A method of concealing bit errors in a signal is provided. The method comprises encoding a signal parameter according to a set of constraints placed on a signal parameter quantizer. The encoded signal parameter is decoded and compared against the set of constraints. Finally, the method includes declaring the decoded signal parameter invalid when the set of constraints is violated. Training binned ranges of gain values provide a threshold for selecting data segments to examine for violation of constraints on gain differences. Further, an additional method comprises training a threshold function T(qlg(m−1), Δqlg(m−1) used in a codec bit error detecting technique. The threshold function is based upon a first training file having N signal segments. The method includes encoding the first training file and determining gain values qlg(m) of each of the N signal segments within the encoded first training file. The gain values form a range and the range is divided into bins. Next, the gain values are stored in a second training file. The method associates each of particular ones of the gain values and gain differences within the sequence qlg(m−1) and Δqlg(m−1) with a corresponding one of the bins.

1. Field of the Invention
This invention relates to digital communications, and more specifically to the enhancement of speech quality when a bit stream representing a speech signal is subject to bit errors.
2. Related Art
In speech coding, sometimes called voice compression, a coder encodes an input speech or audio signal into a digital bit stream for transmission or storage. A decoder decodes the bit stream into an output speech signal. The combination of the coder and the decoder is called a codec. When a transmission channel or storage medium introduces bit errors to the bit stream received by the decoder, the decoded speech will be degraded compared with the speech decoded from an error-free bit stream.
There are various ways for addressing bit errors. One well-known approach is forward error control, where a transmitter transmits additional redundant bits in such a way that allows a corresponding receiver to detect or even correct certain bit errors. With enough redundant bits transmitted, this scheme can be made very robust to bit errors. However, a drawback is that the overall bit rate is significantly increased by the transmission of redundant bits.
A second approach is to optimize quantizers within the codec for noisy channels with bit errors. Given a target bit error rate, in the design phase, the codec quantizers can be optimized to give a decoded signal that is better in the mean-squared error (MSE) sense, without the need to transmit redundant bits for forward error control. The problem is that such noisy-channel-optimized quantizers often have dynamic ranges smaller than the dynamic ranges of quantizers optimized for clear channel (i.e. channel free of bit errors). As a result, although the codec's performance is improved for the target bit error rate, for clear channel there is often a noticeable degradation in performance.
What is needed therefore is a technique for concealing bit errors in signals that exploits the natural redundancy in the transmitted signal parameters but does not degrade codec performance.

Bit error concealment methods for speech coding


A method to improve the stacking of containers comprising thermoplastic plastic, and the transfer of the stacks to a successive device. Stacks of a predetermined number are intended to be produced without disturbances, even with a high cycle number of the shaping tool. This is achieved in that the containers are stacked in a first stack magazine, which is exchanged for an adjacent stack magazine between two cycles of the shaping tool after the predetermined number has been reached. The containers are stacked in the stack magazines directly from the shaping tool, or by an intermediate transfer device.

The invention relates to a method for stacking containers that have been shaped and punched from a sheet of thermoplastic plastic in a shaping tool, and guided to stack magazines, as defined in the preamble to the main claim. The invention further relates to an apparatus for executing the method.
It is known to stack containers that have been shaped and punched from a sheet of thermoplastic plastic in stack magazines, and to remove the stacks from the stack magazines when a specific length or specific piece number is attained, then supply them to successive devices. In these successive devices, either processing takes place, such as bordering of the container edge, or the rods are packaged in foil and transferred to cartons. It is also known to shape the containers in a plurality of rows, with several containers per row, and to guide the stacks consecutively with a transfer device, so they pass through a single bordering station, for example. Stack magazines for receiving the total batch of containers shaped per cycle in the shaping tool are disposed in front of the shaping tool, which is pivoted into the transfer position.
Transporting stacks of specific lengths out of the stack magazines stipulates a certain amount of time. During this time, the shaping tool must continue producing, and the containers must be able to be stacked. German utility model application DE 298 02 318 U 1 proposes to arrange a stationary stack magazine in the stacking station, and above it, a movable stack magazine, with the movable stack magazine being displaceable in both the stacking direction and the direction transverse thereto. The containers are first transferred into the stationary stack magazine, then enter the movable stack magazine after a specified stack height has been attained.
German Patent DE-PS 26 48 563 C 2 likewise discloses transferring the containers into a stationary, lower stack magazine initially, then into a stack magazine that is adjustable in height and lifts a stack once it reaches a specific length or a specific number of containers. A lateral sliding element transfers these stacks to a horizontal receiving sheet.
Handling stacks in this manner does not provide consecutive guidance of the stacks. They would have to be taken up again, a process that would be susceptible to disturbances. A disadvantage of the two cited publications is that, during the time in which the stacks are transferred from the stack magazines, the number of stacked containers depends on the cycle number of the shaping tool. The transfer time of the stacks is constant because of the established paths and speeds of the drives. This means, however, that a varying number of containers is shaped and stacked during this transfer time. This is significant, and is associated with control problems, if stacks are to be formed from a specific number of containers. A further drawback of the two stacking methods is that the containers must be pressed over two stacking edges, which always poses a risk of deformation. As the movable stack magazine returns, it must be pushed across the standing stacks, which can also cause deformation, because each container edge of the standing containers must be guided by these retaining elements. This method of gripping containers is highly susceptible to disturbances, which may necessitate shutting down the shaping machine, cleaning the stack magazines or organizing the containers located in the stack magazines.
It is the object of the invention to execute the method in order to create stacks of a predetermined number of containers, regardless of the cycle number of the shaping tool, and independently of the time required for transferring the stacks to successive devices, even if the apparatus is shut down. The method is intended to be insusceptible to disturbances, and able to be executed even with high cycle numbers of the shaping tool. Furthermore, the method should permit the transfer of container stacks in rows to a successive device, and a fast changeover of the apparatus for a different batch of containers.
The above object generally is achieved according to a first aspect of the invention by a method for stacking containers that have been shaped and punched from a sheet of thermoplastic plastic in a shaping tool, and guided to stack magazines, and for transferring the stacks to a successive device, wherein the containers are transferred into a first stack magazine at a stacking station; after a predetermined number of containers per stack has been attained in the first stack magazine, the first stack magazine is displaced into a stack-removal station, and a second stack magazine is transferred out of the stack-removal station into the stacking station, between two cycles of the shaping tool; and while the containers are being stacked in the second stack magazine at the stacking station, the first stack magazine is emptied, and the removed stacks are guided to a successive device.
The above object generally is achieved according to a second aspect of the invention by an apparatus for stacking containers that have been ejected from a shaping tool after being shaped and punched out with, for executing the method according to the invention wherein two stack magazines, which can be displaced between a stacking station and a stack-removal station are provided.

Method and apparatus for stacking containers comprising thermoplastic, and apparatus for executing the method


A magnetically permeable material comprising a substantially amorphous permalloy film is disclosed. The substantially amorphous permalloy film is formed by ion-beam sputtering. The substantially amorphous permalloy film exhibits improved output amplitude and noise characteristics.

This application was filed under 35 U.S.C. 371 from PCT/US93/11968 filed Dec. 9, 1993.
The present invention relates to permalloy films and more particularly to an amorphous permalloy film which can be used in magnetic recording systems.
A recent trend in magnetic storage system design is the use of magneto-resistive (MR) heads to read data from a magnetic storage medium in a magnetic storage device. Use of MR heads, instead of inductive sensor heads, has enabled manufacturers to increase recording densities in magnetic storage systems. Various materials and methods of fabricating thin films from these materials are being used to produce MR heads which can be used to meet the higher recording density requirements which will be needed in future magnetic storage systems.
Permalloy is a name for any of a large number of highly magnetically permeable alloys containing a combination of nickel and iron. Permalloy is frequently used as magnetic circuit material for applications such as thin film MR heads because of its high magnetic permeability and its superior frequency characteristics. Specifically, permalloy has been used as a thin film magneto-resistive element (MRE) in MR heads. The MRE of a thin film MR head is the portion which exhibits a change in resistance as it passes through magnetic fields emanating from the magnetic storage media and other favorable magnetic and electrical properties.
Although many magnetic films are currently made from permalloy, other types of materials are also frequently used. For example, amorphous materials have been used to make magnetic thin films because of their advantageous properties, particularly with regard to magnetic properties. These amorphous materials usually have naturally occurring amorphous or nearly amorphous crystalline structures. Examples of naturally occurring amorphous materials used in thin film magnetic heads includes CoZr, CoZrRh, and CoZrNb. These essentially amorphous materials are frequently used in thin film magnetic heads because of their high magnetic permeability and other favorable magnetic and electrical properties.
Ion-beam sputtering is a technology which is being increasingly used in the deposition of thin films, and particularly in the deposition of MREs for MR head magnetic storage devices. Ion-beam sputtering deposition techniques employ collimated beams of nearly monoenergetic ions which are directed and focused onto a target up to 60 cm (24 inches) away from the source of ion generation. The large separation distance between the target and the ion or plasma generation region allows ion-beam sputtering to be conducted at significantly lower pressures than other standard sputtering techniques such as rf-diode sputtering techniques. The lower pressures translate to fewer collisions between ions in the ion-beam and gas molecules before the ions collide with the target. This results in higher energy films. The reflection of ions and neutrals from the target also helps increase energy levels of the thin films fabricated using ion-beam sputtering techniques. Consequently, ion-beam sputtered thin films exhibit higher densities, improved corrosion resistance, reduced impurity levels and altered stresses in comparison to films sputtered under standard techniques such as rf-diode sputtering.
Ion-beam sputtering has been used in various thin film applications such as optical coatings, fabrication of magneto-optic media and fabrication of MR heads. Ion-beam sputtered MREs have shown higher outputs and greater corrosion resistance than rf-diode sputtered MREs.
Ion-beam techniques have been used to deposit a number of different thin film materials. For example, high permeability amorphous materials such as CoZr, CoZrRh and CoZrNb have been successfully deposited by ion-beam sputtering techniques. Additionally, ion-beam sputtering of permalloy, or NixFe1xe2x88x92x, has been used to obtain permalloy films with improved characteristics. Several articles have been written on the properties of ion-beam sputtered permalloy films.
A first article, by Jerry Lo et al., is entitled xe2x80x9cMagnetic and Structural Properties of High Rate Dual Ion-Beam Sputtered NiFe Filmsxe2x80x9d, Journal of Applied Physics, Vol. 61, No. 8, Apr. 15, 1987. In this article, the authors noted that by varying the target angle relative to the substrate surface, the magnetic properties of the Nixe2x80x94Fe films can be altered. The authors also found that no significant changes in magnetic and electrical properties were observed in films deposited with beam voltages between 200 and 2,000 V (beam energies between 200 and 2,000 electron-volts). This article also discussed the results of adding nitrogen to the sputtering process to reduce the x-ray diffraction  less than 111 greater than  peak. Ultimately, the authors concluded that, in the case of sputtering without the addition of nitrogen, the x-ray diffraction  less than 111 greater than  peak intensity remained relatively constant for diffraction angles of less than 45xc2x0, and that this implies that the Nixe2x80x94Fe films with diffraction angles of less than 45xc2x0 have similar  less than 111 greater than  textures.
A second article, by Christopher V. Jahnes et al., is entitled xe2x80x9cIon Beam Sputter Deposited Permalloy Thin Filmsxe2x80x9d, IEEE Transactions on Magnetics, Vol. 28, No. 4, July 1992. In this article, the authors describe the ion-beam sputtering procedures used in their research and discuss the properties of the resulting ion-beam sputter deposited permalloy films. The authors of that paper noted that, under certain conditions, ion-beam sputtering could be used to deposit permalloy films with characteristics suitable for use in thin film heads. In this article, the authors made a number of observations concerning ion-beam sputtered permalloy films. One important observation was that there is little change in the magnetic properties of ion-beam deposited films as a function of the film deposition rate which is dependent upon the energy level of the ion beam.
A third article, by G. C. Chi et al. is entitled xe2x80x9cThe magnetoresistivity, structure, and magnetic anisotropy of RF sputtered and E-beam evaporated NiFe filmsxe2x80x9d, Journal of Applied Physics, Vol. 52, No. 3, March 1981. In this article, the authors describe the differing structural and magnetic properties of NiFe films formed by RF sputtering and E-beam evaporation. The use of permalloy thin films as bubble detectors is mentioned.
A fourth article, by M. Takahashi et al. is entitled xe2x80x9cFabrication and Magnetic Properties of Thin Films Sputtered on the Substrate Excited by SAWxe2x80x9d, IEEE Translation Journal on Magnetics in Japan, Vol. 6, No. 2, February 1991. In this article, the authors describe the deposition of NiFe films by d.c. magnetron sputtering onto substrates excited by surface acoustic waves. The author found that the physical structure of the film could be made to change dramatically as a function of the excitation amplitude of the surface acoustic waves and that these structural changes altered the magnetic properties of the film.
As recording density requirements continue to increase, magnetic thin films with improved magnetic and electrical properties must be found in order to manufacture MR heads capable of meeting these increasing density requirements. Use of materials such as permalloy films and/or naturally occurring amorphous films must be further developed to achieve higher recording capabilities.
The present invention is based upon the recognition that a thin magnetic film with the desirable magnetic and electrical properties of permalloy films and with increased digital and analog output amplitudes provides an important tool in the design of magnetic storage and recording systems capable of meeting the high density requirements needed for the future. An amorphous or substantially amorphous permalloy film with magnetic and electrical properties similar to magnetic and electrical properties of nonamorphous permalloy films, but with improved output amplitude and noise characteristics, provides a magnetic material which can be used to achieve the desired increased recording densities.
The present invention is a permalloy film with an amorphous or substantially amorphous crystalline film structure. The permalloy film, which has an atomic composition comprising a combination of nickel and iron, is substantially amorphous in the face centered cubic  less than 111 greater than  plane, with the face centered cubic  less than 111 greater than  plane lying substantially parallel to the surface of a substrate. In preferred embodiments of the present invention. the substantially amorphous permalloy film has a composition which includes between 30 and 86 percent nickel.
In some preferred embodiments of the present invention, the substantially amorphous permalloy film is formed by ion-beam sputtering. The ion-beam sputtering is, in preferred embodiments, conducted with ion-beam energies below 500 electron-volts. In at least one preferred embodiment, the substantially amorphous permalloy film is formed by ion-beam sputtering with ion-beam energies of approximately 300 electron-volts. In another preferred embodiment, the substantially amorphous permalloy film is formed by ion-beam sputtering with an angle of incidence between the ion-beam and a permalloy target of approximately 30xc2x0.
In some preferred embodiments, the substantially amorphous permalloy film of the present invention is used as a magneto-resistive element in a magneto-resistive head. In these preferred embodiments, magneto-resistive elements comprised of the amorphous permalloy films exhibit improved output amplitude and noise characteristics.

Amorphous permalloy films and method of preparing the same


A weight-activated tying shoe wherein user who, upon sliding his foot inside the shoe, will depress a movable inner sole. This activates a side mechanism composed of a winch with a cable system used to close the tongue of the shoe towards the user's foot, thus lacing the shoe. The user simply uses his weight to activate the mechanism. Using his other foot, the user can move a pedal to release the mechanism's tension. Most of the mechanical components are located on both sides of the shoe body.

1. Field of the Invention
The invention relates generally to footwear, but more particularly to a weight-activated system intended to tie shoes, boots and snow shoes.
2. Prior Art
Lacing shoes can be difficult or impossible for some people, and several inventors have tried over the years to simplify the matter.
U.S. Pat. No. 11,078,986 by the present inventor shows a self tying shoe on which the lacing device is activated by the weight of the user. The weight is transmitted to a mechanism located within the sole, underneath the foot. The large number of moving parts makes the mechanism vulnerable to breakage. In addition, the underneath location of the mechanism causes some discomfort to the foot. For these reasons, this patent has been abandoned.
U.S. Pat. No. 4,741,115 shows a ski boot with an operating assembly for closing and adjustment, and comprises a power source supported by the ski boot which operates a driving gearwheel which is selectively engageable with driven gearwheels for the winding of cables of closing and/or adjustment devices of the boot.
U.S. Pat. No. 5,205,055 shows a shoe member including a plurality of securement webs directed about a lacing gap within the shoe upper, wherein the webs are each mounted slidably within associated cavities, with tether lines mounted to the webs operative above a crank pulley, with the crank pulley in operative engagement with a slidable actuator rod to effect projection of the securement webs forcibly within each respective cavity, wherein a gas cylinder is operative to effect rotation of the crank pulley by use of an associated slide rod within a guide cylinder to effect winding of each associated tether line relative to each associated securement web.
U.S. Pat. No. 5,335,401 shows a device for quickly tightening shoelaces on a shoe and for locking the tightened laces without the need for tying a bow or other knot. The device includes a body unit with a slotted opening formed with a chamfered edge along one ide of the slot. A rotatable shaft which includes a set of chamfered ridges rolls laterally across the width of the slot. A shoelace introduced through the slot becomes pinched between the chamfered edge of the slotted opening and the chamfered ridges of the shaft. The shaft is spring biased to automatically lock the laces in place upon being tightened to the desired tension. A quick release lever retracts the shaft to unpinch the lace.
U.S. Pat. No. 5,511,325 shows a shoe having a central rotary closure arranged on the heel of the upper in the area above the location at which the heel bone is received and having at least one tightening element which has a tightening section running from the central rotary closure towards each side of the shoe. The tightening sections are coupled by a coupling element with at least one strap which runs from each tightening section or coupling element over the instep and/or by the arch to the other tightening section or coupling element.
U.S. Pat. No. 5,600,874 shows a central closing device for shoes with a rotationally supported cord disc for at least one cord-type tensioning member for closing the shoe in such a way that the number of rotations of the cord disc is limited without any increase in the space required. Both the cord disc and a stationary member each have mutually-cooperating tooth profiles having the same tooth pitch but of different diameters. Located in the intermediate space created due to the different diameters of the tooth profiles is an idling pinion of the same pitch, which meshes with the two tooth profiles. At least one stop is provided to limit the travel of the idling pinion.
U.S. Pat. No. 5,718,021 shows a device for tying a shoelace on a shoe. The device includes a base and a cover hingedly mounted on the base so as to be pivotable between an open position and a closed position. The base includes a top surface, a bottom surface and first and second holes which are sized and shaped so that the shoelace can be inserted therethrough. The cover includes a top surface, a bottom surface and first and second pins which are aligned so as to project into the first and second holes, respectively, when the cover is in the closed position. The cover also includes a locking tab which engages with a tip on the base to releasably lock the cover in the closed position.
U.S. Pat. No. 5,839,210 shows a shoe incorporating adjustable straps that are positioned to tighten the shoe casing around a wearer's instep. A retractor mechanism incorporates elastic members. The elastic members are charged when the wearer loosens the shoe by pulling on the straps. The stored energy is released when a catch is disengaged and releases the elastic members to tighten and cinch the shoe on the wearer's foot.
U.S. Pat. No. 6,202,953 shows a footwear lacing system that includes a lace attached to a tightening mechanism. The lace is threaded through a series of opposing guide members positioned along the top of the foot and ankle portions of the footwear. The lace and guide preferably have low friction surfaces to facilitate sliding of the lace through the guide members so that the lace evenly distributes tension across the footwear member. The tightening mechanism allows incremental adjustment of the tension of the lace. A release mechanism allows a user to quickly loosen the lace.
U.S. Pat. No. 6,467,194 shows an automated tightening shoe with crisscrossed laces and a tightening mechanism which operates in one direction to cause automatic tightening of the crisscrossed laces to tighten the shoe about a wearer's foot, and which can be released easily so that the shoe can be removed from the wearer's foot.
Some inventions involve a manual tightening mechanism which is integrated into the outsole area while others use retractable heels latched on the shoe. Other systems uses a central closing device that requires manual winding. All these inventions need to be operated by hand. Another system involves the use of pneumatic means.


A camera configuration for a machine vision vehicle wheel alignment system which does not dispose all of the cameras on a single rigid structure, such that cameras disposed to view the left side of a vehicle are movable independently of the cameras disposed to view the right side of the vehicle, while maintaining a common reference coordinate system for determining vehicle wheel alignment angles.

The present invention relates to machine vision vehicle wheel alignment systems configured to measure the locations and orientation of the vehicle wheels in a three dimensional coordinate system, and more particularly, to configurations of machine vision cameras and optical targets disposed about a vehicle undergoing an alignment inspection.
Machine vision vehicle wheel alignment systems have been in use by the vehicle service industry for several years. A typical machine vision vehicle wheel alignment system, such as the Series 811 wheel alignment system, configured with the DSP600 sensors manufactured by Hunter Engineering Co. of Bridgeton, Mo. consists of a console unit, cameras, and optical targets. The console unit contains a computer configured with image processing and vehicle wheel alignment software applications, and incorporates various operator interfaces, including a keyboard, a mouse, a printer, and a display device. The cameras are coupled to the computer, and the optical targets are disposed in the field of view of the cameras, typically mounted to the wheels of a vehicle undergoing an alignment inspection.
Commonly, to view the left and right sides of a vehicle, one or more cameras are disposed on opposite sides of the vehicle, each having a field of view encompassing one or more wheels of the vehicle. In alternative configurations, two cameras are provided on each side of the vehicle, each having a field of view encompassing a single vehicle wheel, i.e. a left front, left rear, right front, and right rear wheel, respectively. To facilitate vehicle wheel alignment, optical targets are mounted on the vehicle wheels, and observed by the cameras. The optical targets preferably have predetermined features which are identified in images obtained by the cameras, and which facilitate a determination of the position and orientation of the optical targets. The image processing may take place in the camera modules, in an interface computer, or in the console computer. Once the position and orientation of each optical target is determined, the position and orientation of the associated vehicle wheel can be determined, and correspondingly, the various vehicle wheel alignment angle measurements may be either determined or calculated. These angles typically include camber, caster, and toe angles for each vehicle wheel, the vehicle centerline, and the vehicle rear thrust line.
With conventional machine vision vehicle wheel alignment systems, the positional relationship between each camera utilized in the system is fixed and known, permitting the computer to transform coordinates identified in one camera field of view to corresponding coordinates in a second camera field of view, or to a common coordinate reference system. To establish and maintain the positional relationship between each camera, the cameras in a conventional vehicle wheel alignment system are typically mounted to a common rigid support structure, such as a cross member or frame. If movement of the cameras is required, the rigid support structure ensures that the camera to camera positional relationship is maintained.
For some applications and installations of machine vision vehicle wheel alignment systems, the utilization of a single rigid support structure which is sufficiently large so as to dispose cameras in operative positions to view both the left and right sides of a vehicle is impractical. For example, in drive-through vehicle service bays, a vehicle is typically driven into the bay from one side, and continues out the bay through the opposite side. This prohibits placement of fixed structures in front of the vehicle, unless such structures are suspended from the ceiling. If the ceiling is too high, too low, or not sufficiently stable, this becomes impractical. Correspondingly, in some service "pit" applications, the vehicle is driven onto supporting structures of a runway disposed with an open "pit" or service bay. In such applications, the "pit" or bay may extend around the front of the vehicle to the forward wall of the service area, preventing the placement of fixed or rigid mounting structures in front of the vehicle if there is insufficient clearance between the vehicle and the forward wall.
Prior art systems which utilize independent support structures for cameras displaced to view opposite sides of a vehicle are known. Typically, these systems rely upon calibration procedures carried out prior to measuring vehicle wheel alignment angles. The calibration procedures may utilize one or more cross-looking cameras and/or associated reference targets to determine a positional relationship between each of the camera support structures, which is stored for subsequent use. However, such systems inherently rely upon the assumption that once the positional relationship between the cameras or between the cameras and a corresponding optical target is calibrated, it does not change. Alternatively, the calibration procedures must be repeated after each change in position of the cameras, or change in position of a camera and a corresponding optical target, before vehicle wheel alignment measurements can be determined.
Accordingly, there is a need in the vehicle service industry for machine vision vehicle wheel alignment systems which do not require that all cameras be mounted to a single rigid structure, and that cameras disposed to view one side of a vehicle be movable independently of the cameras disposed to view the opposite side of the vehicle, while maintaining, in real-time, a common reference coordinate system for determining vehicle wheel alignment angles without the need to repeatedly recalculate and store positional calibration data.

Common reference target machine vision wheel alignment system


A high speed, luminescence detection arrangement for sequentially measuring the luminescence emitted from a plurality of luminescence sources under test. A tray holder contains a plurality of cup-like sample wells, from which the luminescent radiation is emitted, and each of the cup-like sample wells is sequentially positioned in a predetermined location to allow the detection and measurement of the intensity of the luminescence emitted therefrom. Display means are provided to provide a detectible display, having a magnitude proportional to the intensity of the luminescence detected. Fluid dispensing means are operatively interconnected to allow injection of one or more fluids into each of the cup-like sample wells at a predetermined time before measurement of the luminescence emitted therefrom.

1. Field of the Invention
This invention relates to the luminesence detection and measurement art, and, more particularly, to a high speed luminescence detection arrangement for sequentially measuring the luminescence from a plurality of luminescence emitting samples.
2. Description of the Prior Art
As a method of precise analysis in both clinical and research laboratories, Luminescence Immunoassay (LIA) offers extraordinary potential. LIA combines the specificity of immunoassay and the sensitivity of luminescent light detection. Moreover, applications are almost limitless in that all that is needed is a procedure to link a luminescence reactant, such as isoluminol or peroxidase, to the analyte or its antibody availability of antibody to the analyte; and an instrument to measure the luminescent light emitted.
Both bioluminescent (BL) and chemiluminescent (CL) reactions can be utilized in these assays. Bioluminescent reactions are enzymatically mediated by bacterial or firefly luciferase, and involve oxidation of a substrate (usually luciferin) to form products which include light. Luciferase-bound analytes or ATP can be quantitated by correlating the amount of light produced to concentrations of standards. Detection limits of 10.sup.-16 mol ATP, 10.sup.-18 mol TNT, and 10.sup.-17 mol DNP are reported.
Chemiluminescent reactions involve a similar light production, commonly by oxidation of a phthalhydrazide derivative, such as luminol, in the presence of hydrogen peroxide and peroxidase. With naphthalhydrazide and phthalhydrazide derivatives as chemiluminescent labels, detection limits in the range of 10.sup.-16 mol are reported. Analytes include digoxin, thyroxine, IgG, cortisol, insulin, progesterone, and alpha-fetoprotein.
While there have been many procedures offering the specificity inherent to antibody binding, until the development of LIA, radioactive labelling (RIA) was the method of choice due to its sensitivity. LIA has all of the advantages of RIA, including comparable or better sensitivity. In addition, it features low reagent volumes (hence low cost), and nontoxic, stable reagents. Luminescence reagents offer a shelf life of about 2 years as compared with .sup.125 I, a common RIA label, which has an effective shelf life of about thirty (30) days.
The clinical chemist is involved in measuring a variety of substances by many different analytical techniques. Although different, these techniques share the common principle of an interface between chemistry and physics. The most commonly used such interface in clinical chemistry is absorptiometry, both at visible and ultraviolet wavelengths, but emission flame photometry and radioactivity are also commonly used.
Analyses based on the measurement of emitted light, such as luminescent light, offer several advantages over conventional techniques: high sensitivity, wide linear range. low cost per test, and relatively simple and inexpensive equipment.
Luminescence detection has application in several areas of clinical analysis. It has a role as a replacement for conventional colormetric or spectrophotometric indicator reactions in assays for substrates of oxidases and dehydrogenases. In this type of assay the sensitivity of the luminescence indicator reaction may be used either to quantitate substrates not easily measured by conventional techniques (e.g., prostaglandins and vitamins) or to reduce the quantities of specimen and reagent required in the initial enzymatic step, thus reducing the cost of the assay. Another application of luminescence is the utilization of luminescent molecules as replacements for radioactive labels in immunoassay, as noted above.
An important feature of the luminescence as an analytical technique is that its usefulness is not confined to clinical chemistry. Further, luminescence detection has applications in roles in other pathology disciplines, e.g., hematology, immunology, bacteriology, and pharmacology.
Chemiluminescence may be simply defined as the chemical production of light. In the literature it is often confused with fluorescence. The difference between these two processes is the source of energy that is producing molecules in an excited state. In chemiluminescence, this is the energy of a chemical reaction, and the decay from the excited state back to the ground state is accompanied by emission of light (luminescence). In contrast, incident radiation is the source of the energy that, in fluorescence, promotes molecules to an excited state. Analytically, the types of luminescence that have engendered the most interest are chemiluminescence and bioluminescence. The latter is the name given to a special form of chemiluminescence found in biological systems, in which a catalytic protein increases the efficiency of the luminescent reaction. Indeed, in certain cases the reaction is impossible without a protein component.
Of the several advantages of luminescent methods over their conventional counterparts, their extreme sensitivity is the most important. For example, as compared with spectrophotometry, the BL assay of NADH is estimated to be some 25,000-fold more sensitive, and BL assays for glucose and alcohol are, respectively, 55- and 10-fold more sensitive than conventional assays. The minimal detectable concentration for an assay ultimately depends on how sensitively light can be detected, and on the quantum efficiency of the reaction. Generally BL reactions are much more efficient than CL reactions; typical quantum efficiencies are in the ranges 0.1-0-8 and 0.01-0.05, respectively.
Since CL is an emission process (as opposed to absorption), response is usually linearly proportional to concentration from the minimal detectable concentration up to the point where it is no longer possible to maintain an excess of other reactants relative to the analyte. In the case of ATP assay by the firefly reaction, response is linear over six orders of magnitude.
The speed of analysis largely depends on the type of luminescent reaction. In some instances a rapid flash is obtained (1 s), the peak height of which may be related to analyte concentration; in other cases a more protracted glow occurs when a time course lasting several minutes. In the latter case, the integral or partial integral of the light-time curve has been used as a measure of analyte concentration because it is much less sensitive to mixing efficiency, but this drastically reduces the through-put and speed of analysis.
The major cost benefit of luminescent assays arises from their extreme sensitivity, which allows assays to be performed with much less reagents, hence reducing the cost per test. For example, luminescence offers a means of reducing the cost of cholesterol assays involving cholesterol oxidase (EC 220.127.116.11), because the sensitivity of CL detection of peroxide allows the initial peroxide-producing reaction involving cholesterol oxidase to be scaled down.
Specificity is conferred on BL and CL by using the luminescence as an indicator reaction coupled to intermediates (such as ATP, MADH, and H.sub.2 O.sub.2) produced enzymatically. Generally, BL reactions are specific because they are enzymic processes, but CL reactions are nonspecific. Luminol, for example, will undergo a CL reaction with various oxidants (oxygen, peroxide, superoxide, iodine) and its reactions are subject to interferences by reducing agents such as uric acid.
In practical applications of the principles of bioluminescence and chemiluminescence as above described, it is necessary to provide a detection and measuring arrangement for detecting and measuring the luminescence emitted from the sample under test. Further, the arrangement should include a display for displaying the signal indicative of the intensity of the luminescence emitted. One prior art device, utilized for such luminescence detection measuring applications, required that each separate sample under test be separately placed into the device. Reagents necessary to achieve luminescence with the sample under test could be added prior to insertion of the sample into the device or after insertion. The luminescence from the one sample was then detected and measured, and a display indicative of the amount of luminescence was provided. The sample was then removed and another sample could then be installed. Such sampling on a one-at-a-time basis was time consuming, and did not lend itself to applications requiring high speed, rapid, determination of the luminescence emitted from a plurality of samples.
Accordingly, there has long been a need for a luminescence detection measuring arrangement in which a plurality of samples under test may be rapidly subject to measurement of the luminescence emitted therefrom and a display, indicative of the intensity of the luminescence from each separate sample under test be provided.


The invention relates to a method and apparatus for the handling of individual flat articles coming out of a production machine (3). The articles may be particularly letter envelopes, which are assembled and, if needed further processed and packaged. The core of the invention resides in that initially a plurality of flat articles or letter envelopes (2, 2a) are lifted as partial stacks (8, 8a) and then are deposited at another location, and in that the partial stacks, during lifting and/or depositing (rearranging), are moved in such a way that the flat articles or letter envelopes (2, 2a) are standing, following the deposition, on the same side or edge (b) as originally or on another side or edge (a).

The invention relates to a method and apparatus for handling and more particularly packaging flat articles such as stationery envelopes.
Stationery envelopes of paper, that is to say both letter envelopes and also mailing bags, are as a rule produced of single-piece, multi-folded cutouts. It is a known practice to connect together neighboring edges of the folded cutouts with the aid of folded over adhesive flaps. At the openings for filling, the closing flaps which lie flat, are kept in the unbonded condition. After manufacture in a production machine the stationery envelopes are packed in stacks of for instance 500 or 1000 pieces in cartons. In the area of the closing flaps of each stationery envelope in a stack only two paper plies rest on top of each other, whereas in the area of the adhesively bonded side edges three paper plies are resting on top of each other. Thus, one and the same stationery envelope has in the empty state at different locations differences in thickness which amount to a third of the maximum thickness. A stack with many stationery envelopes is for this reason substantially thicker in the area of the bonded flaps than adjacent to edges which are merely folded. In order to compensate for this different thickness of the letter envelopes it is a known practice to manually pack the envelopes in small stacks, which are offset by 180xc2x0, directly in shipping cartons.
Furthermore, the European Patent Publication EP 0 506 606 B1 discloses a method and a device for packaging stationery envelopes in boxes, wherein the stationery envelopes coming from a production machine as an upright endless stack are first divided up into partial stacks and then pushed off the conveyor belt into an auxiliary device while maintaining their position. The auxiliary device holds the partial stack pushed off the conveyor belt until it is accepted by a movable entraining carrier, which deposits the stack in a movably arranged collecting basket, which is at least alternatingly able to be turned about a basket axis which is perpendicular to the stack. In this collecting basket the partial stacks in different positions are then first collected and then jointly removed from it, then pressed together and pushed into a box held ready.
This method and the respective device are expensive and complicated. The device comprises a plurality of different components, which are not only expensive to produce but are also problematical in operation and liable to failure. A particular problem is the ever recurring need for resetting to different stationery envelope formats.
The invention aims at providing a simple, reliable, low-cost method for a positionally accurate turning over of flat articles and more particularly stationery envelopes. The method shall be easily adaptable to different formats. The invention also aims at providing a suitable device for these purposes with a compact construction for the handling of articles or stationery envelopes coming from a production machine. They can then be further processed or preferably put in stacks and packaged. At least in the case of stationery envelopes the articles will have the same or a different thickness of their material at the same positions.
In order to achieve this object the invention provides, that first a plurality of flat articles or stationery envelopes are lifted up as partial stacks and then deposited at another location and that the partial stacks on raising and/or lowering (rearranging) are so moved that the articles or stationery envelopes after depositing stand on the same side or edge as originally or on another side or edge.
In accordance with the invention the stationery envelopes are no longer first collected in groups of partial stacks in a collecting basket serving as an intermediate storage, with, respectively, different alignments and then directly transferred to a shipping carton. Rather, the articles are placed immediately after the production machine in groups of partial stacks selectively on any desired edge or, respectively, selectively on one of their margins. Stacks of any desired size may be then formed from the partial stacks, for example for packing and after reaching the intended size may for example be transferred to a packing station.
Instead of stationery envelopes it is however also possible for hygienic articles and other flat articles, in the case of which there may be similar problems, to be processed using the intermediate steps in accordance with the invention and then further processed and/or packed in any desired fashion. This possibility-covers cases in which the articles or, respectively, stationery envelopes are not made ready for a boxing device but also for a bundling device, where they may be provided with a band and held together, whereupon they are either packaged as a small partial stack in cellophane or boxed as a larger stack.
For lifting and lowering the partial stacks a turning station is employed in accordance with the invention, which comprises at least one movable carrier, which may be a movable arm. At the free end of this arm or carrier at least one also movable gripper is arranged, which is capable of gripping a partial stack and after the rearrangement releasing it again.
As a further development of the invention it is possible for the gripper to be movable about a gripper axis parallel to a pivot or rotation axis of the carrier and/or about a gripper axis perpendicular thereto, whereby it is possible to satisfy any conceivable requirements.

Method and device in particular for packaging flat objects


The sulfur content of liquid cracking products, especially the cracked gasoline, of a catalytic cracking process is reduced by the use of a catalyst having a product sulfur reduction component containing a metal component in an oxidation state greater than zero, wherein the average oxidation state of the metal component is increased by an oxidation step following conventional catalyst regeneration. The catalyst is normally a molecular sieve such as a zeolite Y, REY, USY, REUSY, Beta or ZSM-5. The metal component is normally a metal of Groups 5, 7, 8, 9, 12 or 13 of the periodic table, preferably vanadium or zinc. The sulfur reduction component may be a separate particle additive or part of an integrated cracking/sulfur reduction catalyst. A system for increasing the oxidation state of the metal component of a Gasoline Sulfur Reduction additive is also provided.

This invention relates to the reduction of sulfur in gasoline and other petroleum products produced by the catalytic cracking process. In particular, the invention relates to an improved method which employs catalytic compositions for reducing product sulfur content.
Catalytic cracking is a petroleum refining process which is applied commercially on a very large scale, especially in the United States where the majority of the refinery gasoline blending pool is produced by catalytic cracking, with almost all of this coming from the fluid catalytic cracking (FCC) process. In the catalytic cracking process, heavy hydrocarbon fractions are converted into lighter products by reactions taking place at elevated temperature in the presence of a catalyst, with the majority of the conversion or cracking occurring in the vapor phase. The feedstock is converted into gasoline, distillate and other liquid cracking products as well as lighter gaseous cracking products of four or less carbon atoms per molecule. The gas partly consists of olefins and partly of saturated hydrocarbons.
During the cracking reactions some heavy material, known as coke, is deposited onto the catalyst. This reduces its catalytic activity and regeneration is desired. After removal of occluded hydrocarbons from the spent cracking catalyst, regeneration is accomplished by burning off the coke to restore the catalyst activity. The three characteristic steps of a typical catalytic cracking process can be identified as follows: a cracking step in which the hydrocarbons are converted into lighter products, a stripping step to remove hydrocarbons adsorbed on the catalyst and a regeneration step to burn off coke from the catalyst. The regenerated catalyst is then reused in the cracking step.
Catalytic cracking feedstocks normally contain sulfur in the form of organic sulfur compounds such as mercaptans, sulfides and thiophenes. The products of the cracking process correspondingly tend to contain sulfur impurities even though about half of the sulfur is converted to hydrogen sulfide during the cracking process, mainly by catalytic decomposition of non-thiophenic sulfur compounds. Although the amount and type of sulfur in the cracking products are influenced by the feed, catalyst type, additives present, conversion and other operating conditions, a significant portion of the sulfur generally remains in the product pool. With increasing environmental regulation being applied to petroleum products, for example in the Reformulated Gasoline (RFG) regulations, the allowable sulfur content of the products has generally been decreased in response to concerns about the emissions of sulfur oxides and other sulfur compounds into the air following combustion processes.
One approach has been to remove the sulfur from the FCC feed by hydrotreating before cracking is initiated. While highly effective, this approach tends to be expensive in terms of the capital cost of the equipment as well as operationally since hydrogen consumption is high. Another approach has been to remove the sulfur from the cracked products by hydrotreating. Again, while effective, this solution has the drawback that valuable product octane may be lost when the high octane olefins are saturated.
From an economic point of view, it would be desirable to achieve sulfur removal in the cracking process itself since this would effectively desulfurize the major component of the gasoline blending pool without additional treatment. Various catalytic materials have been developed for the removal of sulfur during the FCC process cycle but, so far, most developments have centered on the removal of sulfur from the regenerator stack gases. An early approach developed by Chevron used alumina compounds as additives to the inventory of cracking catalyst to adsorb sulfur oxides in the FCC regenerator; the adsorbed sulfur compounds which entered the process in the feed were released as hydrogen sulfide during the cracking portion of the cycle and passed to the product recovery section of the unit where they were removed. See Krishna et al, Additives Improve FCC Process, Hydrocarbon Processing, November 1991, pages 59-66. The sulfur is removed from the stack gases from the regenerator but product sulfur levels are not greatly affected, if at all.
An alternative technology for the removal of sulfur oxides from regenerator removal is based on the use of magnesium-aluminum spinels as additives to the circulating catalyst inventory in the FCCU. Under the designation DESOX(trademark) used for the additives in this process, the technology has achieved a notable commercial success. Exemplary patents on this type of sulfur removal additive include U.S. Pat. Nos. 4,963,520; 4,957,892; 4,957,718; 4,790,982 and others. Again, however, product sulfur levels are not greatly reduced.
A catalyst additive for the reduction of sulfur levels in the liquid cracking products is proposed by Wormsbecher and Kim in U.S. Pat. Nos. 5,376,608 and 5,525,210, using a cracking catalyst additive of an alumina-supported Lewis acid for the production of reduced-sulfur gasoline but this system has not achieved significant commercial success. The need for an effective additive for reducing the sulfur content of liquid catalytic cracking products has therefore persisted.
In application Ser. No. 09/144,607, filed Aug. 31, 1998, catalytic materials are described for use in the catalytic cracking process which are capable of reducing the sulfur content of the liquid products of the cracking process. These sulfur reduction catalysts comprise, in addition to a porous molecular sieve component, a metal in an oxidation state above zero within the interior of the pore structure of the sieve. The molecular sieve is in most cases a zeolite and it may be a zeolite having characteristics consistent with the large pore zeolites such as zeolite beta or zeolite USY or with the intermediate pore size zeolites such as ZSM-5. Non-zeolitic molecular sieves such as MeAPO-5, MeAPSO-5, as well as the mesoporous crystalline materials such as MCM-41 may be used as the sieve component of the catalyst. Metals such as vanadium, zinc, iron, cobalt, and gallium were found to be effective for the reduction of sulfur in the gasoline, with vanadium being the preferred metal. When used as a separate particle additive catalyst, these materials are used in combination with an active catalytic cracking catalyst (normally a faujasite such as zeolite Y and REY, especially as zeolite USY and REUSY) to process hydrocarbon feedstocks in the fluid catalytic cracking (FCC) unit to produce low-sulfur products. Since the sieve component of the sulfur reduction catalyst may itself be an active cracking catalyst, for instance, zeolite Y, REY, USY, and REUSY, it is also possible to use the sulfur reduction catalyst in the form of an integrated cracking/sulfur reduction catalyst system, for example, comprising USY as the active cracking component and the sieve component of the sulfur reduction system together with added matrix material such as silica, clay and the metal, e.g. vanadium, which provides the sulfur reduction functionality.
In application Ser. Nos. 09/221,539 and 09/221,540, both filed Dec. 28, 1998, sulfur reduction catalysts similar to the ones described in application Ser. No. 09/144,607 were described, however, the catalyst compositions in those applications also comprise at least one rare earth metal component (e.g. lanthanum) and a cerium component, respectively.
An improved catalytic cracking process has now been developed which is capable of improving the reduction in the sulfur content of the liquid products of the cracking process, including the gasoline and middle distillate cracking fractions. The present process employs sulfur reduction catalysts similar to the ones described in application Ser. Nos. 09/144,607, 09/221,539 and 09/221,540, each of which is incorporated herein by reference in their entirety, in that the cracking catalyst employed in the present invention contains a product sulfur reducing component containing a metal component in an oxidation state greater than zero, with preference being given to vanadium. Preferably, the sulfur reduction component will include a molecular sieve containing the metal component within the interior of the pore structure of the sieve. The improvement, according to the present invention includes a step of increasing the average oxidation state of the metal component after the catalyst has been regenerated. It has been found that by increasing the oxidation state of the metal component, there is an increase in the sulfur reduction activity of the catalyst.
The present invention may employ sulfur reduction catalysts which are in the form of a gasoline sulfur reduction (GSR) additive in combination with an active cracking catalyst in the cracking unit, that is, in combination with the conventional major component of the circulating cracking catalyst inventory which is usually a matrixed, zeolite containing catalyst based on a faujasite zeolite, usually zeolite Y, REY, USY and REUSY. Alternatively, the catalyst may be in the form of an integrated cracking/product sulfur reduction catalyst system.
The sulfur reduction component can comprise a porous molecular sieve which contains a metal in an oxidation state above zero within the interior of the pore structure of the sieve. The sulfur reduction component can also comprise a metal in an oxidation state above zero dispersed anywhere on the catalyst support structure, including porous oxide supports. The molecular sieve, when used, is in most cases a zeolite and it may be a zeolite having characteristics consistent with the large pore zeolites such as zeolite beta or zeolite USY or with the intermediate pore size zeolites such as ZSM-5. Non-zeolitic molecular sieves such as MeAPO-5, MeAPSO-5, as well as the mesoporous crystalline materials such as MCM-41 may be used as the sieve component of the catalyst. Metals such as vanadium, zinc, iron, cobalt, manganese and gallium are effective. If the selected sieve material has sufficient cracking activity, it may be used as the active catalytic cracking catalyst component (normally a faujasite such as zeolite Y) or, alternatively, it may be used in addition to the active cracking component, whether or not it has any cracking activity itself.
In one embodiment, at least a portion of the catalyst inventory having the product sulfur reducing component is exposed to oxidative treatment by contact with an oxygen containing gas, which treatment is in addition to the treatment employed in regenerating the cracking catalyst. Preferably, the additional oxidative treatment is carried out under conditions sufficient to substantially fully oxidize the metal component of the sulfur reducing component.
In another embodiment, in which the sulfur reducing component is in the form of a separate GSR additive to the active cracking catalyst, an oxidation device is used to separate the GSR additive from the regenerated cracking catalyst and to selectively oxidize the GSR additive, prior to returning both the oxidized GSR additive and the regenerated cracking catalyst to the catalytic cracking zone (e.g. the riser) of the FCC unit.
In accordance with the present invention, an improved catalytic cracking process is provided for reducing the sulfur content of the liquid products produced from a hydrocarbon feed containing organosulfur compounds. The present process employs a catalyst system having a sulfur reduction component containing a metal component in an oxidation state greater than zero. The sulfur reduction activity of the catalyst system is increased by increasing the oxidation state of the metal component prior to introducing the catalyst system into the catalytic cracking zone.
FCC Process
Apart from the process changes in accordance with the present invention, as discussed below, the manner of operating the process will generally be consistent with a conventional FCC process. Thus in an embodiment of the present invention, conventional FCC cracking catalysts may be employed, for example, zeolite based catalysts with a faujasite cracking component as described in the seminal review by Venuto and Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1 as well as in numerous other sources such as Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Publ. Co. Houston, 1995, ISBN 0-88415-290-1.
Generally, in a conventional fluid catalytic cracking process the heavy hydrocarbon feed containing the organosulfur compounds will be cracked to lighter products by contacting the feed in a cyclic catalyst recirculation cracking process with a circulating fluidizable catalytic cracking catalyst inventory consisting of particles having a size ranging from about 20 to about 100 microns. The significant steps in such a cyclic process are:
(i) the feed is catalytically cracked in a catalytic cracking zone, normally a riser cracking zone, operating at catalytic cracking conditions by contacting feed with a source of hot, regenerated cracking catalyst (hereinafter referred to as an equilibrium catalyst or xe2x80x9cE-Catxe2x80x9d) to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons;
(ii) the effluent is discharged and separated, normally in one or more cyclones, into a vapor phase rich in cracked product and a solids rich phase comprising the spent catalyst;
(iii) the vapor phase is removed as product and fractionated in the FCC main column and its associated side columns to form liquid cracking products including gasoline,
(iv) the spent catalyst is stripped, usually with steam, to remove occluded hydrocarbons from the catalyst, after which the stripped catalyst is oxidatively regenerated to produce E-Cat which is then recycled to the cracking zone for cracking further quantities of feed.
In addition to the conventional FCC process, discussed above, the present invention employs a catalyst having a sulfur reduction component containing a metal component in an oxidation state greater than zero and includes a step for increasing the average oxidation state of the metal component after the catalyst is regenerated, and prior to recycling the catalyst to the cracking zone.
In an embodiment of the present invention, the step for increasing the average oxidation state of the metal component comprises exposing at least a portion of the catalyst containing the sulfur reduction component to additional oxidative treatment by contacting the catalyst with an oxygen containing gas. The conditions for the additional oxidative treatment include an O2 partial pressure in the range of about 1 to 20 psia, preferably about 8 to 16 psia; a total system pressure of about 20 to 100 psia, preferably about 40 to 70 psia; a catalyst residence time of about 1 to 60 minutes, preferable about 1 to 10 minutes; and a temperature in the range from about 1100 to 1550xc2x0 F., preferably about 1200 to 1450xc2x0 F.
Preferably, the catalyst will be exposed to additional oxidative treatment under conditions sufficient to substantially fully oxidize the metal component, i.e. raise the oxidation state of the metal cation to its highest level.
FCC Cracking Catalyst
The present invention can employ a sulfur reduction component in the form of a separate particle additive (GSR additive) which is added to the main cracking catalyst (E-Cat) in the FCCU or, alternatively, may be a component of the cracking catalyst to provide an integrated cracking/sulfur reduction catalyst system. The cracking component of the catalyst which is conventionally present to effect the desired cracking reactions and the production of lower boiling cracking products, is normally based on a faujasite zeolite active cracking component, which is conventionally zeolite Y in one of its forms such as calcined rare-earth exchanged type Y zeolite (CREY), the preparation of which is disclosed in U.S. Pat. No. 3,402,996, ultrastable type Y zeolite (USY) as disclosed in U.S. Pat. No. 3,293,192, as well as various partially exchanged type Y zeolites as disclosed in U.S. Pat. Nos. 3,607,043 and 3,676,368. Cracking catalysts such as these are widely available in large quantities from various commercial suppliers. The active cracking component is routinely combined with a matrix material such as silica or alumina as well as a clay in order to provide the desired mechanical characteristics (attrition resistance etc.) as well as activity control for the very active zeolite component or components. The particle size of the cracking catalyst is typically in the range of about 10 to 100 microns for effective fluidization.
Sulfur Reduction Systemxe2x80x94Sieve Component
The sulfur reduction component will preferably comprise a porous molecular sieve which contains a metal in an oxidation state above zero within the interior of the pore structure of the sieve. The molecular sieve is in most cases a zeolite and it may be a zeolite having characteristics consistent with the large pore zeolites such as zeolite Y, preferably zeolite USY, or zeolite beta or with the intermediate pore size zeolites such as ZSM-5, with the former class being preferred.
The molecular sieve component of the present sulfur reduction catalysts may, as noted above, be a zeolite or a non-zeolitic molecular sieve. When used, zeolites may be selected from the large pore size zeolites or intermediate pore zeolites (see Shape Selective Catalysis in Industrial Applications, Chen et al, Marcel Dekker Inc., New York 1989, ISBN 0-8247-7856-1, for a discussion of zeolite classifications by pore size according to the basic scheme set out by Frilette et al in J. Catalysis 67, 218-222 (1981)). The small pore size zeolites such as zeolite A and erionite, besides having insufficient stability for use in the catalytic cracking process, will generally not be preferred because of their molecular size exclusion properties which will tend to exclude the components of the cracking feed as well as many components of the cracked products. The pore size of the sieve does not, however, appear to be critical since, as shown below, both medium and large pore size zeolites have been found to be effective, as have the mesoporous crystalline materials such as MCM-41.
Zeolites having properties consistent with the existence of a large pore (12 carbon ring) structure which may be used to make the present sulfur reduction catalysts include zeolites Y in its various forms such as Y, REY, CREY, USY, of which the last is preferred, as well as other zeolites such as zeolite L, zeolite beta, mordenite including de-aluminated mordenite, and zeolite ZSM-18. Generally, the large pore size zeolites are characterized by a pore structure with a ring opening of at least 0.7 nm and the medium or intermediate pore size zeolites will have a pore opening smaller than 0.7 nm but larger than about 0.56 nm. Suitable medium pore size zeolites which may be used include the pentasil zeolites such as ZSM-5, ZSM-22, ZSM-23, ZSM-35, ZSM-50, ZSM-57, MCM-22, MCM-49, MCM-56 all of which are known materials. Zeolites may be used with framework metal elements other than aluminum, for example, boron, gallium, iron, or chromium.
The use of zeolite USY is particularly desirable since this zeolite is typically used as the active cracking component of the cracking, catalyst and it is therefore possible to use the sulfur reduction catalyst in the form of an integrated cracking/sulfur reduction catalyst system. The USY zeolite used for the cracking component may also, to advantage, be used as the sieve component for a separate particle additive catalyst as it will continue to contribute to the cracking activity of the overall catalyst present in the unit. Stability is correlated with low unit cell size (UCS) with USY and, for optimum results, the UCS for the USY zeolite in the finished catalyst should be from about 2.420 to 2.458 nm, preferably about 2.420 to 2.445 nm, with the range of 2.435 to 2.440 nm being very suitable. After exposure to the repeated steaming of the FCC cycles, further reductions in UCS will take place to a final value which is normally within the range of about 2.420 to 2.430 nm.
In addition to the zeolites, other molecular sieves may be used although they may not be as favorable since it appears that some acidic activity (conventionally measured by the alpha value) is required for optimum performance. Experimental data indicate that alpha values in excess of about 10 (sieve without metal content) are suitable for adequate desulfurization activity, with alpha values in the range of 0.2 to 2,000 being normally suitable1. Alpha values from 0.2 to 300 represent the normal range of acidic activity for these materials when used as additives.
1 The alpha test is a convenient method of measuring the overall acidity, inclusive of both its internal and external acidity, of a solid material such as a molecular sieve. The test is described in U.S. Pat. No. 3,354,078; in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980). Alpha values reported in this specification are measured at a constant temperature of 538xc2x0 C.
Exemplary non-zeolitic sieve materials which may provide suitable support components for the metal component of the present sulfur reduction catalysts include silicates (such as the metallosilicates and titanosilicates) of varying silica-alumina ratios, metalloaluminates (such as germaniumaluminates), metallophosphates, aluminophosphates such as the silico- and metalloaluminophosphates referred to as metal integrated aluminophosphates (MeAPO and ELAPO), metal integrated silicoaluminophosphates (MeAPSO and ELAPSO), silicoaluminophosphates (SAPO), gallogermanates and combinations of these.
Another class of crystalline support materials which may be used is the group of mesoporous crystalline materials exemplified by the MCM-41 and MCM-48 materials. These mesoporous crystalline materials are described in U.S. Pat. Nos. 5,098,684; 5,102,643; and 5,198,203.
Amorphous and paracrystalline support materials are also contemplated, such as amorphous refractory inorganic oxides of Group 2, 4, 13 and 14 elements, for example, Al2O3, SiO2, ZrO2, TiO2, MgO and mixtures thereof, and paracrystalline materials such as the transitional aluminas.
Metal Components
The metal component contained in the sulfur reduction component of the catalysts useful in the present invention include those metals disclosed in application Ser. Nos. 09/144,607, 09/221,539 and 09/221,540, each of which is incorporated herein by reference. Although any metal cation which exhibits sulfur reduction activity is contemplated, the metal or metals should not exhibit significant hydrogenation activity, because of the concern for excessive coke and hydrogen production during the cracking process. For this reason, the noble metals such as platinum and palladium which possess strong hydrogenation-dehydrogenation functionality are not desirable. Base metals and combinations of base metals with strong hydrogenation functionality such as nickel, molybdenum, nickel-tungsten, cobalt-molybdenum and nickel-molybdenum are not desirable for the same reason. The preferred base metals are the metal values of Period 4 Groups 5, 7, 8, 9, 12 and 13 (IUPAC classification, previously Groups IIB, VB, VIIB and VIIIB) of the Periodic Table. Vanadium, zinc, iron, cobalt, manganese and gallium are effective with vanadium being the preferred metal component. Preferably, the base metal, e.g. vanadium, will be contained within the interior of the pore structure of the porous molecular sieve. It is believed that the location of the vanadium inside the pore structure of the sieve immobilizes the vanadium and prevents it from becoming vanadic acid species which can combine deleteriously with the sieve component; in any event, the present zeolite-based sulfur reduction catalysts containing vanadium as the metal component have undergone repeated cycling between reductive and oxidative/steaming conditions representative of the FCC cycle while retaining the characteristic zeolite structure, indicating a different environment for the metal.
Vanadium is particularly suitable for gasoline sulfur reduction when supported on zeolite USY. The yield structure of the V/USY sulfur reduction catalyst is particularly interesting. While other zeolites, after metals addition, demonstrate gasoline sulfur reduction, they tend to convert gasoline to C3 and C4 gas. Even though much of the converted C3xe2x95x90 and C4xe2x95x90 can be alkylated and re-blended back to the gasoline pool, the high C4xe2x88x92 wet gas yield may be a concern since many refineries are limited by their wet gas compressor capacity. The metal-containing USY has similar yield structure to current FCC catalysts; this advantage would allow the V/USY zeolite content in a catalyst blend to be adjusted to a target desulfurization level without limitation from FCC unit constraints. The vanadium on Y zeolite catalyst, with the zeolite represented by USY, is therefore a particularly favorable combination for gasoline sulfur reduction in FCC. The USY which has been found to give particularly good results is a USY with low unit cell size in the range from about 2.420 to 2.458 nm, preferably about 2.420 to 2.445 nm (following treatment) and a correspondingly low alpha value. Combinations of base metals such as vanadium/zinc as the primary sulfur reduction component may also be favorable in terms of overall sulfur reduction.
The amount of metal in the sulfur reduction component is normally from 0.1 to 10 weight percent, typically 0.15 to 5 weight percent, (as metal, relative to weight of sieve component) but amounts outside this range, for example, up to 10 weight percent may still be found to give some sulfur removal effect. When the sieve is matrixed, the amount of the primary sulfur reduction metal component expressed relative to the total weight of the catalyst composition will, for practical purposes of formulation, typically extend from 0.05 to 5, more typically from 0.05 to 3 weight percent of the entire catalyst. A second metal may be added to the sulfur reduction component, e.g. cerium, which is present within the pore structure of the molecular sieve, as described in application Ser. No. 09/221,540.
When the catalyst is being formulated as an integrated catalyst system, it is preferred to use the active cracking component of the catalyst as the sieve component of the sulfur reduction system, preferably zeolite USY, both for simplicity of manufacture but also for retention of controlled cracking properties. It is, however, possible to incorporate another active cracking sieve material such as zeolite ZSM-5 into an integrated catalyst system and such systems may be useful when the properties of the second active sieve material are desired, for instance, the properties of ZSM-5. The impregnation/exchange process should in both cases be carried out with a controlled amount of metal so that the requisite number of sites are left on the sieve to catalyze the cracking reactions which may be desired from the active cracking component or any secondary cracking components which are present, e.g. ZSM-5.
Use of Separate Additive as Sulfur Reduction Component
Preferably, the sulfur reduction catalyst will be as a separate particle additive (GSR additive) to the catalyst inventory. In its preferred form, with zeolite USY as the sieve component, the addition of the GSR additive to the total catalyst inventory of the unit will not result in significant reduction in overall cracking because of the cracking activity of the USY zeolite. The same is true when another active cracking material is used as the sieve component. When used in this way, the composition may be used in the form of the pure sieve crystal, pelleted (without matrix but with added metal components) to the correct size for FCC use. Normally, however, the metal-containing sieve will be matrixed in order to achieve adequate particle attrition resistance and to maintain satisfactory fluidization. Conventional cracking catalyst matrix materials such as alumina or silica-alumina, usually with added clay, will be suitable for this purpose. The amount of matrix relative to the sieve will normally be from 20:80 to 80:20 by weight. Conventional matrixing techniques may be used.
Use of a GSR additive permits the ratio of sulfur reduction and cracking catalyst components to be optimized according to the amount of sulfur in the feed and the desired degree of desulfurization; when used in this manner, it is typically used in an amount from about 1 to 50 weight percent of the entire catalyst inventory in the FCCU; in most cases the amount will be from about 5 to 25 weight percent, e.g. 5 to 15 weight percent. About 10 percent represents a norm for most practical purposes. The GSR additive remains active for sulfur removal for extended periods of time although very high sulfur feeds may result in loss of sulfur removal activity in shorter times.
Other catalytically active components may be present in the circulating inventory of catalytic material in addition to the cracking catalyst and the sulfur removal additive. Examples of such other materials include the octane enhancing catalysts based on zeolite ZSM-5, CO combustion promoters based on a supported noble metal such as platinum, stack gas desulfurization additives such as DESOX(trademark) (magnesium aluminum spinel), vanadium traps and bottom cracking additives, such as those described in Krishna, Sadeghbeigi, op cit. and Scherzer, Octane Enhancing Zeolitic FCC Catalysts, Marcel Dekker, New York, 1990, ISBN 0-8247-8399-9. These other components may be used in their conventional amounts.
The effect of the present GSR additives is to reduce the sulfur content of the liquid cracking products, especially the light and heavy gasoline fractions although reductions are also noted in the light cycle oil, making this more suitable for use as a diesel or home heating oil blend component. The sulfur removed by the use of the catalyst is converted to inorganic form and released as hydrogen sulfide which can be recovered in the normal way in the product recovery section of the FCCU in the same way as the hydrogen sulfide conventionally released in the cracking process. The increased load of hydrogen sulfide may impose additional sour gas/water treatment requirements but with the significant reductions in gasoline sulfur achieved, these are not likely to be considered limitative.
In one embodiment, the GSR additive particles are preferred to have a higher density or a larger average particle size than the E-Cat particles. This can be accomplished by using a heavier binder (e.g. heavier clay) for the GSR additive than for the E-Cat or by using a GSR additive with a larger average particle size (APS) than the E-Cat, for example, a GSR additive having an APS of about 100 xcexcm and a cracking catalyst having an APS of about 70 xcexcm.
The heavier or larger particles of the GSR additives will allow them to have a relatively longer residence time in the bottom of the regenerator where the O2 partial pressure is higher. This longer residence time can help the regenerator to burn the coke off the GSR additives and to selectively expose these additives to additional oxidative treatment than is typical for a regenerated catalyst. Preferably, the particle density and/or size can be optimized to increase the residence time in the bottom of the regenerator to fully oxidize the metal component of the additive.
In another embodiment, additional air or oxygen can be introduced at various points in a conventional FCC process to provide additional oxidative treatment for the GSR additives. For example, the air or oxygen can be introduced into the regenerator standpipe or the standpipe withdrawal cone to continue to oxidize the GSR additive and E-Cat. Additional air or oxygen can also be added to the second stage of a two-stage regenerator to increase the O2 partial pressure sufficiently to increase the average oxidation state of the metal component of the GSR additive.
In yet another embodiment, the process equipment from a conventional FCC process can be modified or new devices added, in conjunction with adding additional air or oxygen to the system. For example, the regenerator standpipe or standpipe cone can be modified to reduce catalyst fluxes or increase catalyst residence time, while subjecting the catalyst to additional oxidative treatment. In another example, the catalyst cooler can be placed after the regenerator and air or oxygen can be introduced into the catalyst cooler to continue to oxidize the regenerated catalyst before introducing the catalyst into the catalytic cracking zone.
A catalytic cracking process which is particularly well suited for employing a catalyst system which includes a GSR additive according to the improved process of the present invention utilizes a separate oxidizing device, illustrated in accompanying FIG. 1. It should be noted that the oxidizing device depicted in FIG. 1 is intended to be merely exemplary. Although the use of such a device is a preferred embodiment, the present invention can be practiced by any conventional fluidized catalytic cracking unit which is capable of increasing the average oxidation state of the metal component of the catalyst system prior to introduction into the catalytic cracking zone.
Referring now to FIG. 1, the separate oxidizing device 1 comprises a oxidation zone 2 and a freeboard zone 3. Depending on the regenerated FCC catalysts that flow into this vessel through the inlet tube 4 (e.g., the residue carbon, the V level etc.) and their required oxidation conditions (e.g., the catalyst flux and residence time, the air flow rate and its partial pressure, etc.) the size of device 1 can vary from about 5 to 80% of the size of the main regenerator, preferably about 5 to 20% of the size of the main regenerator. The height to diameter ratio of the device 1 can vary from about 1 to 20, preferably about 3 to 7.
The device 1 works in the following manner: the regenerated FCC catalyst blend containing about 0 to 50% of GSR additives, preferably about 0 to 30% of additives, with certain residue carbon on it flow into the device 1 from the bottom of the main regenerator through the catalyst inlet 4. The GSR additives will have a larger average particle size and/or have a higher density than the E-Cat particles. Preferably, the GSR additive particles will have an APS greater than 90 xcexcm and the E-Cat particles will have an APS less than 90 xcexcm. Optionally, a GSR additive rich stream can be separated from the regenerated FCC catalyst blend and only the GSR additive rich stream will be introduced into the device 1. The preheated air enters this device through an air distributor plate 5. In order to maintain the oxidization zone fluidized bed 2 in a suspended and viable state, the superficial gas velocity (SGV) of the air flow through the device generally exceeds the minimum flow rate required for fluidization which is typically from about 0.2 ft/s (0.61 m/s) to 0.5 ft/s (0.153 m/s). Preferably, a high SGV should be maintained at not less than about 1.0 ft/s (0.306 m/s). The high airflow will entrain most of the small E-Cat particles ( less than 90 xcexcm) back to the regenerator immediately through outlet 6. The un-used oxygen will be continually utilized to burn the coke in the regenerator. In addition, the high air flow rate will ensure that the partial pressure of oxygen in the oxidation zone 2 is high enough to burn all the coke off the catalyst and provide an oxidizing environment to completely oxidize the metal on the bigger size additive particles ( greater than 90 xcexcm). The SGV should preferably not exceed about 10.0 ft/s (3.0 m/s), more preferably not more than about 5.0 ft/s (1.5 m/s). The completely oxidized GSR additives rich catalyst 7 will flow back to the bottom of the standpipe of the regenerator and mix with the main stream of the regenerated catalyst 8 through the catalyst outlet tube 9. The flux of this catalyst stream 7 will be in the range of about 1 to 50% of the flux of the main regenerated catalyst stream 8; preferably around 10% of the main flux 8.

Method for reducing gasoline sulfur in fluid catalytic cracking


A web cleaner (20) is presented that removes debris that clings to the surface of a substrate in a printing process. The cleaner uses a number of idlers (26) holding a web (22) taut therebetween with the web driven at high speeds by a printing press (24). The cleaner utilizes a pair of counter rotating textured rollers (28) positioned between the idlers with one roller positioned on each side of the web in close proximity therewith and each roller rotates in an opposite direction to that of the webs flowpath. A air separating bar (36) is positioned at right angles to the web bordering each roller in adjacent relationship for directing the air into a plenum (44) that covers each roller and skiving bar. The plenum is used to collect the debris detached from the web surface by air currents formed by rotation of the rollers creating an air film on the web surface. The same air currents produce a positive air pressure within the plenum. A dust collector (50) is connected to each plenum for accumulating debris dislodged from the web surface.

The present invention relates to web cleaners in general and more specifically, to a treatment system that lifts debris from the surface of a web of substrate material without touching either of its upper and lower surfaces.
Previously, many types of web cleaners have been used to provide an effective means for removing unwanted particles from the surface of a web in the printing discipline. A number of approaches have been used with limited or little success. Bristles, in the form of a brush rotating at a speed of 600 to 800 rpm, have been employed to lightly brush the surface of the web. Compressed air has been somewhat successful, however it was found that almost 2 pounds per square inch of pressure was required, which required considerable energy and had other complications. The combination of a rotating brush and vacuum was considered to be a viable solution, however it was also complicated and required vacuum blowers at high volume and brushes that contacted the surface of the web.
A search of the prior art did not disclose any patents that possess the novelty of the instant invention, however the following U.S. patents are considered related:
Wieloch, et al. in U.S. Pat. No. 6,162,303 teaches a process for cleaning a web having surfaces on opposite sides of the web with a cleaner roller against a major surface in one direction while the transport of the web remains uninterrupted and rolling the contact cleaner roll against the major surface in an opposite direction while the transport of the web is uninterrupted.
U.S. Pat. No. 6,178,589 issued to Kaim is for a track assembly that permits a pair of cleaning devices to operate on either side of a paper web moving upward through the floor of a press. The track assembly facilitates mounting and rapid removal of web cleaning buffs from beneath a press.
Baum in U.S. Pat. No. 6,193,810 discloses a method of cleaning tissue webs in a in rewinder utilizing the Coanda effect with a thin layer of air that scrubs off dust and lint imbedded and entangled in the web surface while stabilizing the web in its travel.
Ziegelmuller, et al. in U.S. Pat. No. 6,195,527 teaches a web cleaning device with a nesting structure that supports a coil of web fabric. A lip member forms a part of the nesting structure and a pay out end of the coil is wrapped around the lip member with a take up spindle spaced from the coil.
U.S. Pat. No. 6,207,227 issued to Russo; et al. presents a cleaning sheet with tacky surface coating that cleans feed rollers
U.S. Pat. No. 6,259,882 of Lindblad, et al is for removing electrostatically charged particles from a surface of an image bearing belt.
In the printing discipline which includes lithographic offset printing, flexographic printing, gravure printing, letterpress printing and the like, blanket piling is a source of wasted time and lost production due to the necessity of frequent blanket washes. Lint, paper fibers and coating on the surface of the substrate can cause halftone plugging and so called xe2x80x9chickeysxe2x80x9d, which requires removal and washing of the blanket. Frequent blanket washes shorten the blanket""s life and place unnecessary wear and premature deterioration of the printing press.
In view of the above disclosure, it is the primary object of the invention to completely clean the surface of the web prior to entering a print unit, which considerably reduces blanket washing. It has been found that the invention can increase the number of impressions run before a blanket wash is required.
An important object of the invention is directed to condition high speed webs by penetrating the surface barrier of the web without actual contact. The invention produces an air flow that directs air currents in a turbulent washing film over the web surface, thus completely removing slitter dust, loose clay coating and other debris. The invention is designed to be completely functional with almost any substrate used in printing, without damage to its surface such as paper, mylar and plastic.
Another object of the invention is to apply the use of air currents that are produced by a roller with a textured surface. The roller creates a narrow, pressurized area immediately at an extremely close space existing between the roller and the web, which, due to such a limited sector develops immense energy to the web that dislodges debris and moves loose particles without touching the web. The roller may have any textured surface that will cause air movement above its surface, however it has been found by extensive testing that a roller similar in design to a jewelry polishing wheel which is constructed of soft cotton buffing material, has proven optimum. Once the contaminants are lifted from the surface of the web they may be easily directed to a separate device that receives and stores the debris. The roller works best when the roller""s surface speed is at least 20 percent greater than the surface speed of the web.
Still another object of the invention is that the rollers rotate in the opposite direction as the moving web this feature permits the air currents that surround the rotating roller to be easily directed into a plenum, which includes a air separating bar that separates the air containing particles that have been removed from the web from the roller and directs the airflow into the plenum and on into a dust collector under negative pressure.
Yet another object of the invention is that by having a clean web, print quality is enhanced and a consistent color is obtained. The conditioned web, as provided by the inventive web cleaner, reduces contamination in not only the ink train and dampers but also specifically the blankets of the printing equipment.
These and other objects and advantages of the present invention will become apparent from the subsequent detailed description of the preferred embodiment and the appended claims taken in conjunction with the accompanying drawings.