or VPTS with the ADTS or APTS.
Accordingly, there is a need for an improved synchronization device and synchronization method in a digital broadcast receiver that estimates and reproduces a Program Clock Referencing for controlling decoding timing.

Synchronization device and synchronization method in digital broadcast receiver


The present invention provides an improved process for the synthesis of aryl pyridine bases by reacting an aromatic aldehyde or ketone and allylic alcohol or aldehyde in presence of ammonia in gas phase, in high yield and selectivity with catalyst obtained by optionally modifying a zeolite having an atomic ratio of Si to Al, 2.5 to 12.5 and /or with at least one metal ion and/or metal compound selected from the group consisting of lead and lanthanum. This process provides an eco-friendly, more economical and highly selective heterogeneous method.

The present invention relates to a process for the synthesis of an aryl pyridine base using a zeolite catalyst. More particularly, the present invention relates to a method for synthesizing phenyl pyridines directly from acetophenone and allyl alcohol in an eco-friendly, zeolite catalyzed heterogeneous method with high yields and selectivity. This invention provides a non-corrosive, eco-friendly process, where the life time of the catalyst is longer, it can be recycled and reused for many times, no-wastage of compounds (i.e. high atom selectivity) and high selectivity of the products.
Phenyl pyridines have emerged as the integral backbone of several potent azapeptide HIV protease inhibitors with anti HIV activity such as BMS-232632a. Strategies for the synthesis of these phenyl pyridines by condensation and substitution reactions frequently afford low yields and cannot facilitate the synthesis of the 2-position selectively. A few homogeneous catalysts like Rh(1) have been reported for use in the selective alkylation of phenyl pyridine with olefins.
Zeolites of ZSM series are available from Conteka (Sweden). The methods for producing them are described in detail in U.S. Pat. Nos. 3,702,886 (ZSM-5), 3,709,979 (ZSM-11). HY is available from (PQ Corporation USA). HBEA is available from (Sud Chemie, India). HX is available from Aldrich. The synthesis of MCM-41 is disclosed in J. S. Beck et al, Nature 359 (1992) 710.
It is known that crystalline alumino silicate (zeolite) is used as a catalyst for producing pyridine bases from an aliphatic aldehyde and/or ketone and ammonia. ( U.S. Pat. No. 4,220,783 and Japanese patent application kokai (Laid-open) No. 38,362/85).
However, there are no reports available for the production of phenyl pyridines over a solid acid catalyst, except Japanese patent JP 01261367A/98 which discloses the synthesis of 2-phenyl-6-methyl pyridine over Si:Al catalyst starting with acetophenone, formaldehyde and acetone. The selectivity towards the phenyl pyridines in this patent is low. Another disadvantage of the process disclosed in JP 01261367A/98 is that it suffers from the selective synthesis of 2-phenyl pyridine without methyl group. Although a process for the synthesis phenyl pyridine using benzaldehyde and acetaldehyde is described in Ullmann""s encyclopaedia A22, the major yield was only 4-phenyl pyridine.
Prior art processes suffer from the following disadvantages:
(a) in all the cases mineral acids are used as catalysts that are highly corrosive,
(b) non-reusability of the catalyst,
(c) in all the cases tedious work-up procedure is required, such as neutralization of acid etc.,
(d) in some cases more than a single step is require to synthesize phenyl pyridines selectively.
Increasing applications of these phenyl pyridines demands an eco-friendly, economical and free handling process. The present invention provides a eco-friendly process which can overcome all the above drawbacks.
The main object of the present invention is to provide a process for the synthesis of phenyl pyridine bases by using a specific zeolite catalyst, which is an eco-friendly heterogeneous catalytic method.
Another object of the present invention is to improve selectivity of the product.
Accordingly the present invention relates to a process for the synthesis of an aryl pyridine base said process comprising reacting an aromatic ketone of the formula R1COR2 wherein R1 is phenyl or alkyl phenyl, R2 is alkyl with 1 to 2 carbon atoms with the formula R3CHxe2x95x90CHCH2 OH wherein R3 is selected from the group consisting of hydrogen, methyl, ethyl and aryl, with ammonia in a gaseous phase, the mole ratio of the aromatic ketone to allylic alcohol being in the range of 1:1 to 1:5, the mole ratio of ammonia to aromatic aldehyde and/or ketone being in the range of 0.5 to 5.0, the reaction temperature is in the range of 350xc2x0 C. to 500xc2x0 C., in the presence of a catalyst consisting of modified or unmodified zeolite having an atomic ratio of Si to Al in the range of 2.5 to 12.5 with at least one ion of and/or at least one compound of a metal selected from lead and lanthanum to obtain sais aryl pyridine base.
In one embodiment of the invention, the aryl ketone used is selected from acetophenone and methyl acetophenone.
In one embodiment of the invention, the aromatic aldehyde is phenyl acetaldehyde.
In one embodiment of the invention, the allylic alcohol is selected from allyl alcohol and crotyl alcohol.
In one embodiment of the invention, the aromatic ketone used comprises acetophenone and the allylic alcohol used comprises allyl alcohol to obtain 2-Phenyl pyridine.
In a further embodiment of the invention, the molar ratio of Acetophenone:allyl alcohol: ammonia is in the range of 1:1-3:0.5-5.
In one embodiment of the invention, the aromatic ketone used comprises acetophenone and is reacted with acrolein to obtain 2-phenyl pyridine.
In one embodiment of the invention, the aromatic aldehyde used comprises phenyl acetaldehyde and the allylic alcohol used comprises allyl alcohol to obtain 3-phenyl pyridine.
In one embodiment of the invention, the aromatic aldehyde used comprises phenyl acetaldehyde and is reacted with acrolein to obtain 3-phenyl pyridine.
In one embodiment of the invention, acetophenone is reacted with crotyl alcohol to yield 2-phenyl 4-methyl pyridine.
In one embodiment of the invention, acetophenone is reacted with crotonaldehyde to yield 2-phenyl 4-methyl pyridine.
In a further embodiment of the invention, methanol is added to the starting materials in an amount of up to 0.5 mole per mole of acetaldehyde.
In another embodiment of the invention, the zeolite used is in alkali ion form or ammonium ion form or proton form.
In a further embodiment of the invention, the alkali ion form of the zeolite is selected from sodium and potassium.
In a further embodiment of the invention, the zeolite catalyst is ion exchanged with a metal ion of a metal selected from the group consisting of lanthanum, thallium, lead and cobalt.
In yet another embodiment of the invention, the zeolite catalyst used is treated with at least one compound of a metal selected from the group consisting of lanthanum, lead and cobalt by impregnation, immersion, deposition or evaporation to dryness.
In yet another embodiment of the invention, the metal compound of lanthanum, lead and/or cobalt is at least one metal compound selected from the group consisting of oxides, halides, sulfates and phosphates.
In a further embodiment of the invention, the metal compound of lanthanum, lead and/or cobalt comprise oxides.
In yet another embodiment of the invention, the content of the metal compound of lanthanum, thallium, lead and/or cobalt is 0.1 to 5 wt % equivalent per g of the zeolite.
In yet another embodiment of the invention, crotyl alcohol is used as the allylic alcohol to obtain aryl picoline.
In another embodiment of the invention, the proportion of Si to Al in the zeolite is in the range of 2.5 to 140.
In yet another embodiment of the invention, the zeolite is selected from the group consisting of ZSM-5, ZSM-11, HYxe2x80x94a crystal structure of faujasite, HBEA Al-MCM-41, MCM-41 and HX.
In another embodiment of the invention, the catalyst comprises amorphous silica-alumina.
The present invention also relates to develop a process for the preparation of phenyl pyridines of the formula
from acetophenone and allyl alcohol over a zeolite catalyst.
Aryl pyridine bases are obtained according to the process of this invention by reacting an aryl aldehyde and/or ketone with allylic alcohols (alkenyl alcohol or aldehyde) in presence of ammonia in gaseous phase in the presence of a catalyst, which is selected from varied Si :Al ratio in the range 2.5 to 140 or a catalyst with a particular Si/Al ratio modified with at least one metal compound selected from the group consisting of lanthanum compounds, lead compounds and cobalt compounds by impregnation or ion exchange methods. Among zeolites, those having an atomic ratio of Si to Al 2.5 to 140 can be used as the starting materials for preparing the catalysts to be used in the present invention, which show a high catalytic performance.
The zeolites which can be used as the starting materials for preparing the catalysts to be used in the present invention are exemplified as several zeolites including aluminosilicate such as ZSM-type, HY, Al-MCM-41, H-BEA, HX. From these except MCM-41 other zeolites are easily commercially available, and also are prepared by methods known in the literature. For example, zeolites of ZSM series are available from Conteka (Sweden). The methods for producing them are described in detail in U.S. Pat. Nos. 3,702,886 (ZSM-5), 3,709,979 (ZSM-11), HY is obtained from (PQ corporation USA), HBEA was obtained from (Sud chemie, India), HX was from Aldrich and MCM-41 was synthesized by known art according to (J. S. Beck et. al., Nature 359 (1992) 710).
Furthermore, the zeolite used in the present invention may be in any of the alkali ion form such as sodium, potassium or ammonium ion form and proton form. The alkali ion, however, is not preferably because it lowers the catalytic activity, and hence it is desirable to eliminate the alkali ion before, during or after modifying the zeolite with ion of and/or compound of metal selected from the group consisting of lanthanum, lead and/or cobalt. The zeolite to be subjected to impregnation is treatment with lanthanum, lead and/or cobalt ions may be in any one of alkali ion form, ammonium ion form or proton form, and the most preferable is ammonium form zeolite. Accordingly, it is desirable that a zeolite of an alkali ion form or proton form is previously ion exchanged into ammonium form by dipping it repeatedly for several times in an aqueous solution of an ammonium salt such as ammonium chloride, ammonium nitrate, ammonium acetate or in aqueous ammonia and then filtering it.
A zeolite alkali ion form, ammonium form or proton form, preferably of proton form is added to an aqueous solution of at least one metal compound selected from the group consisting of lanthanum compounds, lead compounds and cobalt compounds with a concentration of 0.5 to 10 wt % per gram catalyst and soaked for several hours finally evaporated the water. After the procedure, the modified zeolite is usually dried at 100xc2x0 C. to 200xc2x0 C. and if desired, calcined at 350 to 450xc2x0 C. to obtain a catalyst.
Though the calcination is conducted usually in air or in a gas such as nitrogen or the like at 350xc2x0 C. to 500xc2x0 C. for several hours, the calcination is not always necessary because the catalyst is heated in a reactor.
The content of lanthanum, lead and/or cobalt in the zeolite which has been modified with the corresponding metallic ions and/or compounds is about 0.5 to 10 wt % equivalent/g, though the preferable region varies depending on the kind of the zeolite and of the metal ion and compound.
The zeolite which has been ion exchanged with lanthanum ion, lead ion and/or cobalt ion or the zeolite which has been treated with at least one metal compound selected from thallium compounds, lead compounds and/or cobalt compounds by a method of impregnation, deposition or evaporation to dryness is molded as it is or after pelletization to a tablet and made it to 18-30 mesh.
In either method, the molded product is calcined in the atmosphere or in a gas such as nitrogen or the like at 350xc2x0 C. to 600xc2x0 C. for several hours to impart strength to the molded product and to eliminate volatile components which had been contained in the binder. However, because the catalyst is heated in a reactor, the calcination is not always necessary.
The aryl ketone used in the present invention includes acetophenone, methyl acetophenone and alkenyl alcohol or aldehydes and allyl alcohol, crotyl alcohol, acrolein or crotonaldehyde.
The combination of aromatic aldehydes and/or ketones as the starting materials with alkenyl alcohol determines the main phenyl pyridine bases produced. Typical examples are shown in the Table 1.
The reaction of the present invention is conducted in a mode of fixed bed.
The molar ratio of ammonia to the aromatic aldehyde and/or ketone is 0.5 to 5 mol/mol. The weitht hourly space velocity (WHSV) used is 0.25 to 1.00. The reaction temperature is preferably 300xc2x0 C. to 400xc2x0 C. Although the pressure of the reaction gases can be used in the range of from below the atmospheric pressure to several atmospheric pressures, usually the pressure in the range of from the atmospheric pressure to about 2 atmospheric pressures is used conveniently.
In particular, preferable combination of an aromatic aldehyde or ketone with alkenyl alcohol or aldehyde for the production of phenyl pyridine or phenyl picolines the molar ratio of acetophenone: allylalcohol: ammonia is adjusted to 1:1-3: 0.5-5.
In particular, in this reaction one other side product observed is 3-picoline which is also an important drug intermediate.
Although deposition of carbon on the catalyst is detected during the reaction, the amount of the carbon deposited on the catalyst is smaller as a result of which higher yield of 2- phenyl pyridine is obtained.
The regeneration of the catalyst is easily effected by any conventional method such as burning out the carbon deposited on the catalyst by passing air through the catalyst layer at a temperature of 450xc2x0 C. to 550xc2x0 C. The products were trapped by cooling at the bottom and analyzed by GC, confirmed by NMR and GC-MS.
By using the catalyst of the present invention, as shown, for example, in Example 1, the yield of 2 phenyl pyridine is 63% and 81%, respectively, the yields being shown as the value calculated based on the conversion of acetophenone.
2-phenyl pyridine can be obtained in a higher yield as compared with in conventional processes. Also, the amount of carbon deposited on the catalyst is small and the regeneration of the catalyst is easy.
The present invention is described below in more detail referring to Examples, to which the present invention is not limited. The results in examples are calculated based on the conversion of acetophenone.

Process for the synthesis of an aryl pyridine base using a zeolite catalyst

Council of Scientific and Industrial Research


Embodiments of the present disclosure provide a method and apparatus for determining position and orientation of a bucket of an excavator, an electronic device and a computer readable medium. The method may include: acquiring an image of a bucket of an excavator collected by a camera provided on an excavator body, the image of the bucket including a preset marker provided on the bucket; determining position and orientation information of the camera relative to the bucket on the basis of the image of the bucket and pre-acquired three-dimensional feature information of the preset marker; and converting the position and orientation information of the camera relative to the bucket into position and orientation information of the bucket relative to the excavator body.

An unmanned excavator is an intelligent excavating device that senses an excavation object by means of various sensors, plans an operational behavior, and executes an operation instruction. When executing a task of excavating a material pile, the unmanned excavator needs to control a bucket to move to a target area of a mound for excavation. Therefore, it is necessary to accurately and quickly determine position and orientation of the bucket relative to an excavator body. The current solution is to install angle sensors on a big arm, a small arm and the bucket of the excavator, and determine the position and orientation of the bucket according to readings in such sensors.

Method and apparatus for determining position and orientation of bucket of excavator

BEIJING BAIDU NETCOM SCIENCE AND TECHNOLOGY CO., LTD.


A device for dynamically measuring the bubble content of a flowing liquid is arranged in a conveyance passage for a flowing liquid or provided in a simple bypass for the conveyance passage of the liquid so that the bubble content of the flowing liquid and the bubble quantity of dissolved gas in the flowing liquid can be dynamically measured due to a change in the pressure of the liquid in the passage or the bypass without extracting any of the liquid therefrom.

The present invention relates to a device for dynamically measuring the bubble content of a flowing liquid. More particularly, the invention relates to a device provided in a conveyance passage for a flowing liquid, as may be used in the chemical or mechanical industries, or provided in a simple bypass for the conveyance passage, so that the bubble content of the flowing liquid and the bubble quantity of dissolved gas in the flowing liquid can be dynamically measured without extracting any of the liquid therefrom.
When a liquid such as a lubricating oil and a liquid containing a polymer, a surface active agent or the like flows through a passage with agitation, bubbles are likely to be produced in the liquid. The bubbles contained in the liquid are likely to cause various problems, such as an inaccurate measurement of the flow rate of the liquid, or, in the case that the liquid is a lubricating oil, a drop in the efficiency of operation of a hydraulic apparatus operated by the liquid and abnormal wear of the lubricated sliding surfaces of the machine. Although it is often necessary to dynamically, quickly and accurately measure the bubble content of a liquid, no appropriate measuring device has heretofore been available. Conventionally, a sample of the liquid has been extracted from a passage for the liquid and subjected to a gas chromatography or a static separation process. However, such procedures are time consuming, the bubbles in the liquid are likely to disappear, and it is difficult to accurately measure the bubble content of the liquid.
Accordingly, to overcome the above problems, a method and a device for dynamically measuring the bubble content of a flowing liquid without extracting any of the liquid from a passage were disclosed in U.S. Pat. No. 5,041,990. The device is installed in a conveyance passage of a bubble-containing liquid or in a bypass of the passage. The device includes a density sensor sensitive to the density of the bubble-containing liquid, a pressure sensor, a temperature sensor, a pressure calculation circuit, a temperature calculation circuit, a bubble content calculation circuit, a control panel, and a bubble content display panel. The density of the liquid, which changes depending on the bubble content of the liquid, is first measured. The pressure calculation circuit, the temperature calculation circuit, and the bubble content calculation circuit then carry out calculations in accordance with a predetermined formula and an instruction from the control panel to determine the bubble content of the flowing liquid at a standard pressure and a standard temperature. The bubble content determined in this manner is indicated on the bubble content display panel.
Although the bubble content of the liquid at high pressure can be measured by the method and device disclosed in the above-mentioned patent, there is still such a problem that it is difficult for the method and the device to dynamically measure the bubble content of the liquid at low pressure and the quantity of dissolved gas in the liquid.

Device for dynamically measuring bubble content of flowing liquid


A mask for use on a layer of imaging material which is located on at least a portion of one surface of a substrate in a lithography process in accordance with one embodiment of the present invention includes a layer of a masking material which has an optical density of at least 4.0 for wavelengths at or below about 180 nm and a thickness of less than about 1000 angstroms. Materials, such as tungsten and amorphous silicon, can be used for the mask.

Lithography is a process for producing a pattern on a semiconductor wafer. The pattern is produced by first exposing a pattern etched into a mask onto a semiconductor wafer coated with a resist material. The projected image of the pattern changes the composition of the resist material on the semiconductor wafer which is then removed to leave a matching pattern on the semiconductor wafer for further processing.
Depending upon the particular lithography application, the mask needs to satisfy several different requirements. The challenge is in finding a material or materials for use as the mask which will satisfy these requirements.
Historically, optical masking has been performed using a layer of chromium rich chromium nitride over fused silica, overcoated with a chromium oxinitride anti-reflective ("AR") layer to reduce reflectivity below 10%. Chromium ("Cr") is an excellent choice from optical the thermomechanical standpoints at wavelengths where it is sufficiently opaque, i.e. wavelengths generally above 180 nm. The spectra of chromium metal shown in FIG. 1 illustrates why it has been such a good mask from about 193 nm to about 436 nm. Referring to FIG. 2, the optical density (plotted here at log (transmission)) of a 1000 Å Cr metal film is shown. Again for wavelengths between about 193 nm and 500 nm, chromium is an excellent choice. The optical density of Cr film is near 5.0 in the ultraviolet ("UV") range and it decreased to ˜4.5 at 193 nm. As thinner Cr metal films are used in manufacturing (800 Å for instance), the optical density above 190 nm may still be sufficiently high (above 4.0).
However, as shown in FIG. 1, chromium metal is a less desirable choice as a mask for wavelengths below 193 nm. Additionally, as shown in FIG. 2, at 157 nm, the optical density of the Cr metal film is 3.5 for a 1000 Å film and as low as 3.0 for a 800 Å film. At these optical densities, mask modulation is likely to be low for imaging of fine feature geometry. Unfortunately, a masking film thickness of over about 800 Å is undesirable for 157 nm applications because of the aspect ratio requirements of features smaller than 300 nm. Accordingly, it appears that chromium mask materials may not be adequate below 193 nm, in particular at potential vacuum ultraviolet ("VUV") wavelengths, i.e. from about 120 nm to 180 nm, such as 157 nm.
Another factor in selecting a mask for use in optical lithography below 180 nm is the etch characteristics of the mask. The mask must have suitable etch characteristics with selectivity to the underlying substrate and to the resist material. In other words, the film on the substrate which forms the mask must be made of a material or materials which can be etched to form the pattern to be replicated on semiconductor wafers without significant loss to the underlying substrate or to the resist material.
As yet, an appropriate replacement material or materials for chromium films for use as the mask for lithography at or below 180 nm, i.e. a mask with the desired optical properties and etch characteristics, has not been found.

Masks for use in optical lithography below 180 nm


A multi-layer device is provided for connecting to an electrical unit enclosed within the multi-layer device. A first wafer has a first outer terminal and a second outer terminal with etch pits. A first insulator has a first surface bonded to the first wafer and a first inner terminal located on an opposing second surface. A second wafer has a first surface bonded to the second surface of the first insulating layer and includes a pillar electrically connected to the first wafer. A second insulator has a first surface bonded to a second surface of the second wafer and a second inner terminal located on the first surface of the second insulator. The first outer terminal is electrically connected to the first inner terminal, and the second outer terminal is electrically connected to the second inner terminal. The first and second outer terminals are adapted for connecting to an electrical unit. A reinforcement is positioned adjacent to at least one of the first and second outer and, inner terminals to provide for reinforcement of the at least one of the first and second outer and inner terminals.

1. Field of the Invention
This invention relates generally to multi-terminal, multi-layer devices, and more particularly to multi-terminal, multi-layer devices, which can withstand greater mechanical shocks or mechanical loads to their terminals.
2. Description of the Related Art
In certain applications, electrical devices or sensors are used to measure or detect various operating or performance parameters such as, for example, temperature, pressure, or acceleration. These devices can be actuators or electronic devices such as magnetic field sensors. Typically, the electrical functions of the devices are communicated to support electronics and/or some recording apparatus that allows an operator to monitor the parameters being measured by the sensors. In many instances, the device is provided with terminals, which are simply connected to lead wires extending from the support electronics or recording apparatus.
Some electronic devices are made of multiple layers of semiconductor material. These devices or sensors typically include an interior operating unit. The electrical function of the unit may occur at various layers of the device, which must be connected, to the external electronics. For example, lead wires may be connected to interior terminals on one or more surfaces of the interior operating unit, and then fed through access holes in the layers to the outside of the device. However, when electrical functions are communicated from surfaces on opposite sides, for example, an upward and a downward surface, of the interior operating unit, wiring to the unit becomes inconvenient during the assembly process.
Some assembly processes use a "flip-chip" technique in which the inner terminals of the interior operating unit are presented on one surface. Patterns of conductor lines extend from the inner terminals up an insulated surface of a semiconductor layer that is adjacent to the interior operating unit to an outer surface of the semiconductor layer. It has been proposed to electrically connect the interior operating unit to the outside by using metal thin films that coat oxide-insulated holes of semiconductor layers positioned next to the interior operating unit. Such connections, however, introduce large capacitance coupling which can be troublesome, for example, for systems working at radio frequencies. Furthermore, extending the conductor lines through several layers is not easily accomplished.
There is a need to provide an improved multi-terminal, multi-layer device. There is a further need to provide an improved multi-terminal, multi-layer device, which can withstand greater mechanical shocks or mechanical loads to its terminals.


The invention relates to a process 1-olefins by telomerization of compounds having conjugated double bonds with a telogen in the presence of a noble metal telomerization catalyst, hydrogenation of the telomer and cleavage of the hydrogenated intermediate. Use of the 1-olefin as comonomer.

1. Field of the Invention
The invention relates to a process for preparing 1-olefins by telomerization of compounds having conjugated double bonds with a telogen in the presence of a noble metal telomerization catalyst, hydrogenation of the telomer and cleavage of the hydrogenated intermediate.
2. Description of the Background
1-Olefins such as 1-octene are used in large quantities in the production of various chemical products. For example, surface-active substance, plasticizers, lubricants and polymers are produced from 1-octene. Another large application is its use as comonomer in polymers, in particular in polyethylene.
Virtually all processes used commercially at the present time for producing 1-octene are based on the raw material ethene. Ethene is oligomerized to give a product spectrum of α-olefins as main products. With appropriate choice of catalyst and process conditions, the amount of 1-octene in the product can be optimized and is then about 25%. Apart from these processes by means of which the major part of the 1-octene produced is obtained, the isolation of 1-octene from the product mixture from the Fischer-Tropsch reaction has attained some importance.
Apart from the ethene-based processes, processes which use 1,3-butadiene as raw material for preparing 1-octene are also known from the literature. However, 1-octene is not obtainable directly from butadiene, for example by means of dimerization, but is obtained after a plurality of process steps. Thus, the patent application WO 92/10450 describes a process in which 1,3-butadiene is reacted preferably with methanol or ethanol to form a 2,7-octadienyl ether which is then hydrogenated to the octyl ether and is then cleaved to give 1-octene. EP-A-0 440 995 follows an analogous route, but the reaction in the first step is with a carboxylic acid. The first process step, which is generally referred to as telomerization, is involved in both the processes. In telomerization, a telogen (in EP-A-0 440 995 the carboxylic acid) is generally reacted with a taxogen (1,3-butadiene, 2 equivalents) to form a telomer.
Examples of telomerization reactions are described, inter alia, in E. J. Smutny, J. Am. Chem. Soc. 1967, 89, 6793; S. Takahashi, T. Shibano, N. Hagihara, Tetrahedron Lett. 1967, 2451; EP-A-0 561 779, U.S. Pat. Nos. 3,499,042, 3,530,187, GB 1 178 812, NL 6 816 008, GB 1 248 593, U.S. Pat. Nos. 3,670,029, 3,670,032, 3,769,352, 3,887,627, GB 1 354 507, DE 20 40 708, U.S. Pat. Nos. 4,142,060, 4,146,738, 4,196,135, GB 1, 535 718, U.S. Pat. No. 4,104,471, DE 21 61 750 and EP-A-0 218 100.
In the known processes for preparing 1-octene on the basis of butadiene, as described, for example, in WO 92/10450 or EP-A-0 440 995, the 1-octene is obtained by cleavage of an n-octane substituted in the 1 position. The selectivities in this step are often unsatisfactory. Thus, WO 92/10450 reports a selectivity to octenes of 66% at a conversion of 80% in the cleavage of 1-methoxyoctane.
Catalysts which have been found to be effective for telomerization are halogen-free palladium(0) and palladium(II) compounds (A. Behr, in "Aspects of Homogeneous Catalysis"; editor R. Ugo, D. Reidel Publishing Company, Doordrecht/Boston/Lancaster, 1984, Vol. 5, 3). In addition, compounds of other transition metals such as cobalt (R. Baker, A. Onions, R. J. Popplestone, T. N. Smith, J. Chem. Soc., Perkin Trans. II 1975, 1133-1138), rhodium, nickel (R. Baker, D. E. Halliday, T. N. Smith, J. Organomet. Chem. 1972, 35, C61-C63; R. Baker, Chem. Rev. 1973, 73, 487-530; R. Baker, A. H. Cook, T. N. Smith, J. Chem. Soc., Perkin Trans. II 1974, 1517-1524) and platinum have also been used as catalysts. However, the latter systems are inferior to palladium complexes in terms of activity and selectivity.
WO 91/09822 describes a continuous process using palladium acetylacetonate/2 equivalents of triphenylphosphine as catalyst. Catalyst productivities (turnover numbers) of up to 44,000 are achieved here. However, the chemoselectivities to the target product at such catalyst turnover numbers are <85%. The use of palladium complexes or palladium salts in combination with carboxylic acids for the telomerization of butadiene is known from EP 0 440 995. However, the complexing agent is not specified.
A process for the preparation of octadienyl ethers was described in 1987 by National Distillers and Chem. Corp. (U.S. Pat. Nos. 4,642,392, 4,831,183). The product mixture was separated from the catalyst (palladium acetate/5 equivalents of triphenylphosphine) by distillation, leaving the catalyst as a solution in a high-boiling solvent. The catalyst can be reused up to twelve times when supplementary phosphine is added each time. However, the initial batch (Example 1) gave the linear ether in a yield of only 57% (corresponding to a TON of 2000). The n/iso ratio of the telomers is in this case only 3.7:1. In U.S. Pat. No. 4,831,183, the mixture was separated from the reaction solution by, for example, extraction with hexane. The telomerization was carried out in dimethylformamide or sulfolane using the catalyst mixture palladium(II) acetate/3 equivalents of triphenylphosphinemonosulfonate. Longer-chain primary alcohols such as ethanol, propanol and butanol (J. Beger, H. Reichel, J. Prakt. Chem. 1973, 315, 1067) also form the corresponding telomers with butadiene. However, the catalytic activity of the known catalysts is even lower here than in the abovementioned cases. Thus, under identical reaction conditions [Pd(acetylacetonate)2/PPh3/butadiene/alcohol =1:2:2000:5000; 60° C./10 h], the telomers of methanol are formed in a yield of 88%, those of propanol are formed in a yield of 65% and those of nonanol are formed in a yield of only 28%.
Like alcohols, carboxylic acids are suitable nucleophiles in telomerization reactions. Acetic acid and butadiene give the corresponding octadienyl derivatives in good yields (DE 2 137 291). The ratio of linear and branched products (n/iso ratio) can be influenced via the ligands on the palladium (D. Rose, H. Lepper, J. Organomet . Chem. 1973, 49, 473). A ratio of 4/1 was achieved using triphenylphosphine as ligand, and the ratio could be increased to 17/1 when using tris(o-methylphenyl) phosphite. Other carboxylic acids such as pivalic acid, benzoic acid and methacrylic acid, and also dicarboxylic acids, can likewise be reacted with butadiene.
Shell Oil has described a process for preparing α-olefins based on the telomerization of conjugated dienes with carboxylic acids in U.S. Pat. No. 5,030,792.
Telomerization reactions in which water is used as nucleophiles have been intensively studied by, inter alia, the Kuraray company (U.S. Pat. Nos. 4,334,117, 4,356,333, 5,057,631). In these reactions, phosphines, usually water-soluble phosphines, or phosphonium salts (EP 0 296 550) are used as ligands. The use of water-soluble disphosphines as ligands is described in WO 98/08794. DE 195 23 335 discloses the reaction of alkadienes with water in the presence of phosphonite or phosphinite ligands.
GB 1 535 718 describes the telomerization of butadiene with amines, catalyzed by palladium(0) complexes. EP 939074 and EP 773211 describes the preparation of octa-2,7-diethyl-1-amine by telomerization of ammonia and butadiene.
The telomerization of butadiene with nucleophiles such as formaldehyde, aldehydes, ketones, carbon dioxide, sulfur dioxide, sulfinic acids, β-keto esters, β-diketones, malonic esters, α-formyl ketones and silanes is likewise described in the literature.
In summary, it can be said that the known palladium-phosphine catalysts do not give satisfactory catalytic turnover numbers (TONs, catalyst productivities) in telomerization reactions of butadienes with alcohols. Industrially desired productivities of >100,000 have rarely been described for known systems. At the same time, high chemoselectivities and regioselectivities of >95% should be achieved in order to obtain an ecologically advantageous process.

Method for producing 1-olefins using palladium carbene compounds