A liner hanger having a mechanical coupling between a liner hanger body and one or more cones is disclosed. The cones are coupled to the liner hanger body to resist axial and relative rotational movement without welding the cones to the hanger body, and without the need to use integral cones. In general, the mechanical coupling includes a hanger body or casing mandrel, a cone assembly journaled on the casing mandrel, at least one slot or groove in an outer wall of the casing mandrel, and at least one partially or fully annular slot on the inside surface of the cone assembly oriented to correspond with the groove(s) in the outer wall of the hanger body. At least one wire, or one or more bearings, is situated in the corresponding slot and the groove. The wire engages the flanks of the slot and groove sufficiently to resist axial or rotational movement of the cones relative to the hanger body.

This invention relates generally to setting liner hangers during well completion or maintenance operations. In particular, the invention is directed to a liner hanger in which the cones of the liner hanger are non-integral to the barrel and attached by mechanical means without welding.
Generally, in a producing well, casing (lengths of steel pipe joined together) runs from the surface to a specified depth in the wellbore. The casing generally has a large diameter. It is installed and cemented in place to seal off drilling and circulating fluids from the borehole and prevent commingling of well fluids, and to prevent the walls of the borehole from caving. The casing string is generally hung from a hanger on the surface.
A liner is a length of casing that is hung inside existing casing. Unlike the casing string, the liner generally does not extend to the surface, but is anchored, suspended, and supported by a liner hanger that is installed near the bottom of the casing in which the liner is suspended, or near the location where the liner string is desired to isolate problems such as from other zones such as lost circulation or high pressure. The liner also provides capital savings in reducing the cost of the steel pipe needed since it does not run to the top of the well.
A liner hanger holds the liner in place once the liner is in the desired location in the well, and carries the weight of the liner after it is hung off. Mechanical or hydraulic slips on the hanger hold the liner in place by gripping the inside wall of the casing in which the liner is suspended. Hangers may be set hydraulically by creating pressure in the hanger, activating hydraulic pistons that move the slips against the casing. During the running process the slips are retained in a retracted position. Once the liner is in the desired position, the slips are driven across the cones by the activation mechanism, which may be mechanical or hydraulic, thereby increasing the diameter of the slips and forcing the teeth on the outer surface into the casing. Liner hangers generally include one or more sets of cones and slips.
The cones are wedge-shaped sections on the liner hanger's outer wall. Generally in the past, the cones have been integral to the barrel of the liner hanger. For example, in a common type of prior art liner hanger the barrel is made of two piece construction, as shown in FIGS. 1A and 1B. A lower portion of the barrel is threaded onto an upper portion and acts as a hydraulic cylinder. The entire assembly contains a longitudinal throughbore that allows for the passage of fluids during the running process. The slips and cones are slotted to allow the passage of fluid in the annulus around the liner hanger during the running in/removal or cementing processes.
With the hydraulic version, when the liner hanger is in the desired position, the operator creates an increased pressure, generally by dropping a ball or dart into a ball seat or other receptacle in a landing collar below the liner hanger. At a particular increased pressure a setting piston moves upward to an extended position. The setting piston drives a setting sleeve, connected by one or more slip arms to the slips. This drives the slips, which expand out over the wedge-shaped cone pads until fully gripping the inside of the casing. Downward motion transfers the full liner weight through the cones and slips into the supporting casing.
Alternatively, the hanger can be mechanically set. In one such hanger, the work string attached to the liner hanger is rotated. Rotation may be right-hand set or left hand set depending on the desired embodiment. The rotation causes a J-Cage mechanism in contact with the casing to disengage a lug from the short leg of the J-Cage and allows the slips to align with the cones. Downward motion then allows the slips to expand over the cones and grip the casing's inner wall, transferring the weight of the liner to the supporting casing.
A disadvantage of such prior art liner hangers is that they must be constructed using a very thick-walled steel tube stock, for example a six inch inner diameter might require an eight inch outer diameter, in order for the wall to have sufficient thickness in the area of the cones and the cylinder once the steel tube is machined inside and out. This creates expense in the material, in the machining time, and in the construction.
Other liner hangers have been constructed with a single-piece mandrel or barrel. In this case, the cylinder or J-Cage is connected to the barrel using mechanical means such as set screws, wirelocks, or welding. The cones are generally integral to the barrel as described above, but in some prior art embodiments the cones may have been welded to the barrel, which adds cost and time to the production. In addition, because of the complexity and cost of the tool construction, it is impractical to create stock items.
Welding the cones or the cylinder to the barrel or casing mandrel requires multiple welds. These welds add time and expense to the manufacture of the liner hanger. More importantly, welding can affect the metallurgy of the barrel, making the welded area subject to attack, for example by corrosive well fluids. As such, welding to the barrel or to a casing mandrel is at minimum undesirable, and may be prohibited under certain industry standard regulations. As such, mechanical connections are preferable.
The disadvantages of two-piece liner hanger, and the single-piece welded liner hanger, are overcome by the present invention.


A door assembly for a vehicle includes a door panel, a primary assist handle, a secondary assist handle, and a first and second extension. The primary assist handle and the secondary assist handles are configured for being grasped by the user of the vehicle. A first extension extends from the door panel. A second extension extends from a second mounting portion of the secondary assist handle, in spaced relationship to the first extension. The extensions pivotally support ends of the primary assist handle. The primary assist handle pivots relative to each of the extensions and the door of the vehicle, between a retracted position and an extended position. A first mounting portion of the secondary assist handle pivotally extends from the door panel.

Some vehicles have doors that, when in an open position, are open so far away from a seat within the vehicle that a user may have a difficult time reaching and grasping an interior door handle to pull the door closed when seated in the seat. The seats within these vehicles may also be so far off of the ground that some users have a difficult time gaining leverage to climb into or out of the seats of the vehicle.

Door assist assembly for being grasped by a user of a vehicle


An automated vehicle return system wherein status information of a rented vehicle is automatically tracked during the rental period and is transmitted to a selected destination computer upon driving the vehicle into a return area. Electronic vehicle monitoring circuitry is tied to existing components within the vehicle to keep track of the status of the vehicle during the rental period. The status information includes, miles driven, fuel level, pick up time, drop off time, wear and tear on the vehicle, etc. The status information is used by the destination computer to generate a bill for the rented vehicle.

In the modern era, the need and desire to travel for business as well as pleasure has increased significantly. With growing global business pressures, individuals are often asked by companies and firms to travel on short one or two day trips to handle immediate business needs. The increased travel has made the need for efficient air and ground transportation essential. For instance, recent trends in the airline industry has lead to ticketless travel which reduces the transactional time it takes to obtain and present a paper ticket when flying. With respect to ground transportation, car rental establishments have continued to attempt to improve the pick-up and drop-off procedures to minimize unnecessary delays.
Although current car rental drop off procedures are fairly effective, there are still several delays and/or costs which have not been overcome. For instance, upon returning a vehicle an individual must write down or memorize the current mileage and fuel level and then enter the car rental establishment so that an attendant can properly calculate the final cost and print a receipt. This, of course, often leads to delays and inaccuracies in the return. To save time and improve reliability, some car rental establishments employ workers to wait outside for car returns and then have the employee physically check the mileage and fuel level of the returned car. Then, using a wireless portable computer, this information is instantaneously sent to the computer of the attendant inside the rental establishment so that the customer can quickly obtain his/her receipt. Although more efficient, this situation results in increased labor and equipment costs which are ultimately passed along to the customer.
Thus, what is needed is an improved vehicle return system which overcomes the shortcomings discussed above.


The invention provides a heterogeneous immunoassay for detection of antibodies and antigens based on specific antigen-antibody immune complex formation with multiple antigen-bearing conjugate components. The invention further provides means for optimizing the assay format for the detection of both low and high-affinity antibodies, and provides means for quantitative detection of both antibody and the corresponding antigen present in a sample.

Antibodies are protein molecules which specifically bind antigens that initiate the formation of the antibodies. Antibodies are produced by B-lymphocytes and plasma cells, and are present in blood plasma (as secretory antibodies or cell bound), lymphatic fluids, cerebrospinal fluid, mucus and other extracellular secretions (e.g., saliva), and in some instances, urine. Assays for antibodies have been widely applied to the examination and diagnosis of many infections, and autoimmune and allergic conditions.
There are currently several known immunoglobulin classes, IgG, IgM, IgA, IgE and IgD. These immunoglobulins are involved in different types of immune responses, and their involvements are dependent, for example, on antigen structures, type of organisms which bear these antigens, time after immunization, and presence of other antigenic molecules in the microorganisms. It is believed that antibody classes important for serological testing and secretory immunoglobulins contain two or more identical antigen-combining sites. In particular, it is believed that there are two sites for IgG and IgE, four for IgA, and up to 10 for IgM. This mean that at least two antigen molecules or specific antigenic (epitopic) substances can bind simultaneously to one antibody molecule.
It should be noted that affinity of antibodies to specific antigens may not be constant. Beside the spectrum of polyclonal antibodies which can differ in affinity at varying stages of an immune response depending on the particular pathogen/immunogen, affinity of antibodies can change with time, from low to high affinity, for instance, during the antibody maturation process. Moreover, several antibody classes can simultaneously recognize the same antigen. In the case of bacterial, viral, protozoan, parasitic, or fungal infection, the IgM class can appear at the early stages of an immune response, usually as antibody with a low affinity constant, while the IgG class can appear later in the immune response. For serological testing constant, while the IgG class can appear later in the immune response. For serological testing of many infections, the ability to detect antibodies at the earliest stages of seroconversion can be very important in determining a treatment. Because the IgM class antibodies often appear during the early stages of infection, their presence is often considered as a serological indication of early stage of infection.
Antibodies can be detected using a variety of immunoassay protocols. Among conventional methods, the most widely used works on principles of solid phase immunoassay using immobilized antigens and secondary class-specific anti-immunoglobulins conjugated with detector labels, such as, enzyme, fluorophores, chemiluminescent, metal sols, dyed polymeric particles, or labeled proteins which bind to immunoglobulins (protein A and G). A disadvantage of such a method is that a falsely positive result can be obtained due to non-specific and cross-reactive reactions related to simple adsorption of non-specific antibodies on coated solid phase, or the presence of unwanted antigenic substances in antigens used for adsorption on solid phase. This can happen even in case of using relatively pure antigens obtained by methods of recombinant technology. Moreover, the presence of, for instance, autoantibodies, rheumatoid factor, or polyspecific/polyreactive antibodies, can lead to false results. Even in case of using very specific small peptide antigens, false positives can arise as result of contaminations in the reagents used for immobilization on solid phase.
In order to reduce the occurrence of false positives, steps, such as, selection of sample dilution, incubation time, temperature, and diluents used, have been taken to reduce potential cross-reactive reactions. However, such steps can require the application of many serological tests and can reduce detection sensitivity. For example, in a solid phase immunoassay using solid phase immobilized antigens, the presence of conjugates antigen-specific antibodies with detector label can compete with antibodies in a sample to be detected to bind with the immobilized antigens. As a result, although this competitive test is relatively simple and may be less susceptible to non-specific reactions, its sensitivity for detection can be relatively low.
In another immunoassay for specific antibody detection based on competitive binding, a specific antibody may be immobilized in a solid phase. However, during incubation, labeled antigens in the sample and the antibody to be detected in the sample can compete to bind with the immobilized antibody. As with the previous example, sensitivity of detection may be affected due to competitive binding, and as a result, may require a significant amount of pure anti-antigen antibodies for use.
In another immunoassay, the solid phase may be coated with a class specific immunoglobulins. Labeled antigens may be used in the sample of the antibody to be detected to form an immune complex with the class specific immunoglobulins in the solid phase. One disadvantage of this immunoassay is the limited binding capacity of the class specific immunoglobulins in the solid phase, which can limit the sensitivity of specific antibody detection.
A further variation of solid phase immunoassay involves the use of solid phase coated antigens to capture specific antibody and subsequent detection of captured/bound antibody with a labeled antigen. However, a prozoning phenomenon may be a problem for this approach. In particular, the density of antigen on solid phase should be carefully optimized to protect the antibody from binding with the solid phase antigen through all combining sites (e.g., IgG class) on the antibody, which reduce number of sites available on the antibody to bind with labeled antigen. A second incubation with labeled antigen is described in U.S. Pat. No. 6,121,006 as a way for increasing sensitivity of this type of assay.
U.S. Pat. No. 6,030,770 discloses a method for antibody detection using labeled antigen and a solid phase capture system. In this method, the solid phase comprises immobilized antigens and anti-immunoglobulin antibodies introduced into the capture system through an additional bridge. The bridge, as disclosed, includes analyte-specific antibodies capable of recognizing ligand-labeled anti-species class specific antibodies.
U.S. Pat. No. 4,778,751 discloses a method for detection of circulating antibodies, which method is based on the use of a ligand-labeled polymeric matrix. In this method, the matrix is conjugated with multiple antigen molecules, a ligand-binding partner immobilized on solid phase, and anti-immunoglobuline detector reagent.
In U.S. Pat. No. 4,945,042, a three reagents antibody detection system is disclosed. The detection system, as disclosed, comprises two components of a specific binding pair. One component is included in the capture system as a conjugate of StrAv with thermo polymerized BSA of anti-immunoglobulin antibodies, while the second component is conjugated to the antigen. A third reagent is labeled and is a conjugate of the antigen.
U.S. Pat. No. 5,236,849 discloses a detection method utilizing an antigen containing simultaneously two different labels belonging to two affinity pairs, each with its counterparts distributed between separate solid phases. This approach permits for significant reduction of non-specific reaction by using immune-complex transfer (dissociation-recapture) for detection in a second container.
Lyphophilic bridges, such as liposomes or some other reversible bridge, are disclosed in U.S. Pat. Nos. 5,312,730 and 5,705,338 as a way to dissociate an immune complex from a first solid phase to permit transfer into a second solid phase for detection.
Small peptide antigens, containing specific epitopes, mono or limited amount, can be powerful instrument for development of highly specific serological test. The role of these peptides, whether obtained by chemical synthesis or recombinant technology, have become increasingly important. However, affinity of antibodies against these small epitopes is sometimes lower than the affinity to a sequence in whole protein. Moreover, affinity of antibodies to selected peptide antigens can vary due to the presence of various strains of pathogens and its genetic variability. Accordingly, it is desirable to provide simple methods, which can permit the detection of antibodies that may have low affinity to selected epitopes.

Systems and methods for detection of analytes in biological fluids


A package includes a body with a key position and a lock position on one side thereof, and multiple positioning members on the other side of the body. The positioning members position a card. The body has at least one installation hole which has at least one contact portion. A hasp has at least one contact member. When the hasp extends through the at least one installation hole, the contact member is engaged with the at least one contact portion. The shackle of the lock is connected to the hasp and the hasp is adjustable relative to the installation hole according to the size of the lock. The body and hasp are modularized so as to be cooperated with different locks and reduce manufacturing cost.

1. Field of the Invention
The present invention relates to a package, and more particularly, to a package for accommodating a lock and a key for the lock.
2. Descriptions of Related Art
The conventional way to sell a lock usually has a package or a box in which the lock is received, and the package is designed to attract the consumers attentions and to protect the lock from being damaged during transportation. U.S. Pat. Nos. 7,743,917, 7,516,843 and 7,905,351 disclose a package for a lock which has a shackle. The package has a card with a front side and a back side, and the card has a positioning member which has a slot defined in the front side of the card. A bag has a room which extends from the front side of the card so as to accommodate the key of the lock. A locking member is used to secure the key in the bag.
For the three disclosures mentioned above, the shackle is hiked to the slot so as to connect the lock to the positioning member which is integrally formed on the front side of the card. Therefore, the positioning member cannot be adjustable relative to the card, so that the card can only be used for a certain type of lock. When a new type lock is to be displayed or packed, a new package has to be developed and manufactured, and this means new molds are needed and higher cost is involved. Besides, in order to restrict the lock to be rotated clockwise or counter clockwise, the lock is separated from the positioning member. However, there is an opening defined through the card and the lock is located corresponding to the opening, so that the lock swings horizontally and toward the card during transportation. When there are multiple locks connected to the positioning members are overlapped, the packages and/or the locks may be damaged by hit during transportation.
Another package for a lock is disclosed in FIG. 1 and comprises a card 10 which has a hasp 101 and a positioning portion 102 on the front side of the card 10. A hole 1011 is defined through the hasp 101 and two blocks 1021 are respectively located on two sides of the positioning portion 102. An opening 103 is defined in the lower end of the positioning portion 102. An accommodating portion 104 is formed in the card 10.
When in use, the shackle of the lock (not shown) is hooked to the hasp 101 via the hole 1011, and the positioning portion 102 is located to be enclosed by the shackle. The accommodating portion 104 accommodates the key for the lock. The card 10, the hasp 101 and the positioning portion 102 are integrally formed so that the height of the hasp 101 relative to the card 10 is fixed; The shape of the hasp 101 is also fixed, so that only the lock with the specific size of the shackle and lock can be used to the package. The package can only be used for certain type of lock, and a new package has to be developed when a different lock is to be packed. It takes time and has poor compatibility. Besides, when the shackle is hooked in the hasp 101, the opening 103 allows the lock to swing and this can hit other packages and locks during transportation.
The present invention intends to provide a package for a lock and a key, and the package improves the shortcomings mentioned above.


A door-opened-prevention mechanism comprises a lever member, and a biasing member biasing the lever member toward a set position. The lever member is assembled to a connection lever. The lever member is movable between the set position and a fallback position which is in a vehicle outer direction to the set position. When an inertia force, exerted on an outer handle toward the vehicle outer direction at the time of vehicle impact, is not exerted on the outer handle, the lever member is kept in the set position to enable a necessary and sufficient movement of the connection lever in a direction for opening a door, and when the inertia force is exerted on the outer handle, the lever member moves to the fallback position prior to movement of the outer handle for opening the door so as not to enable the necessary and sufficient movement of the connection lever.

Such a type of the door outer handle apparatus is disclosed in, for example, the Patent Document 1 described below. In the Patent Document 1, the door-opened-prevention mechanism comprises inertia stopper member (lever member) provided on the base member so as to be rotatable between a set rotational position (initial position) and a lock rotational position which is in the outer direction of the vehicle to the set rotational position; and a biasing member biasing the inertia stopper member toward the set rotational position. In the door outer handle apparatus disclosed in the Patent Document 1, when the inertia stopper member rotates from the set rotational position to the lock rotational position, which is in the outer direction of the vehicle to the set rotational position, against the biasing force of the biasing member in a case where an inertia force (a force toward the outer direction of the vehicle) is exerted on the inertia stopper member at the time of impact of the vehicle, a part of the inertia stopper member moves within a movement locus in a direction for opening the door of a structural member of the linkage mechanism (connection clip provided on a connection rod), and therefore a movement of the linkage mechanism in a direction for opening the door is restricted by the inertia stopper member. With this, at the time of impact of the vehicle, the door-opened-prevention mechanism restricts the movement of the outer handle for opening the door by use of inertia force that works toward the outer direction of the vehicle, so as to prevent the door from being opened.


A module having a housing, a battery, control circuitry and electrical conductors. The battery and control circuitry are contained in the housing. The housing is adapted to be removably connected to the frame of a firearm. The electrical conductors are located on the housing and allow the battery and control circuit to be electrically connected to other components of the firearm. The housing can be connected at a hand grip section of the firearm and forms a substantial portion of at least one exterior side of the firearm at the hand grip section.

1. Field of the Invention
The present invention relates to firearms and, more particularly, to a module having a battery and control circuitry that is removably connected to the rest of the firearm
2. Prior Art
U.S. Pat. No. 5,052,138 discloses a magazine module with a microprocessor and a grip module with electronic circuitry The magazine module also houses batteries U.S. Pat. No. 5,461,812 discloses a firearm with a transmitter and a receiver, a ring having a transponder worn by a user, and a safety solenoid to block movement of a trigger mechanism


A multiple-compartment container includes an upper rim defining an upper plane, a lower rim defining a lower plane, a perimeter wall connecting the upper rim to the lower rim. The perimeter wall forms an outer surface of the container. The container further includes at least one internal wall dividing the container into multiple compartments. An upper edge of the internal wall is an uppermost feature of the container. The upper edge of the internal wall is deformable to present a widened sealing surface during a sealing operation.

The present disclosure relates generally to the field of containers for food products, and more particularly to a multiple-compartment container for separating two or more food products within a single package.
In the past, multi-compartment containers have been used for packaging complementary food products (e.g., cheese and crackers, chips and salsa, cottage cheese and fruit, etc.). One of the food products is contained within a first compartment and the complementary food product is contained within a second compartment. Conventional containers often include an upper rim to which a removable cover or lid is attached. Typically, the cover is bonded or sealed to the upper rim after the container is filled.
Conventional containers suffer from the disadvantage that the cover often fails to adequately separate the first compartment from the second compartment. For example, the cover may be bonded to an outer perimeter of the container without providing an airtight seal between compartments. The lack of an airtight seal between compartments can result in moisture from one compartment undesirably equilibrating into another compartment.


The present invention provides a metal halide lamp in which the change of the color temperature is suppressed regardless of the orientation of the light emitting bulb in use. The metal halide lamp includes a light emitting bulb of translucent ceramics that includes a light emitting portion and tubular portions that are connected to the light emitting portion. The light emitting portion includes a liquid holding portion on the inner surface of the light emitting portion so as to hold a liquefied substance that moves on the inner surface toward one of the tubular portions. The internal diameter d of the light emitting bulb at the liquid holding portion satisfies 0.4D<d<0.7D, where D is an internal diameter of the light emitting bulb at the maximum internal diameter portion of the light emitting portion.

Translucent ceramics such as alumina are used for a light emitting bulb of a metal halide lamp. As shown in FIG. 10, a light emitting portion 31a and tubular portions 31b of the light emitting bulb are molded in one piece to increase heat efficiency and improve lamp characteristics.
A metal halide lamp that includes an integrally molded light emitting bulb is shown in FIG. 11 and a sectional view of this light emitting bulb is shown in FIG. 12.
The light emitting bulb 31 is placed in an outer bulb 32 and lead wires 33a and 33b are attached to the tubular portions of the light emitting bulb 31. The lead wires 33a and 33b are connected to electrodes 17a and 17b in the bulb 31. One end of the outer bulb 32 is closed by a base 34. A stem 36 holds stem leads 35a and 35b, and one of the stem leads 35a is connected to the lead wire 33a and the other stem lead 35b is connected to the lead wire 33b via a power supply wire 37.
Mercury and an iodide of cerium, sodium, thallium, indium, or scandium are sealed in the light emitting bulb 31. When turning on the lamp, the mercury is heated and vaporized by an electric discharge between the electrodes 17a and 17b. Then, the iodide is liquefied and a part of the iodide is vaporized. However, another part of the iodide is attached to the inner surface of the light emitting bulb 31 in a liquid state. When a longitudinal direction of the bulb 31 is arranged along a vertical direction as in FIG. 12 and the lamp is turned on, the liquid iodide is dropped into a gap between the inner surface of the lower tubular portion and the electrode 17a. The liquid iodide 38 in the tubular portion reduces a vapor pressure of iodide in the bulb and causes a change in lamp characteristics, especially in color temperature.

Matsushita Electric Industrial Co., Ltd.


A computer-implemented method for processing single message transactions with batch settlement may include receiving a dual-message transaction from a merchant, converting the received dual-message transaction to a single-message transaction, setting a flag on the converted single-message transaction indicating the conversion to a single-message transaction, receiving a batch settlement file from the merchant, for each transaction in the batch settlement file, determining whether the single-message transaction conversion flag is set, upon determining that the single-message transaction conversion flag is not set, storing the transaction for later processing, and upon determining that the single-message transaction conversion flag is set, sending the transaction to a payment network.

Transactions, including card transactions, are used for a great number of purchases and sales between merchants and cardholders. A normal card transaction can involve a number of parties, including an account holder who possesses a card, a merchant, an acquirer processor, an issuer processor, an issuer financial institution and a card association network. Millions of such transactions occur daily at merchants using a variety of payment vehicle types, such as credit cards, debit cards, prepaid cards, digital wallets, and so forth.
Depending on the type of payment vehicle used, the transaction may be processed by the involved parties by exchanging messages in accordance with an appropriate messaging scheme. For example, in a dual-message transaction, which primarily involves signature-based transactions including credit card transactions and signature-based debit card transactions, an electronic message containing the information required for an authorization decision may be submitted at the time of purchase, and a separate electronic message containing additional data required for clearing and settlement may be submitted at a later point in time. In a single-message transaction, which primarily involves debit card transactions including both personal identification number (PIN)-based and PIN-less debit card transactions, a single electronic message containing all data required for the authorization, clearing, and settlement of the transaction may be submitted at the time of purchase.
Under certain circumstances, the fees associated with the dual-message transaction may be higher compared to those associated with the single-message transaction. When a customer initiates a dual-message transaction (e.g., a credit card transaction, a signature-based debit card transaction), the issuer financial institution takes a risk by transferring the funds to the merchant and waiting to collect the funds from the consumer at a later date. The merchant may thus be subjected to a percentage fee charged by the issuer financial institution for taking such a risk and processing the transaction, in addition to the fees charged by other entities for the time and resources used to process the transaction. On the other hand, when a customer initiates a single-message transaction (e.g., a PIN-based or PIN-less debit card transaction), the customer authorizes funds to be transferred from her account to the merchant's account at the time of sale. Accordingly, routing and processing the single-message transaction (for example, in a debit network) may consume less resources, incur less fees, and may allow the merchant to realize cost-savings by routing transactions using alternative domestic networks.
The present disclosure is directed to overcoming one or more of these above-referenced challenges. The background description provided herein is for the purpose of generally presenting the context of the disclosure. Unless otherwise indicated herein, the materials described in this section are not prior art to the claims in this application and are not admitted to be prior art, or suggestions of the prior art, by inclusion in this section.

Systems and methods for single message transactions with batch settlement


An optoacoustic system comprises an optoacoustic transducer including a first array of acoustic transducers and a second array of optical fibers; an acoustic subsystem for controllably exciting at least a first subset of the acoustic transducers to generate acoustic pulses with a prescribed pulse width, and for forming a first image based on return acoustic pulses reflected from a patient; an optical subsystem for controllably generating optical pulses to be transmitted through at least a first subset of the optical fibers toward the patient, and for forming a second image based on light reflected from the patient; and image correlation means for correlating the first and second images. The first and second arrays may take various forms, including the form of an annular array in which the acoustic transducers are arranged coaxially and the optical fibers are disposed around an outer periphery of the first array. The first and second arrays may also take the form of linear arrays.

Optical and acoustic (e.g., ultrasound) imaging have each been used as separate modalities for diagnostic imaging. Each of these modalities has limitations owing to the physics involved.
For example, while ultrasonic energy used for imaging can have very good penetration, e.g., it can penetrate through up to 20 centimeters of tissue without much signal attenuation, the available resolution depends upon the spatial pulse length used. For example, one cycle of a pulse of a 5 MHz signal will provide a resolution of about 0.3 millimeters. (This estimate is based on a propagation speed of 1.5 mm/.mu.s; i.e., one cycle=0.2 .mu.s.times.1.5 mm/.mu.s=0.3 mm.) In other words, with a frequency of 5 MHz, one can not detect anything smaller than 0.3 millimeters or differentiate two features with a separation of less than 0.3 millimeters.
Optical energy, on the other hand, offers good resolution but very limited penetration, due to attenuation and scattering of light in tissue. The resolution possible with optical imaging is based on the wavelength of the light. Typical optical imaging wavelengths are in the micrometer range, and therefore resolutions on the order of micrometers are possible. Moreover, since tissues with different metabolisms (such as cancerous tissues) often exhibit different optical absorption characteristics, different optical wavelengths may be advantageously employed for imaging and detection of abnormal tissue.
Thus, optical imaging is hampered by relatively poor penetrability and difflusion, and ultrasound imaging is hampered by its relatively poor spatial and contrast resolution for defining the physiology of images. These modalities may be combined, however, to provide new and improved systems and methods for imaging. Copending U.S. patent application Ser. No. 08/993,165, filed Dec. 18, 1997, entitled "Optoacoustic Contrast Agents and Methods for Their Use," which is hereby incorporated by reference in its entirety, discloses novel optoacoustic contrast agents and methods of imaging using such contrast agents. The present invention was made during the process of designing an imaging system and associated optoacoustic transducer for use, preferably, with the novel contrast agents.


A communication system may include a first control circuit to detect a break on a first optical link; a first optical source to supply a first optical signal on a second optical link in response to detecting the break on the first optical link, the first optical signal propagating in a first direction on the second optical link; a second control circuit to detect a presence of the first optical signal on the second optical link, and output a control signal in response to detecting the presence of the first optical signal; and a second optical source to supply a second optical signal on the second optical link, the second optical signal propagating in a second direction opposite the first direction, where the Raman pump is disabled in response to the control signal.

Wavelength-division multiplexing (WDM) is a technique where light signals of different wavelengths are combined and simultaneously transmitted over a single optical fiber. Long distance WDM systems often use amplification to amplify the light signals.
One form of amplification is called Raman amplification. With Raman amplification, the amplification effect is achieved by an interaction between the signal and a pump laser within an optical fiber. One type of Raman amplification is commonly referred to as distributed Raman amplification. Distributed Raman amplification uses the transmission fiber as a gain medium by multiplexing a pump light wavelength with a signal wavelength. The pump light may be coupled into the transmission fiber in the same direction as the signal (co-propagating), in the opposite direction (counter-propagating) as the signal, or both.

Automatic laser shutdown and recovery in response to a link break


An inter-rotor bearing assembly includes a first annular member having a circumferential inner surface and a second annular member having a circumferential outer surface. The outer surface is concentric to and disposed radially inward of the inner surface and a bearing is disposed between the surfaces. The bearing has an outer race fixedly attached to the first annular member along the inner surface, an inner race fixedly attached to the second annular member along the outer surface, and rolling elements disposed between the races. A low density high circumferential strength support ring is fixedly attached to the first annular member disposed concentrically outside of the inner race and is preferably made of a titanium matrix composite. The rolling elements may be cylindrical rollers having cylindrical rolling surfaces. The support ring may be fixedly attached around or integral with the first annular member.

1. Field of the Invention
This invention relates to bearing assemblies for bearings disposed between concentric shafts of high and low pressure rotors of a gas turbine engine and particularly to such an assembly having a titanium matrix composite support ring surrounding the outer race of the assembly.
2. Discussion of the Background Art
A conventional gas turbine engine includes a core engine having in serial, axial flow relationship, a high pressure compressor to compress the airflow entering the core engine, a combustor in which a mixture of fuel and the compressed air is burned to generate a propulsive gas flow, and a high pressure turbine which is rotated by the propulsive gas flow and which is connected by a large diameter high pressure shaft to drive the high pressure compressor. A typical bypass turbofan engine also has a low pressure turbine aft of the high pressure turbine and which drives a forward fan forward of the high pressure compressor with a low pressure shaft concentrically disposed within the first shaft.
In order for intershaft differential bearings to function properly, the bearing races must remain in contact with the bearing. Typically, the inner race is positioned on the high pressure shaft which has a higher rotational speed and, thus, the inner race undergoes a higher radial growth or deflection as compared to the outer race which as positioned on the low pressure shaft and running at a lower rotational speed. This configuration is designed to have the inner race deflect or grow more in the radial direction than the outer race and, thus, provide that the races are always engaged. In order to achieve this required bearing support, complex hardware geometry is required to support the outer race on the low pressure shaft (see U.S. Pat. No. 4,558,564 for example). The present invention is designed to eliminate much of this complex hardware, simplify the inter-shaft bearing assembly and provide that the inner and outer races are always engaged with the rolling elements therebetween.


A cutting tool in which a disc-like cutter blade is fixed to a spindle of a rotary electric tool, comprising a first guide plate, which is attached on electric tool side to a cutter blade such that it is capable of rotating freely and makes contact with the reference surface of a cutting object material on a process of cutting progress so as to guide along a cutting direction, an inner flange located between the first guide plate and the cutter blade so as to specify a distance X from the reference surface of the cutting object material to a cut groove and a second guide plate which is provided on an opposite side to the electric tool side of the cutter blade and makes contact with a cut face of the cutting object material on a process of the cutting progress so as to stop moving in the cutting direction to specify a cut groove depth Y.

Conventionally, various kinds of natural stones and artificial marbles (hereinafter referred to as just "stone material") are usually cut out from a slab material 20–40 mm in thickness and 1500–2000 mm long on its side as a square slab plate 70 shown in FIG. 7. When constructing as floor material or wall material on a construction site, a desired area is obtained by bonding their edges 71 together. To bond together stone materials heavy and extremely hard and brittle firmly through a side face having a small bonding area, various devices have been made. For example, as a method easy to apply on a construction site and reliable, a method in which a groove 72 is formed in the side faces to be bonded together and the side faces 71 containing the groove 72 are coated with glue 73 mainly composed of epoxy base resin, polyester base resin and the like and bonded together has been widely adopted (see FIG. 8).
According to the above-described method, by forming the groove in each of the edges faces of the stone materials to be bonded together, the bonding area can be increased and further, glues applied in two grooves merge with each other so as to obtain strict bonding condition. The adhesiveness of the glue supplements the brittleness of the bonding faces of the hard, brittle materials. Further, if the thickness of the stone materials are different, the groove under the above-described method acts as a role as a construction criterion. Thus, it is preferable that the grooves formed in the bonding faces oppose each other accurately while their depths are balanced to a specified one.
The groove for glue formed in the above-mentioned slab plate is generally formed in the width of 4–5 mm and the depth of 7–12 mm and as described above, to intensify the bonding strength, balances of the opposing position and the width and depth of the groove and the like are important factors. However as regards a groove cutting means for a stone material on a construction site, currently, a disc type cutter used for mainly cutting a stone material and the like or an offset type cutter having a concave face in the center of its substrate is employed, and individual worker works manually relying upon his experience using such a handy electric tool. If taking up an extreme example, some worker uses two pieces of diamond saw blades such that they overlap in order to obtain a width of the groove (of course, this is an illegal use), indicating that the cutting depends on the degree of skill accumulated in the worker for a long time.
Upon use, the aforementioned disc cutter or the offset cutter is attached to a handy electric tool which rotates at high speeds such as a grinder and sander. A deflection originating from vibration accompanying the rotation of the electric tool and a distortion of the substrate of the cutter provide a large disturbance on accurate cutting in a cutting object material and additionally, a large burden is born on a worker. Thus, according to an offset type cutter (for example, Japanese Patent Application Laid-Open No. 2002-103235) which has been proposed to solve the problems and used actually, in a rotary cutting tool (for example, Japanese Patent Application Laid-Open No. HEI7-276215) which absorbs vibration and deflection by interposing an elastic body between the cutter blade and spindle or an offset cutter in which a plurality of ultra abrasive layers are formed on the outer periphery of its substrate, by forming ultra abrasive layer by pressurizing at least a portion near the outer periphery of a drawn substrate with a die and sintering, distortion of the substrate is eliminated by sintering so that vibration originating therefrom is reduced.


A magnetic film forming system which can always apply a magnetic field to a substrate in a constant direction is disclosed. The magnetic film forming system includes a vacuum container, a substrate pallet for holding a substrate in the vacuum container and being removable while still holding the substrate, from the vacuum container, and means for supporting the substrate pallet. Magnetic field generation means are fixed to the substrate pallet for applying a magnetic field to the substrate. When the substrate pallet is removed from the vacuum container, the magnetic field generation means are also taken out together with the substrate.

1. Field of the Invention
This invention relates to a system for forming a magnetic film in a magnetic field and more particularly to a magnetic film forming system which comprises a plurality of process chambers, of film forming etc., and transport mechanisms for transporting substrates from one process chamber to another.
2. Description of the Related Art
A conventional inline film forming system is described with reference to FIG. 9. The inline film forming system in FIG. 9 comprises a substrate inlet chamber 2, three process chambers 1a, 1b, and 1c, and a substrate outlet chamber 3 which are linked in order. Sluice valves 8a, 8b, 8c, and 8d are disposed between each of the chambers. Each of the process chambers 1a, 1b, and 1c is provided with a device (not shown) for performing one process such as heating a substrate before film forming, sputtering film forming, ion beam sputtering film forming, or film forming by evaporation. A transport line 5 for transporting a substrate 101 is extended through the substrate inlet chamber 2, process chambers 1a, 1b, and 1c, and substrate outlet chamber 3.
The sequence for forming a film by using the system will be described. First, a substrate 101 on which a film is to be formed is fed into the inlet chamber 2, which is then evacuated by evacuation installation 9a. The process chambers 1a, 1b, and 1c, and the outlet chamber 3 are evacuated by evacuation installations 9b, 9c, 9d, and 9e respectively. After the inlet chamber 2 is evacuated, the separation valve 8a is opened and the transport line 5 is operated to transport the substrate 101 to the process chamber 1a, which has been already evacuated. In the process chamber 1a, predetermined steps such as heating the substrate before film formation and film formation are performed by the processing device installed in the chamber. After the predetermined steps are performed, the separation valve 8b is opened and the substrate 101 is transported to the following process chamber 1b over the transport line 5. Upon completion of processing the substrate 101 in the process chamber 1b, the substrate 101 is transported to the process chamber 1c for further processing. After predetermined processing in the process chamber 1c is complete, the substrate 101 is transported to the outlet chamber 3 from which iti is removed. A large number of substrates 101 can be fed in sequence into the substrate inlet chamber 2 and through the process chambers 1a, 1b, and 1c one after another for processing.
By the way, to form a film whose magnetic orientation is aligned, a film forming method in a magnetic field is used by which a film is formed while magnetic orientation of film particles is being aligned by applying a magnetic field. An example of the film forming system in the related art is given in xe2x80x9cJournal of Vacuum Science and Technology A (Composition distribution and magnetic characteristics of sputtered Permalloy films with substrate angle)xe2x80x9d second series volume 7, number 3, May/June 1989. The article describes a technique in which a permanent magnet is attached to a substrate holder fixed to a film forming system and a substrate is mounted on the substrate holder.
To form a magnetic film in a magnetic field by a conventional inline film forming system, magnetic field generation means is fixed outside or inside a process chamber and a magnetic field is applied to space in the process chamber where a substrate is placed.
For example, the conventional inline system in which magnetic field generation means is attached outside a sputter film forming process chamber will be described with reference to FIG. 7. As shown here, Helmholtz magnetic coils 4a, 4b, 4c, and 4d are disposed outside a process chamber 1d which is provided with a magnetic target 3 and an RF power supply 2 for applying voltage to the magnetic target 3. The Helmholtz magnetic coils 4a, 4b, 4c, and 4d form a magnetic field 6 in a space where a substrate 101 is placed. The substrate 101 is supported by a transport line (not shown). Magnetic sputter particles sputtered from the magnetic target 3 are affected by the magnetic field 6 to form a film magnetically oriented on the substrate 101.
The conventional inline system in which magnetic field generation means is attached inside a sputter film forming process chamber wiil be described with reference to FIG. 8. As shown here, permanent magnets 4e and 4f are disposed at places around a substrate 101 carried in a process chamber 1e. The permanent magnets 4e and 4f are supported by magnetic support means 7 fixed to the process chamber 1e. Since the permanent magnets 4e and 4f form a magnetic field 6 in a space where the substrate 101 is supported by a transport line (not shown), sputter particles sputtered from the magnetic target 3 are affected by the magnetic field 6 to form a film magnetically oriented on the substrate 101.
The conventional film forming system having the magnetic field generation means has the following problem: When a substrate is taken out from the film forming system after a film has been formed, it is placed out of the magnetic field of the magnetic field generation means. Thus, if the substrate is taken out from the film forming system in the state in which it is not completely cooled after the film has been formed, the magnetic orientation of the film is not aligned, degrading the magnetic characteristic. To prevent this inconvenience, the substrate must be left in the film forming system until it is completely cooled after film formation. It takes time until the substrate is completely cooled, substantially lowering the throughput of the system.
To form a magnetic multilayer film by using the conventional inline system having the magnetic field generation means, the following problems occur:
(1) To form a multilayer film, a number of film forming process chambers which differ in film forming source must each be provided with magnetic field generation means. At the time, it is very difficult to completely match all directions of magnetic fields applied to substrates by the magnetic field generation means in the process chambers. This causes orientation of the magnetic film to vary from one layer to another, degrading the magnetic characteristic of the magnetic film. The two main reasons why the directions of the magnetic fields in the process chambers cannot be matched are as follows: First, to completely match the directions of the magnetic fields generated by the magnetic field generation means in the film forming process chambers, the directions of coils and magnets must be matched completely; however, it is technically very difficult to completely match the directions of coils and magnets which are separated from each other and adjustment of the directions requires that the system should be stopped over a long period of time. Second, when a substrate is transported, the substrate turns and its direction will vary.
(2) When the magnetic field generation means is installed outside each film forming process chamber, a magnetic field must be generated within the process chamber, thus large magnetic field generation means needs to be installed, increasing costs.
(3) Process chambers must be located apart from each other to prevent magnetic fields generated by magnetic field generation means in the contiguous process chambers from affecting each other to become uneven magnetic fields. Thus, the line in the system is prolonged compared with a normal inline system having no magnetic field generation means, leading to inconvenient installation of the former system.
(4) When a substrate is transported to the contiguous film forming process chamber after film formation, it is temporarily placed out of magnetic field. Thus, if it is transported to the next process chamber in the state in which the substrate is not completely cooled after film formation, it is cooled out of the magnetic field, and thus the magnetic orientation of the film is not aligned, degrading the magnetic characteristic o f the magnetic material. To prevent this inconvenience, the substrate must be left in the process chamber until it is completely cooled after film formation. It takes time to cool the substrate, substantially lowering the throughput of the line.
Accordingly, it is an object of the invention to provide a film forming system which can form a magnetic film having a high magnetic characteristic by always applying a magnetic field in a constant direction to a substrate in the system.
To this end, according to a first embodiment of the invention, there is provided a magnetic film forming system comprising a vacuum container, a substrate pallet for holding a substrate in the vacuum container and being removable, with the substrate held, from the vacuum container, means for supporting the substrate pallet in the vacuum container, means for forming a film on the substrate, and magnetic field generation means for applying a magnetic field to the substrate. The magnetic field generation means is fixed to the substrate pallet. When the substrate pallet is removed from the vacuum container, the magnetic field generation means is taken out from the vacuum container together with the substrate pallet.
According to a second embodiment of the invention, there is provided a magnetic film forming system comprising a vacuum container, a substrate pallet for holding a substrate, transport means for supporting the substrate pallet in the vacuum container and transporting the substrate pallet, means for forming a film on the substrate, and magnetic field generation means for applying a magnetic field to the substrate. The magnetic field generation means is fixed to the substrate pallet. When the substrate pallet is transported by the transport means, the magnetic field generation means is transported together with the substrate pallet in the vacuum container.
In the magnetic film forming system according to the first embodiment of the invention, a substrate on which a film is formed is retained on the substrate pallet and the substrate together with the substrate pallet can be transported in the vacuum container and taken out therefrom. When a film is formed, the substrate together with the substrate pallet is supported by the support means in the vacuum container. The film forming means forms a film on the substrate on the substrate pallet supported by the support means. The magnetic film generation means applies a magnetic field to the substrate and orients the magnetization direction of a film when it is formed.
In the invention, the magnetic field generation means, which is fixed to the substrate pallet, always applies a magnetic field to the substrate in a constant direction unless the substrate slips off the substrate pallet. Therefore, a magnetic field is always applied to the substrate in a constant direction not only when a film is formed, but also while the substrate pallet is moved in the vacuum container or taken out therefrom. So long as the substrate is held on the substrate pallet, a magnetic field is applied regardless of where the substrate is placed in the vacuum container or whether it is placed inside or outside the vacuum container. Thus, even if the substrate is moved before a film is cooled, film orientation does not vary. Further, since the magnetic field generation means is mounted on the same substrate pallet as the substrate, a magnetic field can be applied at close range. Small magnetic field generation means having a small magnetic field strength can apply a magnetic field efficiently, implementing a small system. Since the magnetic field generation means is taken out from the system together with the substrate pallet, the magnetic field direction can also be adjusted easily.
The magnetic film forming system according to the second embodiment of the invention is provided with means for transporting the substrate pallet in the vacuum container. The vacuum container can also be divided into a number of process chambers. In such an inline film forming system, while a substrate is transported from one chamber to another, a magnetic filed is always applied to the substrate in a constant direction by the magnetic field generation means on the substrate pallet, thus there is no risk of the magnetic field application direction varying slightly between each process chamber. Further, since the magnetic field generation means is mounted on the same substrate pallet as the substrate, a magnetic field can be efficiently applied at close range by small magnetic generation means, implementing a small inline film forming system. Since the magnetic field generation means is taken out from the system together with the substrate pallet, the magnetic field direction can also be adjusted easily even if the inline magnetic film forming system comprises a plurality of process chambers.


The invention relates to a hydrocracking catalyst comprising at least one amorphous or poorly crystallized matrix of the oxide type, at least one element of group VB, preferably niobium, and at least one zeolite Y not globally dealuminized, at least one promoter element chosen from the group consisting of boron, phosphorus and silicon, optionally at least one element chosen from the elements of group VIB and group VIII, optionally at least one element of group VIIA. The invention also relates to the use of this catalyst for hydrocracking hydrocarbon feeds.

The present invention relates to hydrocracking hydrocarbon feeds, with a catalyst comprising at least one amorphous or poorly crystallized matrix of the oxide type, at least one element (metal) of group VB (group 5 according to the new coding of the period classification of the elements: Handbook of Chemistry and Physics, 76th edition, 1995-1996, inside first cover page), preferably niobium, at least one zeolite Y not globally dealuminized, at least one promoter element chosen from the group consisting of boron, phosphorus and silicon, optionally at least one element (metal) chosen from group VIB and/or group VIII (group 6 and groups 8, 9 and 10 according to the new coding of the period classification of the elements), preferably molybdenum and tungsten, cobalt, nickel and iron. The catalyst also optionally comprises at least one element of group VIIA (halogen group, group 17 according to the new coding of the periodic classification of the elements), such as, for example, fluorine.
Hydrocarbon feeds, such as petroleum cuts, cuts produced from coal containing aromatic and/or olefinic and/or naphthenic and/or paraffinic compounds, the said feeds optionally comprising metals, and/or nitrogen, and/or oxygen, and/or sulphur can be beneficially hydrocracked according to the invention.
Hydrocracking of heavy petroleum cuts is a very important process in refining with which, starting from excess heavy feeds of low value, lighter fractions such as gasolines, jet fuels and light gas oils can be produced, which the refiner requires in order to adapt his production to the demand structure. Some hydrocracking processes also allow production of a highly purified residue which can constitute excellent bases for oils. In contrast to catalytic cracking, the advantage of catalytic hydrocracking is that middle distillates, jet fuels and gas oils of very good quality are provided. The gasoline produced has an octane index much lower than that produced from catalytic cracking.
The catalysts used in hydrocracking are all of the bifunctional type combining an acid function and a hydrogenating function. The acid function is carried by supports of large surface area (generally 150 to 800 m2.gxe2x88x921 ) having a superficial acidity, such as halogenated (in particular chlorinated or fluorinated) aluminas, combinations of oxides of boron and aluminium, amorphous silica-aluminas and clays. The hydrogenating function is carried either by one or more metals of group VIII of the periodic classification of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by a combination of at least one metal of group VI of the periodic classification, such as molybdenum and tungsten, and at least one metal of group VIII.
The equilibrium between the two acid and hydrogenating functions is the fundamental parameter which regulates the activity and selectivity of the catalyst. A weak acid function and a strong hydrogenating function give catalysts of low activity working in general at an elevated temperature (greater than or equal to 390xc2x0 C.) and a low hourly volume velocity (the HVV, expressed in volume of feed to be treated per unit volume of catalyst and per hour, is generally less than or equal to 2), but having a very good selectivity in middle distillates. Conversely, a strong acid function and a low hydrogenating function give catalysts which are active but have less good selectivities in middle distillates. The search for a suitable catalyst will therefore be centred on a judicial choice of each of the functions to adjust the catalyst activity/selectivity relationship.
It is thus one of the great advantages of hydrocracking to have a high flexibility at various levels: flexibility at the level of the catalysts used, which leads to a flexibility in the feedes to be treated, and at the level of the products obtained. A parameter which is easy to control is the acidity of the catalyst support.
The conventional catalysts of catalytic hydrocracking are in the great majority made up of weakly acid supports, such as amorphous silica-aluminas, for example. These systems are more particularly used to produce middle distillates of very good quality, and also, if their acidity is very weak, oil bases.
Among the supports of little acidity is found the family of amorphous silica-aluminas. Many catalysts on the hydrocracking market are based on silica-alumina combined either with a metal of group VIII or, preferably, if the contents of heteroatomic poisons in the feed to be treated exceed 0.5% by weight, a combination of sulphides of metals of groups VIB and VIII. These systems have a very good selectivity in middle distillates, and the products formed are of good quality. The less acid catalysts among these can also produce lubricant bases. The disadvantage of all these catalytic systems based on an amorphous support is, as has been said, their low activity.
On the other hand, simple sulphides of elements of group VB have been described as constituents of catalysts for hydrorefining hydrocarbon feeds, such as, for example, niobium trisulphide in the patent U.S. Pat. No. 5,294,333. Mixtures of simple sulphides comprising at least one element of group VB and an element of group VIB have also been tested as constituents of catalysts for hydrorefining hydrocarbon feedes, such as, for example, in the patent U.S. Pat. No. 4,910,181 or the patent U.S. Pat. No. 5,275,994.
Research work carried out on zeolites and on the active hydrogenating phases led surprisingly to the discovery of a catalyst for hydrocracking hydrocarbon feeds comprising at least one amorphous or poorly crystallized, generally porous matrix, such as alumina, at least one element of group VB of the periodic classification of the elements, such as tantalum, niobium and vanadium, preferably niobium, at least one zeolite Y not globally dealuminized and with a unit cell parameter (or crystalline parameter) greater than 2.438 nm, preferably greater than 2.442 nm, and very preferably greater than 2.455 nm, and a global SiO2/Al2O3 ratio of less than 8, preferably less than 7.5, very preferably less than 7, and at least one promoter element chosen from the group consisting of boron, phosphorus and silicon . . .
The catalyst also optionally comprises at least one element of group VIB of the said classification, such as chromium, molybdenum and tungsten, preferably molybdenum or tungsten, and more preferably molybdenum, optionally an element of group VIII, that is to say an element chosen from the group consisting of: Fe, Ru, Os, Co, Rh, Ir, Ni, Pd and Pt, preferably iron, cobalt, nickel or ruthenium, and optionally an element of group VIIA, preferably fluorine.
The catalyst has a hydrocracking activity which is greater than that of catalytic formulations based on an element of group VIB which are known from the prior art.
The catalyst of the present invention generally comprises, in % by weight with respect to the total weight of the catalyst:
0.1 to 99.8%, preferably 0.1 to 90%, more preferably 0.1 to 80%, and very preferably 0.1 to 70% of at least one zeolite Y not globally dealuminized and having a unit cell parameter which is greater than 2.438 nm, preferably greater than 2.442 nm, and very preferably greater than 2.455 nm, and a global SiO2/Al2O3 ratio of less than 8, preferably less than 7.5, very preferably less than 7,
0.1 to 60%, preferably 0.1 to 50%, and more preferably 0.1 to 40% of at least one element chosen from group VB,
0.1 to 99%, preferably 1 to 99% of at least one amorphous or poorly crystallized porous mineral matrix of the oxide type,
0.1 to 20%, preferably 0.1 to 15%, and more preferably 0.1 to 10% of at least one promoter element chosen from the group consisting of boron, phosphorus and silicon, excluding the silicon optionally contained in the zeolite, it being possible for the catalyst also to comprise:
0 to 60%, preferably 0.1 to 50%, and more preferably 0.1 to 40% of at least one element chosen from the elements of group VIB and group VIII, and
0 to 20%, preferably 0.1 to 15%, and more preferably 0.1 to 10% of at least one element chosen from group VIIA, preferably fluorine.
If it is present, the promoter element silicon is in amorphous form and located chiefly on the matrix. The elements of group VB, VIB and of group VIII of the catalyst of the present invention can be present entirely or partly in the metallic and/or oxide and/or sulphide form.
The catalysts according to the invention can be prepared by any methods known to the man skillet in the art.
A preferred process for the preparation of the catalyst according to the present invention comprises the following stages:
a) a solid called the precursor comprising at least the following compounds is dried and weighed: at least one matrix, at least one zeolite Y not globally dealuminized, optionally at least one promoter element chosen from the group consisting of boron, phosphorus and silicon, optionally at least one element chosen from the elements of group VIB and group VIII, and optionally at least one element of group VIIA, the entire mixture preferably being shaped,
b) the dry solid obtained in stage a) is calcined at a temperature of at least 150xc2x0 C., preferably at least 450xc2x0 C.,
c) the precursor solid defined in stage b) is impregnated with a solution comprising at least one element of group VB, preferably niobium,
d) the moist solid is left to stand in a damp atmosphere at a temperature of between 10 and 120xc2x0 C.,
e) the moist solid obtained in stage d) is dried at a temperature of between 60 and 150xc2x0 C.,
f) the solid dried in stage e) is calcined in dry air at a temperature of at least 150xc2x0 C., preferably at least about 250xc2x0 C.
The solid obtained at the end of any one of stages a) to e) can be impregnated by at least one solution comprising all or some of at least one element chosen from the elements of group VIB and group VIII, optionally at least one promoter element chosen from the group consisting of boron, phosphorus and silicon, and optionally at least one element of group VIIA.
The preparation of the precursor of stage a) above can be carried out by any of the conventional methods of the man skilled in the art. According to a preferred preparation process, the precursor is obtained by mixing at least one matrix and at least one non-dealuminized zeolite Y and then shaping, drying, and calcining the mixture. The promoter element or elements chosen from the group consisting of boron, phosphorous, and silicon and that or those chosen from the elements of groups VIB, VIII and/or from the elements of group VIIA are then introduced by any method known to the man skilled in the art at any one of stages a) and e), before or after the shaping and before or after the calcination of the said mixture.
The shaping can be carried out, for example, by extrusion, by pelletizing, by the oil-drop method, by rotary plate granulation or by any other method well-known to the man skillet in the art. At least one calcination can be carried out after any one of the preparation stages, and it is usually carried out in air at a temperature of at least 150xc2x0 C., preferably at least 300xc2x0 C. The product obtained at the end of stage a) and/or of stage e) and/or optionally after introduction of the element or elements chosen from the elements of groups VIB, VIII, and/or from the promoter elements of the group consisting of boron, phosphorus and silicon, and/or from the elements of group VIIA is then thus optionally calcined in air, usually at a temperature of at least 150xc2x0 C., preferably at least 250xc2x0 C., more preferably between about 350 and 1,000xc2x0 C.
The hydrogenating element can be introduced at any stage of the preparation, preferably during mixing, or very preferably after shaping. The shaping is followed by a calcination and the hydrogenating element is introduced before or after this calcination. In all cases, the preparation ends by a calcination at a temperature of 250 to 600xc2x0 C. One of the preferred methods in the present invention comprises kneading at least one zeolite in a moist alumina gel for some minutes and then passing the paste thus obtained through a die to form extrudates with a diameter of between 0.4 and 4 mm. The hydrogenating function can then be introduced only in part (in the case, for example, of combinations of oxides of metals of groups VIB and VIII) or in total at the time of kneading of the zeolite, that is to say of at least one non-dealuminized zeolite Y, with at least one oxide gel chosen as the matrix. It can be introduced by one or more ion exchange operations on the calcined support comprising at least one zeolite dispersed in at least one matrix, with the aid of solutions comprising the precursor salts of the metals chosen, if these belong to group VIII. It can be introduced by one or more impregnation operations on the shaped and calcined support with a solution of the precursors of the oxides of metals of groups VIII (in particular cobalt and nickel) if the precursors of the oxides of metals of group VIB (in particular molybdenum or tungsten) have been introduced beforehand at the time of kneading of the support. Finally, it can be introduced by one or more impregnation operations on the calcined support comprising at least one non-dealuminized zeolite Y and at least one matrix with solutions comprising the precursors of the oxides of metals of groups VIB and/or VIII, the precursors of the oxides of metals of group VIII preferably being introduced after those of group VIB or at the same time as the latter.
Another preferred preparation process comprises introducing at least one element of group VB and at least one element chosen from the elements of group VIII and group VIB into a mixture of at least one matrix with at least one non-dealuminized zeolite Y, before or after shaping and before or after calcination of the said mixture.
Preferably, the support is impregnated with an aqueous solution. The impregnation of the support is preferably carried out by incipient wetness impregnation method well-known to the man skillet in the art. The impregnation can be carried out in a single stage with a solution comprising all the elements making up the final catalyst.
Boron and/or phosphorus and/or silicon and optionally the element chosen from group VIIA of halide ions, preferably fluorine, can be introduced into the catalyst at various stages of the preparation by any technique known to the man skilled in the art.
A method which is preferred according to the invention comprises depositing, for example by impregnation, the promoter element or elements chosen, for example the boron-silicon pair, on the calcined or non-calcined, preferably calcined, precursor. For this, an aqueous solution of at least one boron salt, such as ammonium diborate or ammonium pentaborate, is prepared in an alkaline medium in the presence of hydrogen peroxide and an impregnation, so-called in the dry state, in which the pore volume of the precursor is filled with the solution comprising boron, is carried out. In the case where silicon, for example, is deposited a solution of a silicon compound of the silicone type, for example, will be used.
The deposition of boron and silicon can also be carried out simultaneously using, for example, a solution comprising a boron salt and a silicon compound of the silicone type. Thus, for example, in the case where the precursor is a catalyst of the nickel-molybdenum type supported on alumina and zeolite chosen from the group consisting of non-dealuminized zeolites Y, it is possible to impregnate this precursor with the aqueous solution of ammonium diborate and silicone Rhodorsil E1P from the company Rhxc3x4ne Poulenc, to carry out a drying, for example at 80xc2x0 C., and then to impregnate with a solution of ammonium fluoride, to carry out a drying, for example at 80xc2x0 C., and to carry out a calcination, for example and preferably in air in a flow-through bed, for example at 500xc2x0 C. for 4 hours. The element of group VB is then deposited by any method known to the man skilled in the art.
The promoter element chosen from the group formed by boron, phosphorus and silicon and the element chosen from the halogens of group VIIA can also be introduced by one or more impregnation operations, for example with excess solution, on the calcined precursor.
Thus, for example, it is possible to impregnate the precursor with an aqueous solution of ammonium diborate and/or silicone Rhodorsil E1P from the company Rhxc3x4ne Poulenc, to carry out a drying, for example at 80xc2x0 C., and then to impregnate with a solution of ammonium fluoride, to carry out a drying, for example at 80xc2x0 C., and to carry out a calcination, for example and preferably in air in a flow-through bed, for example at 500xc2x0 C. for 4 hours. The element of group VB is then deposited by any method known to the man skillet in the art.
Other impregnation sequences can be used to obtain the catalyst of the present invention.
For example, it is possible to impregnate the precursor with a solution comprising one of the promoter elements (B, P, Si), to dry it and calcine it, and then to impregnate the solid obtained with the solution comprising another promoter element, and to dry it and calcine it. It is also possible to impregnate the precursor with a solution comprising two of the promoter elements, to dry it and to calcine it, and then to impregnate the solid obtained with the solution comprising another promoter element, to dry it and to carry out a final calcination. The element of group VB is then deposited by any method known to the man skillet in the art.
The catalyst of the present invention can comprise an element (metal) of group VIII, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium or platinum. Among the elements of group VIII, an element chosen from the group formed by iron, cobalt, nickel and ruthenium is preferably employed. Combinations of the following elements are advantageously used: nickel-niobium-molybdenum, cobalt-niobium-molybdenum, iron-niobium-molybdenum, nickel-niobium-tungsten, cobalt-niobium-tungsten and iron-niobium-tungsten, the preferred combinations being: nickel-niobium-molybdenum and cobalt-niobium-molybdenum. It is also possible to use combinations of four elements, for example nickel-cobalt-niobium-molybdenum. Combinations comprising a noble metal, such as ruthenium-niobium-molybdenum, or ruthenium-nickel-niobium-molybdenum, can also be used.
In the case where the elements are introduced in several impregnations with corresponding precursor salts, a stage of intermediate calcination of the catalyst should generally be carried out at a temperature of between 250 and 600xc2x0 C. The impregnation with molybdenum can be facilitated by addition of phosphoric acid into solutions of ammonium paramolybdate, which also enables introduction of phosphorus in a manner which promotes the catalytic activity. Other compounds of phosphorus can be used, as is well-known to the man skilled in the art.
The impregnation with niobium can be facilitated by addition of oxalic acid and optionally ammonium oxalate into solutions of niobium oxalate. Other compounds can be used to improve the solubility and facilitate the impregnation of niobium, as is well-known to the man skillet in the art.
The sulphurization can be carried out by any method known to the man skilled in the art. The method preferred according to the invention comprises heating the non-calcined catalyst in a stream of a hydrogen/hydrogen sulphide mixture or in a stream of a nitrogen/hydrogen sulphide mixture, or also under pure hydrogen sulphide at a temperature of between 150 and 800xc2x0 C., preferably between 250 and 600xc2x0 C., generally in a flow-through bed reaction zone.
The usually amorphous or poorly crystallized porous mineral matrix in general comprises at least one refractory oxide in amorphous or poorly crystallized form. The said matrix is usually chosen from the group formed by alumina, silica, silica-alumina or a mixture of at least two of the abovementioned oxides. Aluminates can also be chosen. Matrices comprising alumina in all these forms known to the man skilled in the art, for example gamma-alumina, are preferably used.
The sources of the element of group VB which can be used are well-known to the man skillet in the art. For example, among the sources of niobium it is possible to use the oxides, such as diniobium pentoxide Nb2O5, niobium acid Nb2O5.H2O, niobium hydroxides and polyoxoniobates, niobium alkoxides of the formula Nb(OR1)3, where R1 is an alkyl radical, niobium oxalate NbO(HC2O4)5 and ammonium niobate. Niobium oxalate or ammonium niobate is preferably used.
The non-dealuminized zeolite Y is characterized by a unit cell parameter greater than 2.438 nm, preferably greater than 2.442 nm, and very preferably greater than 2.455 nm, and a global SiO2/Al2O3 ratio of less than 8, preferably less than 7.5, very preferably less than 7.
Preferaby a zeolite Y not globally deluminized and also having the followin properties is used:
a molar SiO2/Al2O3 ratio of the skeleton greater than the global molar SiO2/Al2O3 ratio and less than about 21 [calculated according to the so-called Fichtner-Schmittler correlation (in Cryst. Res. Techn. 1984, 19, K1)],
a content of alkaline earth or alkali metals of less than 0.2% by weight, determined on the zeolite calcined at 1,100xc2x0 C.,
a specific surface area, determined by the BET method, greater than about 400 m2/g, and preferably greater than 600 m2/g.
The source of sulphur can be elemental sulphur, carbon disulphide, hydrogen sulphide, sulphur hydrocarbons, such as dimethyl sulphide, dimethyl disulphide; mercaptans and thiophene compounds, thiols, polysulphides, such as, for example, ditert-nonyl polysuiphide or TPS-37 from the company ATOCBEM, and petroleum cuts rich in sulphur, such as gasoline, kerosene and as oil, by themselves or in mixtures with one of the abovementioned sulphur compounds. The preferred source of sulphur is carbon disulphide or hydrogen sulphide.
The preferred source of phosphorus is orthophosphoric acid H3PO4, but its salts and esters, such as ammuonium phosphates, are also suitable. The phosphorus can be introduced, for example, in the form of a mixture of phosphoric acid and a basic organic compound containing, nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine and quinoline family and compounds of the pyrrole family.
Numerous sources of silicon can be employed. It is thus possible to use ethyl orthosilicate Si(OEt)4, siloxanes, polysiloxanes, silicones, silicone emulsions and halide silicates, such as ammonium fluorosilicate (NH4)2SiF6 or sodium fluorosilicate Na2SiF6. Silicomolybdic acid and its salts and silicotungstic acid and its salts can also advantageously be employed. Silicon can be added, for example, by impregnation with ethyl silicate dissolved in a water/alcohol mixture. Silicon can also be added, for example, by impregnation with a silicon compound of the silicone type suspended in water.
The source of boron can be boric acid, preferably orthoboric acid H3BO4, ammonium diborate or pentaborate, boron oxide and boric esters. Boron can be introduced, for example, in the form of a mixture of boric acid, hydrogen peroxide and a basic organic compound containing nitrogen, such as ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine and quinoline family and compounds of the pyrrole family. Boron can be introduced, for example, by means of a solution of boric acid in a water/alcohol mixture.
The sources of group VIIA elements which can be used are well-known to the man skilled in the art. For example, fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or an organic compound. In the latter case, the salt is advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid. It is also possible to use hydrolysable compounds which can liberate fluoride ions in water, such as ammonium fluorosihcate (NH4)2SiF6, silicon tetrafluoride SiF4 or sodium tetrafluoride Na2SiF6. The fluorine can be introduced, for example, by impregnation with an aqueous solution of hydrofluoric acid or ammonium fluoride.
The sources of group VIB elements which can be used are well-known to the man skilled in the art. For example, among the sources of molybdenum and tungsten, it is possible to use the oxides and hydroxides, molybdic and tungstic acids and their salts, in particular the ammonium salts, such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid and silicotungstic acid and their salts. The oxides and the ammonium salts, such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate, are preferably used.
The sources of group VIII elements which can be used are well-known to the man skilled in the art. For example, for the non-noble metals the nitrates, the sulphates, the phosphates, the halides, for example chlorides, bromides and fluorides, the carboxylates, for example acetates, and carbonates will be used. For the noble metals the halides, for example the chlorides, the nitrates, the acids, such as chloroplatinic acid, and the oxychlorides, such as ammoniacal ruthenium oxychloride, will be used.
The catalysts obtained by the present invention are shaped in the form of particles of different shape and dimensions. They are in general used in the form of extrudates which are cylindrical or polylobic, such as bilobic, trilobic or polylobic in straight or twisted form, but can also be produced and employed in the form of crushed powder, tablets, rings, beads or coils. They have a specific surface area, measured by adsorption of nitrogen by the BET method (Brunauer, Emmett, Teller, J. Am. Chem. Soc., vol. 60, 309-316 (1938)) of between about 50 and about 600 m2/g, a pore volume, measured by mercury porosimetry, of between about 0.2 and about 1.5 cm3/g, and a pore size distribution which can be monomodal, bimodal or polymodal.
The catalysts obtained by the present invention are used for hydrocracking of hydrocarbon feeds such as petroleum cuts. The feeds employed in the process are gasolines, kerosenes, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, heavy fuels, oils, waxes and paraffins, used oils, deasphalted residues or crude oils, feeds originating from thermal or catalytic conversion processes and their mixtures. They contain heteroatoms, such as sulphur, oxygen and nitrogen, and optionally metals.
The catalysts thus obtained are advantageously used for hydrocracking of, in particular, heavy hydrocarbon cuts of the type of vacuum distillates or deasphalted or hydrotreated residues or equivalents. The heavy cuts preferably comprise at least 80% by volume of compounds of which the boiling points are at least 350xc2x0 C., and preferably between 350 and 580xc2x0 C. (that is to say corresponding to compounds containing at least 15 to 20 carbon atoms). They generally contain heteroatoms, such as sulphur and nitrogen. The nitrogen content is usually between 1 and 5,000 ppm by weight and the sulphur content between 0.01 and 5% by weight.
The hydrocracking conditions, such as temperature, pressure, hydrogen recycling level and hourly volume velocity, can vary widely as a function of the nature of the feed, the quality of the desired products and the installations available to the refiner. The temperature is in general greater than 200xc2x0 C., and preferably between 250xc2x0 C. and 480xc2x0 C. The pressure is greater than 0.1 MPa, and preferably greater than 1 MPa. The amount of hydrogen is at least 50, and often between 80 and 5,000 normal liters of hydrogen per liter of feed. The hourly volume velocity is in general between 0.1 and 20 volumes of feed per volume of catalyst and per hour.
The catalysts of the present invention are preferably subjected to a sulphurization treatment to convert at least a portion of the metallic species into sulphide before they are brought into contact with the feed to be treated. This activation treatment by sulphurization is well-known to the man skilled in the art and can be carried out by any method already described in the literature, either in situ, that is to say in the hydrocracking reactor, or ex situ.
A conventional sulphurization method which is well-known to the man skilled in the art comprises heating in the presence of hydrogen sulphide at a temperature of between 150 and 800xc2x0 C., preferably between 250 and 600xc2x0 C., in general in a flow-through bed reaction zone.
The catalyst of the process of the present invention can advantageously be employed for hydrocracking of cuts of the vacuum distillate type highly charged with sulphur and nitrogen, and more particularly, for example, cuts with a sulphur content greater than 0.1% by weight and a nitrogen content greater than 10 ppm.
In a first embodiment or partial hydrocracking, also called gentle hydrocracking, the conversion level is less than 55%. The catalyst according to the invention is then employed at a temperature in general greater than or equal to 230xc2x0 C., preferably between 300xc2x0 C. and 480xc2x0 C., and more preferably between 350xc2x0 C. and 450xc2x0 C. The pressure is preferably greater than 2 MPa, more preferably 3 MPa, and preferably less than 12 MPa, more preferably less than 10 MPa. The amount of hydrogen is at least 100 normal liters of hydrogen per liter of feed, and preferably between 200 and 3,000 normal liters of hydrogen per liter of feed. The hourly volume velocity is preferably between 0.15 and 10 volumes of feed per volume of catalyst and per hour. Under these conditions, the catalysts of the present invention have a better conversion, hydrodesulphurization and hydrodenitrogenation activity than commercial catalysts.
In a second embodiment, the catalyst of the process of the present invention can be employed for partial hydrocracking, advantageously under conditions of a moderate pressure of hydrogen, of cuts for example of the vacuum-distillate type which are highly charged with sulphur and nitrogen and have been hydrotreated beforehand. In this method of hydrocracking, the conversion level is less than 55%. In this case, the petroleum cut conversion process takes place in two stages, the catalysts according to the invention being used in the second stage. The catalyst of the first stage has a hydrotreatment function and comprises a matrix preferably based on alumina, and preferably does not comprise zeolite, and at least one metal having a hydrogenating function. The said matrix is an amorphous or poorly crystallized porous mineral matrix of the oxide type. There may be mentioned by way of non-limiting example aluminas, silicas and silica-aluminas. Aluminates can also be chosen. Matrices comprising alumina in all these forms known to the man skillet in the art are preferably used, and more preferably aluminas, for example gamma-alumina. The hydrotreatment function is ensured by at least one metal or metal compound of group VIII, such as nickel and cobalt in particular. A combination of at least one metal or metal compound of group VIB (for example molybdenum or tungsten) and at least one metal or metal compound of group VIII (for example cobalt or nickel) of the periodic classification of the elements can be used. The total concentration of oxides of metals of groups VIB and VIII is preferably between 5 and 40% by weight, and more preferably between 7 and 30% by weight, and the weight ratio, expressed in oxide of metal (metals) of group VIB to oxide of metal (metals) of group VIII is preferably between 1.25 and 20, and more preferably between 2 and 10. Furthermore, this catalyst can comprise phosphorus. The phosphorus content, expressed as the concentration of diphosphorus pentoxide P2O5. will preferably be at most 15%, more preferably between 0.1 and 15% by weight, and very preferably between 0.15 and 10% by weight. It can also comprise boron in a B/P ratio of preferably between 1.05 and 2 (atomic), the total contents of boron (B) and phosphorus (P), expressed as oxides, preferably being between 5 and 15% by weight.
The first stage in general takes place at a temperature between 350 and 460xc2x0 C., preferably between 360 and 450xc2x0 C., a total pressure of at least 2 MPa, preferably at least 3 MPa, an hourly volume velocity of between 0.1 and 5 volumes of feed per volume of catalyst and per hour, preferably between 0.2 and 2 volumes of feed per volume of catalyst and per hour, and with an amount of hydrogen of at least 100 normal liters per liter of feed, and preferably between 260 and 3,000 normal liters per liter of feed.
For the conversion stage with the catalyst according to the invention (or second stage), the temperatures are in general greater than or equal to 230xc2x0 C., and often between 300xc2x0 C. and 480xc2x0 C., and preferably between 300 and 450xc2x0 C. The pressure is in general at least 2 MPa, and preferably at least 3 MPa. The amount of hydrogen is at least 100 normal liters of hydrogen per liter of feed, and preferably between 200 and 3,000 liters of hydrogen per liter of feed. The hourly volume velocity is preferably between 0.15 and 10 volumes of feed per volume of catalyst and per hour. Under these conditions, the catalysts of the process of the present invention have a better conversion, hydrodesulphurization and hydrodenitrogenation activity and a better selectivity in middle distillates than the commercial catalysts. The life of the catalysts is also improved in the range of moderate pressure.
In another embodiment, the catalyst of the process of the present invention can be employed for hydrocracking under elevated hydrogen pressure conditions, in general at least 5 MPa. The cuts treated are, for example, of the vacuum distillate type which are highly charged with sulphur and nitrogen and have been hydrotreated beforehand. In this hydrocracking method, the conversion level is greater than 55%. In this case, the petroleum cut conversion process takes place in two stages, the catalyst according to the invention being used in the second stage.
The catalyst of the first stage has a hydrotreatment function and comprises a matrix preferably based on alumina, and preferably not comprising zeolite, and at least one metal having a hydrogenating function. The said matrix can also comprise or contain silica, silica-alumina, boron oxide, magnesia, zirconia, titanium oxide or a combination of these oxides. The hydro-dehydrogenating function is ensured by at least one metal or metal compound of group VIII, such as nickel and cobalt in particular. A combination of at least one metal or metal compound of group VIB (for example molybdenum or tungsten) and at least one metal or metal compound of group VIII (for example cobalt or nickel) of the periodic classification of the elements can be used. The total concentration of oxides of metals of groups VIB and VIII is preferably between 5 and 40% by weight, and more preferably between 7 and 30% by weight, and the weight ratio, expressed in metallic oxide of metal (or metals) of group VIB to metal (or metals) of group VIII is preferably between 1.25 and 20, and more preferably between 2 and 10. Furthermore, this catalyst can optionally comprise phosphorus. The phosphorus content, expressed as the concentration of diphosphorus pentoxide P2O5, will 25 preferably be at most 15%, more preferably between 0.1 and 15% by weight, and very preferably between 0.15 and 10% by weight. It can also comprise boron in a B/P ratio of preferably between 1.02 and 2 (atomic), the total contents of boron (B) and phosphorus (P), expressed as oxides, being preferably between 5 and 15% by weight.
The first stage in general takes place at a temperature between 350 and 460xc2x0 C., preferably between 360 and 450xc2x0 C., a pressure of at least 2 MPa, preferably at least 3 MPa, an hourly volume velocity of between 0.1 and 5 volumes of feed per volume of catalyst and per hour, preferably between 0.2 and 2 volumes of feed per volume of catalyst and per hour, and with an amount of hydrogen of at least 100 normal liters of hydrogen per liter of feed, and preferably between 260 and 3,000 normal liters of hydrogen per liter of feed.
For the conversion stage with the catalyst according to the process of the invention (or second stage), the temperatures are in general greater than or equal to 230xc2x0 C., often between 300xc2x0 C. and 480xc2x0 C., and preferably between 330xc2x0 C. and 440xc2x0 C. This pressure is in general greater than 5 MPa, and preferably greater than 7 MPa. The amount of hydrogen is at least 100 normal liters of hydrogen per liter of feed, and preferably between 200 and 3,000 liters of hydrogen per liter of feed. The hourly volume velocity is preferably between 0.15 and 10 volumes of feed per volume of catalyst and per hour.
Under these conditions, the catalysts of the process of the present invention have a better conversion activity than the commercial catalysts.

Hydrocracking process with catalyst comprising a zeolite Y not globally dealuminized, an element of group VB, and a promoter element of boron, phosphorus and silicon