text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 25, 1984
|Filing date
|Apr 26, 1983
|Priority date
|Apr 26, 1983
|Fee status
|Also published as
|Publication number
|Tai-Sheng Chou
|Original Assignee
|Mobil Oil Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (17), Referenced by (39), Classifications (8), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
This invention relates to an improved process of increasing gasoline octane number and total yield while also increasing operational flexibility in catalytic cracking units by the addition of an additive catalyst to conventional cracking catalysts.
2. Description of the Prior Art
Hydrocarbon conversion processes utilizing crystalline zeolites have been the subject of extensive investigation during recent years, as is obvious from both the patent and scientific literature. Crystalline zeolites have been found to be particularly effective for a wide variety of hydrocarbon conversion processes, including the catalytic cracking of a gas oil to produce motor fuels and have been described and claimed in many patents, including U.S. Pat. Nos. 3,140,249; 3,140,251; 3,140,252; 3,140,253; and 3,271,418. It is also known in the prior art to incorporate the crystalline zeolite into a matrix for catalytic cracking and such disclosure appears in one or more of the above-identified U.S. patents.
It is also known that improved results are obtained with regard to the catalytic cracking of gas oils if a crystalline zeolite having a pore size of less than 7 Angstrom units is included with a crystalline zeolite having a pore size greater than 8 Angstrom units, either with or without a matrix, see, e.g., U.S. Pat. No. 3,769,202. Although the incorporation of a crystalline zeolite having a pore size of less than 7 Angstrom units into a catalyst composite comprising a larger pore size crystalline zeolite (pore size greater than 8 Angstrom units) has indeed been very effective with respect to the raising of octane number, nevertheless it did so at the expense of the overall yield of gasoline.
In order to reduce automobile exhaust emissions to meet federal and state pollution requirements, many automobile manufacturers have equipped the exhaust systems of their vehicles with catalytic converters. Said converters contain catalysts which are poisoned by tetraethyl lead. Since tetraethyl lead has been widely used to boost the octane number of gasoline, refiners now have to turn to alternate means to improve gasoline octane number.
Many methods of octane improvement, however, reduce the yield of gasoline. With the present short supply of available crude oil and the concomitant high demand for unleaded gasoline with a sufficiently high octane number, refiners are faced with a severe dilemma. These trends are likely to continue in the foreseeable future.
One method of increasing octane number is to raise the cracker reactor temperature. This method, however, is very limited, since many units are now operating at maximum temperatures due to metallurgical limitations. Increasing the cracker reactor temperature also results in increased requirements for the downstream gas plant (i.e. gas compressor and separator). Since most gas plants are now operating at maximum capacity, any increased load could not be tolerated by the present equipment.
Improved results in catalytic cracking with respect to both octane number and overall yield are claimed in the process of U.S. Pat. No. 3,758,403. In said patent, the cracking catalyst was comprised of a large pore size crystalline zeolite (pore size greater than 7 Angstrom units) in admixture with ZSM-5 type zeolite wherein the ratio of ZSM-5 type zeolite to large pore size crystalline zeolite was in the range of 1:10 to 3:1.
The use of ZSM-5 type zeolite in conjunction with a zeolite cracking catalyst of the X or Y faujasite variety is described in U.S. Pat. Nos. 3,894,931; 3,894,933; and 3,894,934. The two former patents disclose the use of ZSM-5 type zeolite in amounts up to about 5 to 10 weight percent; the latter patent discloses the weight ratio of ZSM-5 type zeolite to large pore size crystalline zeolite in the range of 1:10 to 3:1.
The processes of U.S. Pat. Nos. 4,309,279 and 4,368,114 are predicated on the criticality of using only miniscule amounts of additive catalyst comprising ZSM-5 class zeolite to achieve improved results with respect to octane number and overall yield. In those processes 0.1 to 0.5% wt of ZSM-5 class catalyst gives the same beneficial results that were once thought obtainable only by adding much larger quantities of ZSM-5 class catalyst.
However, the ZSM-5 type zeolite catalyst, used as an additive catalyst in prior art cracking processes, was injected into the process at such locations that its residence time in the regenerator unit of the process was substantial. This, it is believed, contributed to a rapid aging of the ZSM-5 type zeolite, thereby necessitating frequent additions of substantial amounts of makeup additive catalyst. It is also believed that the circulation of the ZSM-5 type zeolite catalyst through the stripper and the riser mixing zone contributed substantially to the rapid deactivation of the additive catalyst.
It is a primary object of the present invention to decrease the extent of deactivation of the ZSM-5 type zeolite additive catalyst experienced in the prior art cracking processes.
It is an additional object of the present invention to decrease or substantially eliminate the circulation of the ZSM-5 type zeolite catalyst in the riser mixing zone, stripper and regenerator of the cracking reactor.
Other objects of the invention will be apparent to those skilled in the art from the following description of the invention and from appended claims.
FIG. 1 is a schematic illustration of fluid catalytic (FCC) plant utilizing the present invention.
FIG. 2 is a section view, taken along plane A--A, of the regenerator of the plant of FIG. 1.
FIG. 3 is a schematic illustration of a secondary regenerization means wherein the additive zeolite of ZSM-5 type is regenerated.
The ZSM-5 type additive zeolite is introduced into a catalytic cracking riser reactor at a point which is at least 5% of the total riser reactor length downstream from the point of introduction of the hydrocarbonaceous feed into the riser reactor. The additive catalyst, admixed with a conventional cracking catalyst and the feedstock, is then conducted to a conventional downstream reactor separation means wherein a first process stream comprising the ZSM-5 type zeolite and conventional cracking catalyst fines is separated from a second process stream comprised of the remainder of the conventional catalyst. The first process stream is regenerated in a secondary regeneration vessel, separately from the second process stream which is regenerated in a conventional cracking catalyst regenerator.
The ZSM-5 type zeolite is introduced into the riser of the catalytic cracking reactor at a point at least 5%, preferably at least 10%, of the total riser reactor length downstream from the point of introduction of the primary hydrocarbonaceous feed stream into the riser reactor. The term total riser reactor length is defined herein as the length extending from the discharge of the primary feed oil nozzle and terminating at the point of exit of the mixture of the catalyst and cracked feed from the riser. The term primary feed oil nozzle is defined herein as the nozzle discharging the primary relatively high volume feedstock stream in the initial point of the riser reactor. Such a primary feed oil nozzle is to be distinguished from a secondary feed oil nozzle, used under some circumstances to discharge the secondary relatively low volume feedstock stream downstream in the riser reactor of the position of the primary feed oil nozzle. The ZSM-5 type zeolite is added to the catalytic cracking process in the amount of 0.1% to 25%, preferably 0.1% to 10%, by weight of the total catalyst inventory.
The ZSM-5 type zeolite is admixed with the fluidized mixture of the conventional cracking catalyst and the hydrocarbon charge, advancing from the upstream riser mixing zone, and is intimately admixed therewith. The fluidized mixture then proceeds into a conventional catalyst-gas separation means in the downstream, upper section of the cracking reactor. Such conventional separation means is well known to those skilled in the art and it comprises, for example, a riser cyclone, followed by a primary and a secondary stage cyclones. In the primary stage cyclone, the conventional cracking catalyst, having a relatively large particle size, is separated from the mixture comprised of cracked hydrocarbons, ZSM-5 type catalyst and fines of the conventional cracking catalyst. The relatively large size (at least 20 micrometers in diameter) conventional cracking catalyst is withdrawn from the dipleg of the primary stage cyclone. In the secondary stage cyclone, gaseous reaction products are separated from the effluent of the primary stage cyclone and withdrawn from the top of the reactor in a conventional manner. The ZSM-5 type zeolite and the fines of the conventional cracking catalyst are recovered from the dipleg of the secondary stage cyclone. The process stream from the dipleg of the secondary stage cyclone (also referred to herein as the first process stream) comprises about 5 to about 80%, preferably about 5 to about 20% by weight of the conventional cracking catalyst fines. The term conventional cracking catalyst fines, as used herein and in the appended claims, designates the fraction of a conventional cracking catalyst which has the size of less than 20 micrometers (μ) in diameter. It may be possible, e.g., by modifying the cyclone design, to achieve a nearly complete separation of the ZSM-5 type zeolite additive catalyst from the conventional cracking catalyst in the second stage cyclone because of the relatively low density and relatively small diameter of the additive catalyst, as discussed in detail below. Such complete separation could be accomplished, for example, by providing the primary cyclone of a relatively low efficiency and the secondary cyclone of relatively high efficiency. However, any carryover of the ZSM-5 catalyst or conventional cracking catalyst fines to the main distillation column bottoms can be recovered and recycled back to the secondary regeneration vessel.
The conventional cracking catalyst is conducted to a conventional regenerator wherein it is regenerated in a conventional manner, e.g., by passing air or other oxygen-containing gas through the bed of catalyst.
The process stream recovered from the dipleg of the secondary stage cyclone is conducted to a separate secondary regenerator means wherein the ZSM-5 type catalyst is at first separated from the fines of the conventional cracking catalyst while both, the fines and the ZSM-5 type catalyst, are regenerated. The ZSM-5 type catalyst is separated from the fines by density difference. The ZSM-5 type catalyst can be made with a packed density of less than 0.6 gram/cm3 (g/cm3), while packed density of the conventional cracking catalyst is greater than 0.9 g/cm3. Thus, the conventional catalyst fines are accumulated in the lower portion of the secondary regenerator vessel, while the ZSM-5 type zeolite catalyst is accumulated in the top portion thereof. Both catalysts are regenerated in a conventional manner, e.g., by passing air or other oxygen-containing gas in the direction countercurrent to the flow of the catalyst through the secondary regeneration means. The segregation of the conventional cracking catalyst fines from the ZSM-5 type additive catalyst can be carried out efficiently only if the regeneration gas (e.g., air) velocity is about 1.0-1.5 times that of the minimum fluidization velocity of the ZSM-5 type additive catalyst. A flue gas is withdrawn at the top of the secondary regeneration vessel. The regenerated ZSM-5 type catalyst is then recycled to the initial point of introduction thereof into the riser reactor. Accordingly, it bypasses the conventional cracking catalyst regenerator vessel and the riser reactor mixing zone, wherein the hydrocarbon feedstock is admixed with the freshly regenerated conventional cracking catalyst. A suitable gaseous medium, e.g., nitrogen, may be used to aid in the injection of the regenerated additive catalyst into the cracking reactor.
If necessary, fresh additive catalyst may be admixed with the regenerated additive catalyst prior to the introduction of the latter into the cracking reactor. Thus, in this embodiment, the combined additive catalyst stream comprises fresh ZSM-5 type makeup and the regenerated ZSM-5 type catalyst with a minimum amount of conventional FCC catalyst fines entrained therein from the secondary regenerator vessel. The combined additive catalyst stream comprises less than 10% by weight of the conventional FCC catalyst fines.
The ZSM-5 type additive catalyst of this invention comprises a class of zeolites characterized by a silica to alumina ratio of at least 12 and a constraint index, defined hereinafter, of about 1 to 12. The additive catalyst used in the invention has a packed density of less than 0.6 g/cm3 and a particle diameter of less than 40 microns (μm), preferably about 20 to about 40 μm. The relatively small size of the additive catalyst contributes, it is believed, to its longer time on-stream without substantial deactivation. Without wishing to be bound by any theory of operability, it is believed that larger diameter additive ZSM-5 type zeolite catalyst could be transported with the conventional cracking catalyst to the conventional regenerator where hydrothermal aging of the zeolite catalyst is significant. The large diameter ZSM-5 additive catalyst could also pose severe mass transfer limitation, due to its small pore structure. As is known in the art, the addition of a separate additive catalyst comprising one or more members of the ZSM-5 type zeolites is extremely effective in improving octane and total yield of the catalytic cracking operation. Since the zeolites of the additive catalyst are very active catalytically in the fresh state, only relatively small quantities thereof are necessary to obtain substantial octane improvement in a commercial cracking unit. Thus, the refiner is afforded great flexibility in commercial cracking operations, since the additive catalyst can be quickly introduced, because a small quantity thereof is required as compared to the total inventory of catalyst. The refiner can efficiently control the magnitude of octane increase by controlling the rate of additive catalyst. This type of flexibility could be useful in situations where feed composition or rate changes occur, when demand for high octane gasoline (unleaded) fluctuates, or when capacity for alkylation varies due to mechanical problems or changes in overall refinery operation.
The additive catalyst can be injected at any time during the catalytic cracking process. The additive catalyst can be introduced while the cracking unit is down, or while the cracking unit is on stream. Once the additive catalyst is added to the cracking process, the refiner can return to conventional operation or an operation at lower octane number by eliminating or decreasing the use of additive catalyst. Thus, the increase in octane number over the number obtainable under conventional cracking operations can be controlled by controlling the amount of additive catalyst. However, as set forth above, it is important in accordance with the teachings of this invention to introduce the additive zeolite catalyst into the cracking reactor downstream of the riser mixing zone and remove it from the reactor separately from the conventional cracking catalyst to prevent the passage of the additive catalyst into the conventional catalyst regenerator. It is believed that steaming at high temperatue, e.g., during conventional cracking catalyst regeneration, may cause the collapse of the zeolite crystallite structure, thereby rapidly deactivating the catalyst. Bypassing the conventional cracking catalyst regenerator and stripper of the reactor by the additive catalyst, in accordance with the present invention, eliminates contact thereof with likely steam deactivation locations of the cracking process. In this connection, operating conditions of the secondary regeneration means are less severe than those of conventional cracking catalyst regenerator, thereby minimizing steam production in the secondary regenerator. The secondary regenerator is operated at less severe conditions compared with the conventional regenerator, due to a smaller size regenerator required. The secondary regenerator operation may not be dictated by the overall heat balance of the unit. Consequently, better control schemes can be implemented, e.g., a heat exchange means could be provided in the secondary regenerator to maintain the temperature therein within desired limits. The secondary regenerator is operated at 1200� F. or less, and water partial pressure therein is maintained at 3 pounds per square inch (psi) or less. In contrast, the conventional catalyst regenerator is operated at about 1250� F. or higher temperature, and the water partial pressure therein is about 3 psi or higher. It is believed that the lower temperature and water partial pressure of the secondary regenerator operation promotes lower deactivation rate of the ZSM-5 type additive catalyst.
Another possible mechanism of the reduced site utilization of the additive zeolite catalyst by using conventional injection schemes is a possibility of the increased pore plugging of the additive catalyst by adsorbing heavy hydrocarbon molecules near the catalyst/oil mixing zone in the initial, bottom portion of the riser. Secondary injection of the additive catalyst downstream of the mixing zone, in accordance with this invention, prevents the contact of the additive catalyst with such heavy hydrocarbon molecules.
Catalytic cracking units which can be used in the process of this invention operate within the temperature range of about 400� F. to about 1300� F. and under reduced atmospheric or superatmospheric pressure. The catalytic cracking process may be operated batchwise or continuously. The catalytic cracking process can be either fixed bed, moving bed or fluidized bed and the hydrocarbon chargestock flow may be either concurrent or countercurrent to the conventional catalyst flow. The process of this invention is particularly applicable to the fluid catalytic cracking (FCC) process.
The conventional cracking catalyst used in the process of the invention is any suitable cracking catalyst, e.g., an amorphous catalyst, a crystalline aluminosilicate catalyst, a faujasite catalyst or any mixture thereof.
Hydrocarbon charge stocks undergoing cracking in accordance with this invention comprise hydrocarbons generally and, in particular, petroleum fractions having an initial boiling point range of at least 400� F., a 50% point range of at least 500� F. and an end point range of at least 600� F. Such hydrocarbon fractions include gas oils, residual oils, cycle stocks, whole top crudes and heavy hydrocarbon fractions derived by the destructive hydrogenation of coal, tar, pitches, asphalts and the like. As will be recognized, the distillation of higher boiling petroleum fractions above about 750� F. must be carried out under vacuum in order to avoid thermal cracking. The boiling temperatures utilized herein are expressed, for convenience, in terms of the boiling point corrected to atmospheric pressure.
The members of the class of zeolites of the ZSM-5 type additive catalyst of this invention are characterized by a pore dimension greater than about 5 Angstroms, i.e., they are capable of sorbing paraffins having a single methyl branch as well as normal paraffins, and they have a silica to alumina mole ratio of at least 12. Zeolite A, for example, with a silica to alumina ratio of 2.0, is not useful in this invention, and moreover it has no pore dimension greater than about 5 Angstroms.
The members of the class of zeolites of the additive catalyst constitute an unusual class of natural and synthetic minerals. They are characterized by having a rigid crystalline framework structure composed of an assembly of silicon and aluminum atoms, each surrounded by a tetrahedron of shared oxygen atoms, and a precisely defined pore structure. Exchangeable cations are present in the pores.
The additive catalysts are members of a class of zeolites exhibiting some unusual properties. These zeolites induce profound transformations of aliphatic hydrocarbons to aromatic hydrocarbons in commercially desirable yields and are generally highly effective in alkylation, isomerization, disproportionation and other reactions involving aromatic hydrocarbons. Although they have unusually low alumina contents, i.e., high silica to alumina mole ratios, they are very active even with silica to alumina mole ratios exceeding 30. This activity is surprising, since catalytic activity of zeolites is generally attributed to framework aluminum atoms and cations associated with these aluminum atoms. These zeolites retain their crystallinity for long periods in spite of the presence of steam even at such high temperatures which induce irreversible collapse of the crystal framework of other zeolites, e.g., of the X and A type. Furthermore, carbonaceous deposits, when formed, may be removed by burning at higher than usual temperatures to restore activity. In many environments, the zeolites of this class exhibit very low coke forming capability, conductive to very long times on stream between burning regenerations.
An important characteristic of the crystal structure of this class of zeolites is that it provides constrained access to, and egress from, the intracrystalline free space by virtue of having a pore dimension greater than about 5 Angstroms and pore windows of about a size such as would be provided by 10-membered rings of oxygen atoms. It is to be understood, of course, that these rings are formed by the regular disposition of the tetrahedra making up the anionic framework of the crystalline zeolite, the oxygen atoms themselves being bonded to the silicon or aluminum atoms at the centers of the tetrahedra. Briefly, the preferred zeolites useful as the additive catalysts of this invention possess, in combination: a Constraint Index, as hereinafter defined, of about 1 to 12, a silica to alumina mole ratio of at least about 12, and a structure providing constrained access to the intracrystalline free space.
The silica to alumina mole ratio referred to above may be determined by conventional analysis. This ratio is meant to represent, as closely as possible, the ratio in the rigid anionic framework of the zeolite crystal and to exclude aluminum in the binder or in cationic or other form within the channels.
Although additive catalysts comprising zeolites with a silica to alumina mole ratio of at least about 12 are useful, it is preferred to use zeolites having higher ratios of at least about 30. In some zeolites, the upper limit of silica to alumina mole ratio is unbounded, with values of 30,000 and greater, extending at least theoretically up to infinity. Therefore, the silica to alumina mole ratio of the zeolite component of the additive catalyst for use herein may be from about 12 to infinity, preferably from about 30 to infinity. Such zeolites, after activation, acquire an intracrystalline sorption capacity for normal hexane which is greater than that for water, i.e., they exhibit "hydrophobic" properties. It is believed that this hydrophobic character is advantageous in the present invention.
The zeolites comprising the additive catalysts in this invention freely sorb normal hexane and have a pore dimension greater than about 5 Angstroms. In addition, their structure must provide constrained access to some larger molecules. It is sometimes possible to judge from a known crystal structure whether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of oxygen atoms, then access by molecules of larger cross-section than normal hexane is substantially excluded and the zeolite is not of the desired type. Additive catalysts with zeolites with windows of 10-member rings are preferred, although excessive puckering or pore blockage may render these zeolites substantially ineffective.
Additive catalysts comprising zeolites with windows of 12-membered rings do not generally appear to offer sufficient constraint to produce the advantageous conversions desired in the instant invention, although structures can be conceived, due to pore blockage or other cause, that may be operative.
Rather than attempt to judge from crystal structure whether or not a zeolite possesses the necessary constraint access, a simple determination of the "Constraint Index" may be made by continuously passing a mixture of equal weight of normal hexane and 3-methylpentane over a small sample, approximately 1 gram or less, of zeolite at atmospheric pressure according to the following procedure. A sample of the zeolite, in the form of pellets or extrudates, is crushed to a particle size about that of coarse sand and mounted in a glass tube. Prior to testing, the zeolite is treated with a stream of air at 1000� F. for at least 15 minutes. The zeolite is then flushed with helium and the temperature adjusted between 550� F. and 950� F. to give an overall conversion between 10% and 60%. The mixture of hydrocarbons is passed at 1 liquid hourly space velocity (i.e., 1 volume of liquid hydrocarbon per volume of catalyst per hour) over the zeolite with a helium dilution to give a helium to total hydrocarbon mole ratio of 4:1. After 20 minutes on stream, a sample of the effluent is taken and analyzed, most conveniently by gas chromatography, to determine the fraction remaining unchanged for each of the two hydrocarbons.
The "Constraint Index" is calculated as follows: ##EQU1##
The constraint index approximates the ratio of the cracking rate constants for the two hydrocarbons. Zeolites suitable for the present invention are those having a constraint index from 1.0 to 12.0. Constraint Index (C.I.) values for some typical zeolites, including some not within the scope of this invention, are:
______________________________________Zeolite C.I.______________________________________Erionite 38ZSM-5 8.3ZSM-11 8.7ZSM-35 6.0TMA Offretite 3.7ZSM-38 2.0ZSM-12 2Beta 0.6ZSM-4 0.5Acid Mordenite 0.5REY 0.4Amorphous Silica-Alumina 0.6ZSM-23 9.1______________________________________
The above-described Constraint Index is an important and even critical definition of those zeolites which are useful in the instant invention. The very nature of this parameter and the recited technique by which it is determined, however, admit of the possibility that a given zeolite can be tested under somewhat different conditions and thereby have different constraint indices. Constraint Index seems to vary somewhat with the severity of operation (conversion). Therefore, it will be appreciated that it may be possible to so select test conditions to establish multiple constraint indices for a particular given zeolite which may be both inside and outside the above-defined range of 1 to 12.
Thus, it should be understood that the parameter and property "Constraint Index" as such value is used herein is an inclusive rather than an exclusive value. That is, a zeolite when tested by any combination of conditions within the testing definition set forth hereinabove to have a constraint index of 1 to 12 is intended to be included in the instant catalyst definition even though the same identical zeolite tested under other defined conditions may give a constraint index value outside of 1 to 12.
The members of the class of zeolites defined herein which may be used as the additive catalyst are exemplified by ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38 and other similar materials. U.S. Pat. No. 3,702,886 describing and claiming ZSM-5 is incorporated herein by reference. U.S. Pat. No. Re. 29,948 describing and claiming a crystalline material with an X-ray diffraction pattern of ZSM-5, is incorporated herein by reference as is U.S. Pat. No. 4,061,724 describing a high silica ZSM-5 referred to as "silicalite" in such patent.
ZSM-11 is more particularly described in U.S. Pat. No. 3,709,979, the entire contents of which are incorporated herein by reference.
ZSM-12 is more particularly described in U.S. Pat. No. 3,832,449, the entire contents of which are incorporated herein by reference.
ZSM-23 is more particularly described in U.S. Pat. No. 4,076,842, the entire contents of which are incorporated herein by reference.
ZSM-35 is more particularly described in U.S. Pat. No. 4,016,245, the entire contents of which are incorporated herein by reference.
ZSM-38 is more particularly described in U.S. Pat. No. 4,046,859, the entire contents of which are incorporated herein by reference.
Natural zeolites may sometimes be converted to this class of zeolites by various activation procedures and other treatments, such as base exchange, steaming, alumina extraction and calcination, alone or in combinations. Natural minerals which may be so treated include ferrierite, brewsterite, stilbite, dachiardite, epistilbite, heulandite and clinoptilolite. The preferred zeolites of the additive catalyst are ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38, with ZSM-5 being particularly preferred.
The zeolites used as additive catalysts in this invention may be in the hydrogen form or they may be base exchanged or impregnated to contain a rare earth cation complement. Such rare earth cations comprise Sm, Nd, Pr, Ce and La. It is desirable to calcine the zeolite after base exchange.
In a preferred aspect of this invention, the zeolites comprising the additive catalysts are selected as those having a crystal framework density, in the dry hydrogen form, of not substantially below about 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of these criteria are most desired. Therefore, the preferred additive catalysts of this invention are those comprising a zeolite having a constraint index as defined above of about 1 to 12, a silica to alumina mole ratio of at least about 12 and a dried crystal density of not substantially less than about 1.6 grams per cubic centimeter. The dry density for known structures may be calculated from the number of silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on page 19 of the article on Zeolite Structure by W. M. Meier. This paper is included in Proceedings of the Conference on Molecular Sieves, London, April 1967, published by the Society of Chemical Industry, London, 1968. When the crystal structure is unknown, the crystal framework density may be determined by classical pycnometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zeolite in an organic solvent which is not sorbed by the crystal. It is possible that the unusual sustained activity and stability of this class of zeolites are associated with its high crystal anionic framework density of not less than about 1.6 grams per cubic centimeter. This high density, of course, must be associated with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, seems to be important as the locus of catalytic activity.
Crystal framework densities of some typical zeolites, including some which are not within the purview of this invention, are:
______________________________________ Void FrameworkZeolite Volume (cc/cc) Density (g/cc)______________________________________Ferrierite 0.28 1.76Mordenite 0.28 1.7Z5M-5, -11 0.29 1.79ZSM-12 -- 1.8ZSM-23 -- 2.0Dachiardite 0.32 1.72L 0.32 1.61Clinoptilolite 0.34 1.71Laumontite 0.34 1.77ZSM-4 (Omega) 0.38 1.65Heulandite 0.39 1.69P 0.41 1.57Offretite 0.40 1.55Levynite 0.40 1.54Erionite 0.35 1.51Gmelinite 0.44 1.46Chabazite 0.47 1.45A 0.5 1.3Y 0.48 1.27______________________________________
The additive catalysts of this invention may be prepared in various ways. The additive catalyst may be separately prepared in the form of particles, such as pellets or extrudates, for example, and simply mixed in the required proportions. The particle size of the individual component particles may be quite small, for example less than 40 microns in diameter, preferably about 20 to about 40 microns in diameter, when intended for use in fluid bed operation, or they may be as large as up to about 4 milimeter (mm) for fixed bed (or moving bed) operation. The components may also be mixed as powders and formed into pellets or extrudates, each pellet containing both components in substantially the required proportions.
As is the case with many catalysts, it is desirable to incorporate the zeolite component of the additive catalyst in a matrix. Such matrix is useful as a binder and imparts greater resistance to the catalyst for the severe temperature, pressure and velocity conditions encountered in many cracking processes.
Matrix materials include both synthetic and natural substances. Such substances include clays, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates, sols or gels including mixtures of silica and metal oxides. Frequently, zeolite materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin.
In addition to the foregoing materials, the zeolite used in the invention can be composited with a porous matrix material, such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary compositions, such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel. A mixture of clay in combination with silica or any of the above specified cogels to form a matrix is highly preferred.
Conventional cracking catalysts contain active components which may be zeolitic or non-zeolitic. The non-zeolitic active components are generally amorphous silica-alumina and crystalline silica-alumina. However, the major conventional cracking catalysts presently in use generally comprise a crystalline zeolite (active component) in a suitable matrix. Representative crystalline zeolite active component constituents of conventional cracking catalysts include zeolite A (U.S. Pat. No. 2,882,243), zeolite X (U.S. Pat. No. 2,882,244), zeolite Y (U.S. Pat. No. 3,130,007), zeolite ZK-5 (U.S. Pat. No. 3,247,195), zeolite ZK-4 (U.S. Pat. No. 3,314,752), synthetic mordenite and dealuminized synthetic mordenite, as well as naturally occurring zeolites, including chabazite, faujasite, mordenite, and the like. Preferred crystalline zeolites include the synthetic faujasite zeolites X and Y, with particular preference being accorded zeolite Y.
The additive crystalline zeolite employed as a constituent in the cracking catalyst compositions of the present invention is essentially characterized by a high catalytic activity.
In general, the crystalline zeolites are ordinarily ion exchanged either separately or in the final catalyst with a desired cation to replace alkali metal present in the zeolite as found naturally or as synthetically prepared. The exchange treatment is such as to reduce the alkali metal content of the final catalyst to less than about 1.5 weight percent, and preferably less than about 0.5 weight percent. The purpose of ion exchange is to substantially remove alkali metal cations which are known to be deleterious to cracking, as well as to introduce particularly desired catalytic activity by means of the various cations used in the exchange medium. For the cracking operation described herein, preferred exchanging cations are hydrogen, ammonium, rare earth metals and mixtures thereof, with particular preference being accorded rare earth metals. Ion exchange is suitably accomplished by conventional contact of the zeolite with a suitable salt solution of the desired cation, such as, for example, the sulfate, chloride or nitrate salts.
It is preferred to have the crystalline zeolite of the conventional cracking catalyst in a suitable matrix, since this catalyst form is generally characterized by a high resistance to attrition, high activity and exceptional steam stability. Such catalysts are readily prepared by dispersing the crystalline zeolite in a suitable siliceous sol and gelling the sol by various means. The inorganic oxide which serves as the matrix in which the above crystalline zeolite is distributed includes silica gel or a cogel of silica and a suitable metal oxide. Representative cogels include silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary combinations, such as silica-alumina-magnesia, silica-alumina-zirconia and silica-magnesia-zirconia. Preferred cogels include silica-alumina, silica-zirconia or silica-alumina-zirconia. The above gels and cogels will generally comprise a major proportion of silica and a minor proportion of the other aforementioned oxide or oxides, Thus, the silica content of the siliceous gel or cogel matrix will generally fall within the range of 55 to 100 weight percent, preferably 60 to 95 weight percent, and the other metal oxide or oxides content will generally be within the range of 0 to 45 weight percent, and preferably 5 to 40 weight percent. In addition to the above, the matrix may also comprise natural or synthetic clays, such as kaolin type clays, montmorillonite, bentonite or halloysite. These clays may be used either alone or in combination with silica or any of the above specified cogels in a matrix formulation.
Where a matrix is used, content of catalytically active component of a conventional cracking catalyst, e.g., crystalline zeolite, i.e., the amount of the zeolite Y component, in the conventional cracking catalyst, is generally at least about 5 weight percent, and more particularly between about 5 and about 50 weight percent. Ion exchange of the zeolite to replace its initial alkali metal content can be accomplished either prior to or subsequent to incorporation of the zeolite into the matrix.
Where no matrix as such is used, such as where a non-zeolitic cracking catalyst, e.g. silica-alumina, is used, content of catalytically active component will, of course, approach 100 weight percent. Also, since silica-alumina may serve as a matrix material for catalytically active zeolite component, 100 weight percent catalytically active catalyst may exist.
The above compositions may be readily processed so as to provide fluid cracking catalysts by spray drying the composite to form microspheroidal particles of suitable size. Alternatively, the composition may be adjusted to suitable concentration and temperature to form bead type catalyst particles suitable for use in moving bed type cracking systems. The catalyst may also be used in various other forms, such as those obtained by tabletting, balling or extruding.
Additional details of the invention will now be described in conjunction with one exemplory emobodiment thereof illustrated in FIGS. 1-3.
Referring now to FIG. 1, a hydrocarbon feed 2, such as gas oil boiling from about 600� F. up to 1000� F., is passed after preheating thereof to the bottom portion of riser 4 for admixture with hot regenerated conventional cracking catalyst introduced by standpipe 6 provided with flow control valve 8. A suspension of catalyst in hydrocarbon vapors at a temperature of at least about 950� F. but more usually at least 1000� F. is thus formed in the lower portion of riser 4 for flow upwardly therethrough under hydrocarbon conversion conditions.
The suspension initially formed in the lower portion of the riser proceeds upwardly for admixture with a stream 3 comprising a freshly regenerated and a makeup additive catalyst of ZSM-5 type zeolite. The regenerated additive catalyst is passed into the riser 4 from the secondary regenerator 5, while the fresh makeup catalyst is introduced through a conduit 15. A fluidizing stream, e.g., nitrogen, may optionally be introduced through a conduit 13. The operation of the secondary regenerator means 5 is discussed in detail below. The hydrocarbon vapor-catalyst suspension formed in the riser reactor is passed upwardly through riser 4 under hydrocarbon conversion conditions of at least 900� F., and more usually at least 950� F., before discharge into a riser cyclone 20.
In the riser cyclone, the hydrocarbon vapor-catalyst suspension undergoes a preliminary separation of the catalyst and the cracked hydrocarbons. The cracked hydrocarbons and entrained catalysts are then conducted to a primary cyclone 14 and then to a secondary stage cyclone 32. In the secondary stage cyclone, nearly complete recovery of the ZSM-5 catalyst may be achieved due to its low density and relatively small diameter of the catalyst particles of less than 40 microns. The dipleg 34 of the secondary stage cyclone extends into a secondary regeneration means 5 through a conduit 11 for the regeneration of the ZSM-5 additive catalyst and the segregation of the ZSM-5 catalyst from the FCC fines. A minimum amount of the ZSM-5 additive catalyst and of the conventional cracking catalyst fines may be entrained with the stream of cracked hydrocarbons 18 to the main fractionation column bottom, not shown. Provisions can be made in the fractionation column to recover the entrained ZSM-5 additive catalyst and conventional cracking catalyst fines and transport them back to the secondary regeneration vessel 5, e.g., by providing a hydrocyclone, not shown, outside of the fractionation column to treat the fractionation column bottoms stream. In the secondary regeneration means 5, the ZSM-5 type additive catalyst is separated from the FCC conventional catalyst fines (having average diameter of about less than 20 m). It is also possible to separate the ZSM-5 additive catalyst from the FCC conventional catalyst fines by elutriation. However, the segregation by density difference is preferred for the purposes of this invention since the ZSM-5 type additive catalyst can be made with a packed density of less than about 0.6 g/cm3 compared with a packed density of greater than 0.9 g/cm3 for the FCC conventional catalyst.
FIG. 3 illustrates the details of the secondary regeneration means wherein the additive catalyst is regenerated and separated from the conventional cracking FCC catalyst. The coked additive catalyst is conducted into the secondary regenerator 5 through a conduit 11 and is regenerated therein by air introduced into the regenerator by a conduit 9. Due to density difference, the conventional cracking catalyst fines accumulate at the bottom of the regenerator and are removed therefrom by a conduit 7 to the storage for future disposal. In contrast, the lighter additive catalyst tends to accumulate in the upper portion of the fluidized regenerator bed and is removed therefrom by a conduit 3 which conducts it to the initial point of introduction of the additive catalyst in the riser 4 (FIG. 1). A conventional dispersion means 21 is used in the regenerator to aid in dispersing the regeneration gas. In the upper portion of the secondary regenerator, a conventional cyclone means 17 is used to separate the entrained catalyst from the flue gas stream. The catalyst is then returned through the dipleg means into the bed of catalyst being regenerated at the bottom of the regenerator, and the flue gas is withdrawn from the generator by a conduit 19.
In the reactor vessel, separated hydrocarbon vapors are passed from the secondary stage cyclone 32 to a plenum chamber 16 for withdrawal therefrom by a conduit 18. The hydrocarbon vapors, together with gasiform material separated by stripping gas, as discussed below, are passed by conduit 18 to a downstream fractionation equipment, not shown. Catalyst separated from hydrocarbon vapors in the cyclonic separation means is passed by diplegs, such as by dipleg 23, to a dense fluid bed of separated catalyst 22 retained about an upper portion of riser conversion zone 4. Catalyst bed 22 is maintained as a downwardly moving fluid bed of catalyst countercurrent to rising gasiform material. The catalyst passes downwardly through a stripping zone 24 immediately therebelow and countercurrently to rising stripping gas introduced to a lower portion thereof by conduit 26. Baffles 28 are provided in the stripping zone to improve the stripping operation.
The catalyst is maintained in the stripping zone 24 for a period of time sufficient to effect a high temperature desorption of feed compounds deposited thereon which are then carried overhead by the stripping gas. The stripping gas with desorbed hydrocarbons passes through one or more primary cyclonic separating means 14 and then through the secondary cyclonic separating means 32, wherein ZSM-5 type catalyst and entrained conventional cracking catalyst fines are separated and returned to the secondary regenerator vessel 5 by dipleg 34 and conduit 11. The hydrocarbon conversion zone comprising riser 4 may terminate in an upper enlarged portion of the catalyst collecting vessel with the commonly known bird cage discharge device or an open end "T" connection may be fastened to the riser discharge which is not directly connected to the cyclonic catalyst separation means. The cyclonic separation means may be spaced apart from the riser discharge so that an initial catalyst separation is effected by a change in velocity and direction of the discharged suspension so that vapors less encumbered with catalyst fines may then pass through one or more cyclonic separation means before passing to a product separation step. In any of these arrangements, gasiform materials comprising stripping gas hydrocarbon vapors and desorbed sulfur compounds are passed from the cyclonic separation means represented by separator 32 to a plenum chamber 16 for removal with hydrocarbon products of the cracking operation by conduit 18. Gasiform material comprising hydrocarbon vapors is passed by conduit 18 to a product fractionation step, not shown. Hot stripped conventional cracking catalyst at an elevated temperature is withdrawn from a lower portion of the stripping zone by conduit 36 for transfer to a fluid bed of catalyst being regenerated in a conventional cracking catalyst regeneration zone. Flow control valve 38 is provided in coked catalyst conduit 36.
This type of catalyst regeneration operation is referred to as a swirl type of catalyst regeneration due to the fact that the catalyst bed tends to rotate or circumferentially circulate about the vessel's vertical axis and this motion is promoted by the tangential spent catalyst inlet to the circulating catalyst bed. Thus, the tangentially introduced catalyst at an elevated temperature is further mixed with hot regenerated catalyst or catalyst undergoing regeneration at an elevated temperature and is caused to move in a circular or swirl pattern about the regenerator's vertical axis as it also moves generally downward to a catalyst withdrawal funnel 40 (sometimes called the "bathtub") adjacent the regeneration gas distributor grid. In this catalyst regeneration environment, it has been found that the regeneration gases comprising flue gas products of carbonaceus material combustion tend to move generally vertically upwardly through the generally horizontally moving circulating catalyst to cyclone separators positioned above the bed of catalyst in any given vertical segment.
As shown in FIG. 2, the catalyst tangentially introduced to the regenerator by conduit 36 causes the catalyst to circulate in a clockwise direction in this specific embodiment. As the bed of catalyst continues its circular motion, some catalyst particles move from an upper portion of the mass of catalyst particles suspended in regeneration gas downwardly therethrough to a catalyst withdrawal funnel 40 in a segment of the vessel adjacent to the catalyst inlet segment. In the regeneration zone 42, housing a mass of the circulating suspended catalyst particles 44 in upflowing oxygen-containing regeneration gas introduced to the lower portion thereof by conduit distributor means 46, the density of the mass of suspended catalyst particles may be varied by the volume of regeneration gas used in any given segment or segments of the distributor grid. Generally speaking, the circulating suspended mass of catalyst particles 44 undergoing regeneration with oxygen containing gas to remove carbonaceous deposits by burning will be retained as a suspended mass of swirling catalyst particles varying in density in the direction of catalyst flow and a much less dense phase of suspended catalyst particles 48 will exist thereabove to an upper portion of the regeneration zone. Under carefully selected relatively low regeneration gas velocity conditions, a rather distinct line of demarcation may be made to exist between a dense fluid bed of suspended catalyst particles and a more dispersed suspended phase (dilute phase) of catalyst thereabove. However, as the regeneration gas velocity conditions are increased, there is less of a demarcation line and the suspended catalyst passes through regions of catalyst particle density generally less than about 30 lbs. per cu. ft. (lbs/ft3). A lower catalyst bed density of at least 20 lbs/ft3 is preferred.
A segmented regeneration gas distributor grid 50 positioned in the lower cross-sectional area of the regeneration vessel 42 is provided as shown in FIG. 1 and is adapted to control the flow of regeneration gas passed to any given vertical segment of the catalyst bed thereabove. In this arrangement, it has been found that even with the generally horizontally circulating mass of catalyst, the flow of regeneration gas is generally vertically upwardly through the mass of catalyst particles so that regeneration gas introduced to the catalyst bed by any given grid segment or portion thereof may be controlled by grid openings made available and the air flow rate thereto. Thus, oxygen containing combustion gases after contact with catalyst in the regeneration zone are separated from entrained catalyst particles by the cyclonic means provided and vertically spaced thereabove. The cyclone combinations diagrammatically represented in FIG. 1 are intended to correspond to that represented in FIG. 2. Catalyst particles separated from the flue gases passing through the cyclones are returned to the mass of catalyst therebelow by the plurality of provided cyclone diplegs.
As mentioned above, regenerated conventional cracking catalyst withdrawn by funnel 40 is conveyed by standpipe 6 to the hydrocarbon conversion riser 4.
It will be clear from FIG. 1 that the term "circulating inventory of catalyst" referred to herein includes the conventional cracking catalyst and the additive catalyst of ZSM-5 type, i.e., the catalyst mass in riser 4, in the dense bed 22, in the dense bed in stripper 24, in the dense bed in the regenerator 44, in the secondary regenerator vessel 5, in conduits 3 and 11, as well as the catalyst material in conduits 36 and 6 and the catalyst material suspended in dilute phase and cyclones in the reactor section and the regenerator section. This circulating inventory has the temperature substantially above about 600� F., since the regenerator 42 operates at a temperature higher than about 1000� F., usually in the range of about 1050� F. to about 1300� F., and the reactor at a temperature higher than 800� F.
In actual operation, because the catalytic activity of the conventionl cracking catalyst tends to decrease with age, fresh makeup conventional cracking catalyst, usually amounting to about 1 or 2% of the circulating inventory per day, is added to maintain optimal catalyst activity, in the manner similar to that in which the additive makeup catalyst is added through the conduit 15. This catalyst makeup is usually added via a hopper (fresh catalyst storage hopper) and conduit (not shown) into the regenerator.
A recent advance in the art of catalytic cracking is disclosed in U.S. Pat. No. 4,072,600, the entire contents of which are incorporated herein by reference. One embodiment of this patent teaches that trace amounts of a metal selected from the group consisting of platinum, palladium, iridium, osmium, rhodium, ruthenium, and rhenium, when added to cracking catalysts, enhance significantly conversion of carbon monoxide during the catalyst regeneration operation.
In employing this recent advance in the present invention, the amount of said metal added to the conventional cracking catalyst can vary from between about 0.01 ppm to about 100 ppm based on total circulating catalyst inventory. The aforesaid metals can also be introduced into the process via the additive catalyst in amounts between about 1.0 ppm and about 1000 ppm based on total additive catalyst.
After cracking, the resulting product gas is compressed and the resulting products may suitably be separated from the remaining components by conventional means, such as adsorption, distillation, etc.
It will be apparent to those skilled in the art that although the embodiments of FIGS. 1-3 were described above in conjunction with a swirl type conventional cracking catalyst regenerator, the process of the invention can be carried out with any conventional regeneration means used to regenerate a conventional cracking catalyst.
It will be apparent to those skilled in the art that the specific embodiments discussed above can be successfully repeated with ingredients equivalent to those generically or specifically set forth above and under variable process conditions. From the foregoing specification, one skilled in the art can readily ascertain the essential features of this invention and without departing from the spirit and scope thereof can adapt it to various diverse applications.
|Cited Patent
|Filing date
|Publication date
|Oct 28, 1969
|Feb 1, 1972
|Gulf Research Development Co
|Fcc process utilizing divided catalyst injection
|Sep 19, 1969
|Mar 14, 1972
|Exxon Research Engineering Co
|Transferline fluid cracking process employing conventional cracking catalyst and superactive molecular sieve cracking catalyst
|Apr 20, 1971
|Jul 24, 1973
|Mobil Oil Corp
|Dual riser fluid catalytic cracking with zsm-5 zeolite
|Oct 6, 1970
|Sep 11, 1973
|Mobil Oil
|Olites catalytic cracking of hydrocarbons with mixture of zsm-5 and other ze
|May 9, 1966
|Oct 30, 1973
|Mobil Oil Corp
|Catalytic conversion of hydrocarbons
|Mar 16, 1972
|Apr 9, 1974
|Chevron Res
|Catalytic cracking process
|Apr 2, 1974
|Jul 15, 1975
|Mobil Oil Corp
|Method for improving olefinic gasoline product of low conversion fluid catalytic cracking
|Apr 2, 1974
|Jul 15, 1975
|Mobil Oil Corp
|Method for producing light fuel oil
|Dec 19, 1972
|Jul 15, 1975
|Mobil Oil Corp
|Conversion of hydrocarbons with mixture of small and large pore crystalline zeolite catalyst compositions to accomplish cracking cyclization, and alkylation reactions
|Dec 19, 1972
|Dec 16, 1975
|Mobil Oil Corp
|Method and system for controlling the activity of a crystalline zeolite cracking catalyst
|Jul 2, 1973
|Dec 23, 1975
|Mobil Oil Corp
|Catalytic cracking of FCC gasoline and virgin naphtha
|May 6, 1974
|Dec 14, 1976
|Phillips Petroleum Company
|Vaporization of oil feed by addition of regenerated catalyst
|Jul 18, 1977
|Sep 26, 1978
|Mobil Oil Corporation
|Method and system for effecting catalytic cracking of high boiling hydrocarbons with fluid conversion catalysts
|May 31, 1979
|Dec 16, 1980
|Exxon Research & Engineering Co.
|Hydrocarbon cracking catalyst and process utilizing the same
|May 29, 1979
|Mar 24, 1981
|Uop Inc.
|Fluid catalytic cracking process
|Dec 5, 1979
|Jan 5, 1982
|Mobil Oil Corporation
|Octane and total yield improvement in catalytic cracking
|Sep 14, 1981
|Jan 11, 1983
|Mobil Oil Corporation
|Octane and total yield improvement in catalytic cracking
|Citing Patent
|Filing date
|Publication date
|Mar 26, 1986
|Nov 24, 1987
|Union Oil Company Of California
|Process for the catalytic cracking of nitrogen-containing feedstocks
|Sep 3, 1986
|Jan 5, 1988
|Mobil Oil Corporation
|Multiple riser fluidized catalytic cracking process utilizing hydrogen and carbon-hydrogen contributing fragments
|Sep 3, 1986
|Jun 21, 1988
|Mobil Oil Corporation
|Single riser fluidized catalytic cracking process utilizing a C3-4 paraffin-rich co-feed and mixed catalyst system
|Apr 16, 1987
|Jun 28, 1988
|Mobil Oil Corporation
|Process for improving the octane number of cracked gasolines
|Sep 20, 1985
|Jun 28, 1988
|Ashland Oil, Inc.
|Fluid particle material regeneration method and apparatus
|Nov 5, 1987
|Nov 15, 1988
|Mobil Oil Corporation
|Catalytic upgrading of FCC effluent
|Sep 3, 1986
|Nov 29, 1988
|Mobil Oil Corporation
|Process for two-phase fluid catalytic cracking system
|Jan 14, 1988
|Feb 7, 1989
|Mobil Oil Corporation
|Single riser fluidized catalytic cracking process utilizing hydrogen and carbon-hydrogen contributing fragments
|Sep 3, 1986
|May 2, 1989
|Mobil Coil Corporation
|Single riser fluidized catalytic cracking process utilizing a C3-4 paraffin-rich co-feed and mixed catalyst system
|Aug 7, 1987
|May 9, 1989
|Mobil Oil Corporation
|Octane improvement with large size ZSM-5 catalytic cracking
|Feb 19, 1988
|May 16, 1989
|Mobil Oil Corporation
|Upgrading naphtha in a multiple riser fluid catalytic cracking operation employing a catalyst mixture
|Feb 1, 1988
|Aug 1, 1989
|Mobil Oil Corporation
|Multiple riser fluidized catalytic cracking process utilizing hydrogen and carbon-hydrogen contributing fragments
|Aug 29, 1988
|Aug 29, 1989
|Institut Francais Du Petrole
|Process for catalytic cracking of a hydrocarbon charge subjected to a pretreatment with solid particles of low activity
|Feb 8, 1988
|Aug 29, 1989
|Mobil Oil Corporation
|Mixed catalyst system and catalytic conversion process employing same
|Jan 26, 1988
|Sep 5, 1989
|Mobil Oil Corporation
|Fluidized catalytic cracking process utilizing a C3-C4 paraffin-rich Co-feed and mixed catalyst system with selective reactivation of the medium pore silicate zeolite component thereofo
|Feb 8, 1988
|Sep 12, 1989
|Mobil Oil Corporation
|Maximizing distillate production in a fluid catalytic cracking operation employing a mixed catalyst system
|Sep 2, 1987
|Oct 3, 1989
|Mobil Oil Corporation
|Catalytic cracking process employing mixed catalyst system
|Sep 3, 1986
|Dec 19, 1989
|Herbst Joseph A
|Process of stripping in a catalytic cracking operation employing a catalyst mixture which includes a shape selective medium pore silicate zeolite component
|Dec 30, 1988
|May 22, 1990
|Mobil Oil Corporation
|Multiple feed point catalytic cracking process using elutriable catalyst mixture
|May 22, 1989
|Aug 14, 1990
|Institut Francais Du Petrole
|Apparatus for catalytic cracking of a hydrocarbon charge subjected to a pretreatment with solid particles of low activity
|Mar 13, 1989
|Oct 9, 1990
|Mobil Oil Corporation
|Catalytic cracking apparatus employing mixed catalyst system
|Mar 30, 1989
|Oct 30, 1990
|Mobil Oil Corporation
|Multiple riser fluidized catalytic cracking process utilizing a C3 -C4 paraffin-rich co-feed and mixed catalyst system
|Nov 15, 1988
|Feb 5, 1991
|Mobil Oil Corporation
|Process and apparatus for two-phase fluid catalytic cracking system
|May 11, 1988
|Aug 13, 1991
|Institut Francais Du Petrole
|Steam-cracking in a fluid bed reaction zone
|Mar 16, 2001
|May 20, 2003
|Exxonmobil Research And Engineering Company
|Two stage FCC process incorporating interstage hydroprocessing
|Mar 16, 2001
|May 27, 2003
|Exxonmobil Research And Engineering Company
|Cycle oil conversion process
|Mar 16, 2001
|May 27, 2003
|Exxonmobil Research And Engineering Company
|Cycle oil conversion process incorporating shape-selective zeolite catalysts
|Oct 2, 2002
|Nov 2, 2004
|Exxonmobil Research And Engineering Company
|Cycle oil conversion process
|Oct 2, 2002
|Jan 4, 2005
|Exxonmobil Research And Engineering Company
|Cycle oil conversion process
|Mar 23, 2010
|Abb Lummus Global, Inc.
|Processing of different feeds in a fluid catalytic cracking unit
|Mar 8, 2010
|Mar 24, 2015
|Lummus Technology Inc.
|Processing of different feeds in a fluid catalytic cracking unit
|May 5, 2010
|Sep 1, 2015
|Kior, Inc.
|Catalyst/biomass mixing in transport reactor
|Dec 23, 2004
|Jun 29, 2006
|Soni Dalip S
|Processing of different feeds in a fluid catalytic cracking unit
|Mar 8, 2010
|Jun 24, 2010
|Soni Dalip S
|Processing of Different Feeds in a Fluid Catalytic Cracking Unit
|May 5, 2010
|Apr 18, 2012
|Improved catalyst/biomass mixing in transport reactor
|May 5, 2010
|Jul 9, 2014
|Improved catalyst/biomass mixing in transport reactor
|Sep 3, 1987
|Mar 9, 1988
|Mobil Oil Corporation
|Process for fluidized catalytic cracking with reactive fragments
|May 5, 2010
|Mar 21, 2012
|KiOR, Inc.
|Improved catalyst/biomass mixing in transport reactor
|May 5, 2010
|Nov 11, 2010
|Kior Inc.
|Improved catalyst/biomass mixing in transport reactor
|U.S. Classification
|208/75, 208/120.1, 502/49, 208/120.25
|International Classification
|Cooperative Classification
|European Classification
|Apr 26, 1983
Owner name: MOBIL OIL CORPORATION; A CORP OF NY.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CHOU, TAI-SHENG;REEL/FRAME:004123/0235
Effective date: 19830420
|Jul 2, 1985
|Certificate of correction
|Jan 15, 1988
|Fee payment
Year of fee payment: 4
|Jan 16, 1992
|Fee payment
Year of fee payment: 8
|Mar 25, 1996
|Fee payment
Year of fee payment: 12


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Lion Brand® Yarn Company
Item # 80802
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Free Pattern
Starting at
Heathered cream
Lion Brand Knitting Needles- Size 8 [5 mm] - 13.5 inches longLightweight, durable, and flexible pair of knitting needles. Plastic.
Natural cream
Also called tapestry, darning, or finishing needles, these large eye blunt needles are good for weaving in ends and sewing up seams on your knit crochet projects. Nickel-Plated Steel (2 each of sizes 13, 14, 16) Alternative option: Chibi Large Eye Blunt Needles (set of 3)
Warm medium brown
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Soft taupe brushed with gray
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Music video by Nkosi Echoez performing ICON (Official Video).
2013 Nkosi Echoez
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Divine Chocolate Bar
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As seen on Oprah!
A gourmet delight that lives up to its name, Divine Chocolate is made with only the finest quality, fairly traded cocoa beans from Kuapa Kokoo, a cooperative of small-holder farmers in Ghana. The cocoa is grown in the shade of the tropical rainforest, and slowly fermented and dried in the sun by farmers who take great pride in the chocolate company they co-own. Choosing delicious Divine Chocolate gives you guaranteed pleasure -- and the farmers a guaranteed fair deal and chance to invest in a better future.
- Dark Chocolate ingredients: cocoa mass (70% cocoa solids), sugar, cocoa butter, emulsifier: soya lecithin (non GM), vanilla
- Milk Chocolate ingredients: sugar, cocoa butter, dried cream, cocoa mass, whole milk powder, emulsifier: soya lecithin (non GM), vanilla
- White Chocolate ingredients: sugar, cocoa butter, skimmed milk powder, butterfat, emulsifier: soya lecithin (non GM), vanilla
- Fair Trade Certified
- Net wt. 3.5 oz (100g)
- Handmade in and fairly traded from Ghana
May contain trace amounts of nuts and wheat.
Created to help women worldwide gain economic security for themselves and their families by earning fair wages for their handiwork, Global Girlfriend sources women-made, fair-trade imported, eco-friendly products. By supporting long-term partnerships with the artisans, it fosters equal employment opportunities, healthy and safe working conditions, technical assistance, and development strategies to help reduce poverty, one community at a time. Become a "Global Girlfriend" and help build a brighter future for girlfriends around the globe!
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text: Land Rover import opportunityCé hé sin7/30/14 6:09am13EditPromoteDismissUndismissHideShare to KinjaGo to permalink Here we find a 1983 (look at the plate) Defender (look above the grille). More than 25 years old and the perfect car to import to the US. Buyers love Land Rovers and you could import it and sell on for good money. Who can tell me why this might not be quite such a good idea? Reply13 repliesLeave a reply


text:
Segway Tour at Park Zandvoort
Explore the park surroundings in a different way: on a Segway, an electric two-wheeler. It's environmentally-friendly and great fun.
A Segway is an electric two-wheeler that you operate by moving your body. After a brief training session, an experienced guide will take you through the beautiful places in the village and in the region. Feel the refreshing wind through your hair while you ride behind one another as a group of friends, family members or colleagues.
- On the park
- Yes
- age
- From 16 years.
- Price
- Request in park
- Is bookable
- Yes
- Payable with Topping
- No
A Segway tour lasts 1.5 to 2 hours.
Although we have taken the utmost care to ensure the content is accurate the possibility exists that certain information has become outdated or (no longer) correct. Click here for the current information on the website of Center Parcs.


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Media / Product and service news / Atlas Copco introduces new 1 megawatt generator
Atlas Copco introduces new 1 megawatt generator
–Atlas Copco introduced its new QAC 1200 1MW generator at Power-Gen International 2013 in Orlando, Fla., Nov. 12 through 14. To expand upon the standard QAC1MW generator designed for the European market, the QAC 1200 was specifically engineered to U.S. and Canadian specifications. With a wide variety of options, customers can customize the unit based on their situation such as high altitudes or extreme weather conditions. The flexibility of the QAC 1200 makes it ideal for either prime power or critical standby power in the mining, oil and gas, industrial and construction industries, as well as being an excellent rental product.
Another option available is the Qc4002 controller that allows a user to create a Power Management System (PMS). This allows a very simple method to parallel two or more generators beyond 1MW, enhancing the core value of predictable power.
Additional options include battery charger, coolant heater, alternator heater, external fuel supply 3-way valves with quick connections, automatic fuel transfer system, engine lube oil make up system, cold weather package, air inlet shutdown valve and spark arrestor.
The QAC 1200 is designed to deliver predictable power through reliable performance and risk-free operation. "Customers don't need a piece of equipment; they need power. In order to deliver these key benefits and the peace of mind that comes with them, Predictable Power is ingrained in everything we do, from design, testing, building, to commissioning and maintenance," said Atlas Copco Portable Energy's Julio Tome, Product Manager – Generators.
For further information please contact:
Jim Siffring, Product Manager - Generators
Atlas Copco Construction Equipment, USA, LLC
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Atlas Copco Construction Equipment
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Christina Burns, Marketing Communications Director
Atlas Copco Construction Mining Technique USA LLC
Telephone: 720-235-2325; Fax: 623-780-0222
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Liz Martin, Public Relations Specialist
Ellenbecker Communications, Inc.
Telephone: 507-945-0103; Fax: 877-572-9860
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text:
South Korean prosecutors questioned Lotte Group's chairman, Shin Dong-bin, on Tuesday in a corruption probe at the country's fifth-largest business group.
"I am sorry for having caused concern," Shin told reporters in a live televised broadcast outside the Seoul Central District Prosecutors' Office. He said he would cooperate with the investigation.
Lotte started as a chewing gum company in Japan in 1948 but now operates businesses in chemicals, food, shopping and hotels, including South Korea's largest discount and department store chains. Its brands are well recognized not only in Japan and South Korea but around Southeast Asia.
The months-long investigation into allegations of slush funds, embezzlement and tax evasion in the conglomerate was halted temporarily after the group's vice chairman, a top aide to Shin, was found dead in August in a suspected suicide just hours before he was to face questioning.
In June, the probe led Lotte to withdraw an initial public offering plan for Hotel Lotte Co. that could have raised up to 5.7 trillion won ($5.1 billion).
Apart from the probe, Shin and his elder brother, Shin Dong-joo, are embroiled in a bitter battle for control of the Lotte group.


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A Minimalist Design Looks Great for Clearing Tau
Interception of Extracellular Tau by Antibodies May Be Sufficient to Stop the Spread of Tau in AD
Spherical Nucleic Acids Deliver a New Package for Oliognucleotide Therapeutics
SNAs Are a Hopeful First Step in Boosting the Utility of Oligonucleotides to Treat a Variety of Human Diseases
Downstream Issues Still Beset Production
To Protect the Bottom Line, Biomanufacturers Invest in Downstream Purification Technology
GEN Roundup: No Detail Is Too Small in Bioprocess Scaleup
A Change in Scale Can Change Everything
For full access to this article login to GEN Select now.
San Diego Pioneers Cleantech Solutions
Established Biotech Cluster Takes the Lead In Reducing Country's Dependence on Fossil Fuels
- San Diego has been a leading hub of the biotech industry, starting with the formation of Hybritech in 1978, a pioneer in mAb-based diagnostics and treatments. Now the San Diego region is at the forefront of one of the newest biotechnology clusters known as cleantech or greentech, which aims ...
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- Do not put any letters or characters here if you are not a spy program.


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Which Joe gave his name to 'sloppy joes'? We look at five interesting sandwiches and their lexical origins.
proper nounGreek Mythology
An enchantress who lived on the island of Aeaea. When Odysseus visited the island his companions were changed into pigs by her potions, but he protected himself with the magic herb moly and forced her to restore his men to human form.temptress, siren, femme fatale, enchantress, sorceress, delilah, circe, lorelei, mata hariView synonyms
Via Latin from Greek Kirkē.
Further reading
12 synonyms for foolRead more
Are you looking for a word for a foolish person? We explore twelve interesting words to describe the dunderheads in your life.
6 'run' phrases you probably don't knowRead more
Before you run for the hills, let's run through a list of 'run' expressions that are running through our minds.
How brothers became buddies and brosRead more
The definitions of 'buddy' and 'bro' in the OED have recently been revised. We explore their history and increase in popularity.


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- Indian
- Vegetarian
Brick Lane Curry House
Menu for Brick Lane Curry House
Menu for Brick Lane Curry House provided by Allmenus.com
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Ratings and Reviews for Brick Lane Curry House
Jul 07 2015
Vaishali S. via Yelp
This review is long overdue. Brick Lane on the Upper East Side consistently has high quality food. The lunch buffet is creative and delicious. They offer a...read more
Nov 09 2015
Margorie G. via Yelp
Simple, great, and to the point. If you're looking for Indian food in the upper east side this is your place. Not only is the restaurant clean and quaint...read more
Mar 07 2016
Steve L. via Yelp
Unfortunately closed down but there are others in the chain well worth visitingread more
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The Concept of the CivilianTaylor and Francis 2015; US$ 54.95
The Concept of the Civilian: Legal Recognition, Adjudication and the Trials of International Criminal Justice offers a critical account of the legal shaping of civilian identities by the processes of international criminal justice. It draws on a detailed case-study of the International Criminal Tribunal for the former Yugoslavia to explore two key... more...
Rules of RiotPrinceton University Press 2015; US$ 41.95 US$ 33.56
Riots, insurrections, guerrilla movements, civil wars?all forms of internal conflict are increasing throughout the world. The conditions that breed domestic violence in the Third World persist, and events in Ulster and Quebec have shown that more advanced industrial countries are not immune from civil disorder. The subject of James E. Bond's book?how... more...
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Yearbook of International Humanitarian Law 2013T.M.C. Asser Press 2014; US$ 119.75
This volume contains several articles on the topic ?Detention in non-international armed conflict?, including the Copenhagen Process, and moreover features contributions on autonomous weapons systems, Apartheid and the second Turkel Report. It also contains an elaborate Year in Review and a special section on the high-level Boundaries of the Battlefield... more...
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First look at Apple's 'next generation MacBook Pro' with photosAfter announcing the "next generation MacBook Pro" complete with Retina Display, Apple let WWDC attendees spend some quality time with the machine and AppleInsider was there to grab some up-close photos.
"The most beautiful computer we have ever made"
That's what Apple is calling the new Retina Display-toting MacBook Pro, and the company had an example on display at WWDC. The unit was protected by a plexiglass cylinder, but guests were able to get close enough to get a feel for the high-resolution display and redesigned port layout.
First look at the sleek outer design of Apple's new MacBook Pro.
Off-axis screen on the MacBook Pro's 15.4-inch 2,880 by 1,880 pixel screen jams in 220 pixels-per-inch and is quite impressive to the naked eye, though future tests will show just how it compares with current models. Note the deep blacks and reduced glare, which Apple claims is 75 percent less reflective than glossy displays on current machines.
The high-resolution Retina Display is the largest of its kind implemented by Apple and the first in a laptop.
Apple's newly-redesigned MagSafe 2 power connector looks to be physically similar to current offerings, though the revamped internals were not on display at the time of this writing.
Apple's new MagSafe 2 connector.
The uni-body chassis is packed with high-density batteries to accomodate the added draw from the Retina Display that will create a higher level of heat compared to current=generation models. As seen in the photo below, the new unit sports an interesting venting setup on its underside to handle the laptop's unique thermal properties.
Underside view of the next-gen MacBook Pro with side vents.
Upgraded connectivity options include USB 3.0 and a dedicated HDMI-out port along with a high-speed Thunderbolt port and SD card reader. With the nixing of an optical drive, Apple has moved three connector ports to the right side of the machine.
Re-arranged ports with USB 3.0, HDMI-out and SD card slot.
On Topic: MacBook Pro
- Apple registers Russian trademarks for three new MacBooks ahead of Oct. 27 event
- Apple might debut 'MagSafe-like' USB-C adapter with redesigned MacBook Pro line
- New Apple event invite recalls original Macintosh, iMac introductions
- Potential MacBook Pro OLED function row names include 'Magic Toolbar,' 'Control Strip,' 'Touch Bar'
- 'Hello again:' Apple sends invitations for event on Oct. 27, new MacBook Pros expected


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Pure Lube Water Based Lubricant Stimul8
Product description
Pure Lube from Stimul8 is a water-based lubricant of exceptional class! The high quality ingredients are organic and skin friendly, and this excellent gel has a natural gliding effect, responding actively to moisture for better sliding properties. It will leave the skin feeling nice and soft after use, and this lubricant can also be used for a soothing massage. It does not stick, is easy to rinse with water and can be used with latex condoms. Dermatologically tested, fragrance free. Contents: 100 ml.
|Product code:
|Stimul8 Pure Lube:
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|Dermatologically tested, CE certified
|100 millilitre


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Purchase Cards:
Increased Management Oversight and Control Could Save Hundreds of Millions of Dollars
GAO-04-717T: Published: Apr 28, 2004. Publicly Released: Apr 28, 2004.
Additional Materials:
- Highlights Page:
- Full Report:
- Accessible Text:
(202) 512-9505
Office of Public Affairs
(202) 512-4800
From 1994 to 2003, the use of government purchase cards increased from $1 billion to $16 billion. During this time, agencies primarily focused on ways to increase the use of purchase cards. Beginning in 2001, GAO testified and reported that significant weaknesses in internal controls made agencies vulnerable to fraud, waste, and abuse, and inefficient purchasing actions. In response to increased use of purchase cards and serious control weaknesses in the purchase card program, GAO was asked to summarize the growth of the purchase card program, the control weaknesses that led to fraud and misuse of the cards, actions taken to tighten controls and discipline cardholders, and agency actions to leverage the government's buying power when using the purchase card.
Governmentwide efforts to promote increased usage of purchase cards for small and routine purchases have dramatically increased the number of purchase card accounts and spending. The use of a well-controlled purchase card program is a useful tool in streamlining the government's acquisition processes and providing agencies flexibility to make small and routine purchases. However, improvements in program management and oversight could save hundreds of millions of dollars by (1) strengthening controls and monitoring transaction activity to minimize fraudulent, improper, and abusive purchase card transactions and (2) leveraging the government's buying power to achieve discounts with frequently used vendors. GAO's audits of purchase card controls at DOD and four civilian agencies and federal agency Inspectors General audits identified ineffective management oversight and weak internal controls, leaving agencies vulnerable to fraudulent, improper, and abusive purchase card activity. GAO's data mining, forensic audit follow-up, and investigations identified numerous purchases of personal items such as jewelry, designer leather goods, clothing, stereo equipment, food, and entertainment. While agencies responded to these audit reports by issuing and updating purchase card policies and procedures, GAO's work at DOD demonstrated that little disciplinary or administrative action was taken against those who made improper or abusive charges. GAO also found that agencies generally did not take advantage of opportunities to obtain more favorable prices on purchase card buys with frequently used vendors--vendors where an agency spends more than $1 million annually. GAO's examination of six federal agencies that account for over 85 percent of federal government purchase card spending identified isolated examples of agencies negotiating discounts for items such as office supplies and technology purchases. However, a conservative approach indicated that if the six agencies obtained discounts of only 10 percent from vendors where they spent more than $1 million a year, annual savings of up to $300 million could be achieved without sacrificing the ability to acquire items quickly or compromising socioeconomic goals. As shown in the following table, during fiscal year 2002, these agencies spent nearly $3 billion with frequently used vendors.
Oct 6, 2016
Securities and Exchange Commission:Management Has Enhanced Supervisory Controls and Could Further Improve EfficiencyGAO-17-16: Published: Oct 6, 2016. Publicly Released: Oct 6, 2016.
Aug 19, 2016
DOD Financial Management:Improvements Needed in the Navy's Audit Readiness Efforts for Fund Balance with TreasuryGAO-16-47: Published: Aug 19, 2016. Publicly Released: Aug 19, 2016.
Aug 12, 2016
Congressional Award Foundation:Review of the Audit of the Financial Statements for Fiscal Year 2015GAO-16-754R: Published: Aug 12, 2016. Publicly Released: Aug 12, 2016.
Jul 29, 2016
DATA ACT:Improvements Needed in Reviewing Agency Implementation Plans and Monitoring ProgressGAO-16-698: Published: Jul 29, 2016. Publicly Released: Jul 29, 2016.
Jul 28, 2016
Financial Management Systems:HUD Needs to Address Management and Governance Weaknesses That Jeopardize Its Modernization EffortsGAO-16-656: Published: Jul 28, 2016. Publicly Released: Jul 28, 2016.
Management Report:Areas for Improvement in the Bureau of the Fiscal Service's Information Systems ControlsGAO-16-655R: Published: Jul 28, 2016. Publicly Released: Jul 28, 2016.
Jul 13, 2016
Management Report:Improvements Needed in Controls over the Processes Used to Prepare the U.S. Consolidated Financial StatementsGAO-16-621: Published: Jul 13, 2016. Publicly Released: Jul 13, 2016.
Jul 11, 2016
Improper Payments:CFO Act Agencies Need to Improve Efforts to Address Compliance IssuesGAO-16-554: Published: Jun 30, 2016. Publicly Released: Jul 11, 2016.
Jun 13, 2016
Management Report:Improvements Needed in CFPB's Internal Controls and Accounting ProceduresGAO-16-522R: Published: Jun 13, 2016. Publicly Released: Jun 13, 2016.
Jun 6, 2016
Management Report:Areas for Improvement in the Federal Reserve Banks' Information Systems ControlsGAO-16-601R: Published: Jun 6, 2016. Publicly Released: Jun 6, 2016.
Looking for more? Browse all our products here


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You will gain stylish extra storage as well as create a fantastic design feature with the Charly headboard, specifically crafted to sit at the head of the Charly single bed. The lovely light and bright Acacia Oak wood effect finish is complimented by White melamine detail on the cubby cupboard door and trim, and these warm neutral tones will blend with any décor. There is a nifty rack of three shelves concealed in the side of the unit, and then an open shelf and cubby cupboard sit below a full width shelf which is actually the top of the unit.
123cm wide x 93cm height x 29cm depth
Side shelf width: 22.3cm
For complete assembly instructions please click here
Credit is available subject to status to UK residents aged 18 or over. Steinhoff UK Retail Limited trading as Bensons For Beds acts as a credit broker and not as a lender: their registered office is Festival House, Jessop Avenue, Cheltenham, Gloucestershire, GL50 3SH. Credit is provided by Creation Consumer Finance Ltd (Chadwick House, Blenheim Court, Solihull B91 2AA), is authorised and regulated by the Financial Conduct Authority


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If you are a BVA student member at a UK vet school, or a recent graduate, then you can apply for the following grants to carry out research projects overseas:
Also see
travel grants awarded by other bodies
The BVA overseas travel grant scheme gives students the chance to gain experience in the prevention and control of exotic and emerging animal diseases, as well as helping them to develop beneficial life skills such as communication, adaptability and open-mindedness.
International animal charity
Vetwork UK welcomes applications for all types of overseas projects. However projects that specifically reflect the work of Vetwork UK will be given preference.
Examples of Vetwork's areas of interest include:
We award £500 to up to four UK undergraduates every year.
Vetwork UK awards £500 to two overseas research projects every year.
The grants are now available to all UK veterinary students who are BVA members, not just those in their clinical years.
Applications for the 2016 grants have now closed.
For further information email
The following research reports were conducted by previous travel grant recipients in 2015:
Further reports available from
In collaboration with
World Association of Transport Animal Welfare and Studies (TAWS), we award annual travel grants to undergraduates for projects involving working animals used for draught and pack purposes, including transport and cultivation, in developing countries.
Up to £500 per grant.
The selection committee comprises representatives of TAWS.
Applicants must be a BVA student member, in their clinical years at a veterinary school in the UK.
Applications for the 2016 grants have now closed.
The following reports were written by previous TAWS grant recipients:
The Donkey Sanctuary is offering two BVA overseas travel grants in 2016 for:
Travel grants 1 and 2 will support a visit to one of The Donkey Sanctuary's international programmes in Mexico, Egypt, Ethiopia, Kenya or India. Grant recipients are expected to:
Both travel grants will cover the costs of international travel and local subsistence.
Veterinary and social science undergraduates at UK universities may apply. Veterinary student applicants must be BVA student members and preferably in their clinical years.
Applications for 2016 grants have now closed.
For general information about The Donkey Sanctuary contact Angie Garner, International Veterinary Liaison Assistant:
01395 573046
To discuss the type of work that you may undertake or any specific donkey welfare interests, contact Dr Kevin Brown, International Programme Development Manager (Donkey):
01395 57301
The Harry Steele-Bodger Memorial Travel Scholarship was established in September 1953 to honour the memory of Henry W Steele-Bodger, President of the Association from 1939 to 1941, in recognition of his great services to the veterinary profession and agriculture, particularly during World War Two. See
Harry Steele-Bodger's biography (48 KB PDF)
The scholarship is intended to assist a visit to a veterinary or agricultural school, research institute or some other course of study approved by the governing committee.
Penultimate and final year veterinary students, and graduates of UK and Ireland veterinary schools qualified for no more than three years.
Applications for 2016 grants have now closed.
For further information email
RCVS Knowledge
Travel scholarships to attend international veterinary conferences, or pursue themes of clinical or non-clinical research involving short-term visits to veterinary or medical centres or research institutes abroad.
British Veterinary Zoological Society (BVZS) Zebra Foundation
For vet students practising at an institution specialising in zoological medicine or undertaking research projects.
MAH-IVSA Scholarship and Travel Grant Programme
The International Veterinary Students' Association (IVSA) and Merck Animal Health (MAH) provide between 50 and 100 scholarships of $500 to $2,000 for veterinary students to gain international experience.
MSD Animal Health Connect Bursary
A bursary for UK veterinary undergraduates from each of the UK's veterinary schools to undertake research in new and exciting areas of veterinary work. Projects can be overseas or UK based.
The Moredun Foundation scholarship
An annual scholarship for short-term projects to broaden your education and experience in livestock health and welfare and the agricultural industry.
The Winston Churchill travelling fellowship
Offering fellowships to anyone in the UK wishing to gain knowledge and experience overseas in science and technology.
Universities Federation for Animal Welfare (UFAW) animal welfare student scholarships
UFAW invites students at British universities and academic institutions to apply for its student scholarships.
Wellcome Trust Biomedical vacation scholarships
Enables students or trainees in the industry to carry out a project which is aimed at improving the welfare of food animals in markets, during transport or at slaughter.
Laboratory Animals Veterinary Association (LAVA) EMS study scheme
LAVA's scheme covers reasonable expenditure for veterinary students wishing to 'see practice' with veterinarians working in laboratory animal science and medicine, as part of their extramural studies. Placements (for 1 or 2 weeks) are arranged throughout the UK and Ireland.
Dr Hadwen Trust's Summer Studentship Scheme
Assistance for undergraduate students in gaining practical animal-replacement research experience by working in a laboratory environment. Research that requires or involves the use of living animals in any way will not be supported.
World Horse Welfare bursary
The undergraduate bursary scheme is open to veterinary or farriery students studying in the UK or Ireland, who have a special interest in horse welfare. Successful applicants can work at one of World Horse Welfare's (WHW) rescue centres in the UK or as part of WHW's international programme.
Humane Slaughter Association (HSA) grants
HSA offers grants for essential research and other projects aimed at improving animal welfare during transport, in markets and at slaughter.
Stuck? Questions or need help? Contact the membership team on 020 7908 6350 or email firstname.lastname@example.com
There is plenty of valuable advice available if you are considering working abroad.
© 2014: British Veterinary Association
British Veterinary Association is registered in England No 206456 at 7 Mansfield Street London WIG 9NQ
VAT registration number GB 232 7441 80. BVA logo registered trademark numbers 2446548. 2446549A & 2446549B


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George Levings speaks to RA about moving forward with the drum & bass project.
Thu, 14 Jul 2016
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The UK producer's third solo LP will arrive on October 18th.
Tue, 31 May 2016
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Youngsta will also join us for an on-water session at this year's edition of the Croatian festival.
Fri, 05 Feb 2016
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The new London event has released the lineups for three of its eight nighttime sessions.
Mon, 25 Jan 2016
Commix and Flowdan are also confirmed for the ninth edition of the Croatian festival.
Mon, 02 Feb 2015
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BLM will inaugurate the new label with a four-tracker, dropping next week.
Tue, 02 Dec 2014
Calibre, Ital Tek, Loxy and more feature on the new 24-track box set from 31 Recordings.
Tue, 18 Nov 2014
A box set including new tracks and a mix from Friction are among the festivities set to drop in December.
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Goldie's infamous Dnb label.
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12 Years Ago: The Rolling Stones, AC/DC and Rush Rock Toronto
The Rolling Stones led a benefit concert in Toronto on July 30, 2003.
The Rolling Stones led a benefit concert in Toronto on July 30, 2003.
We look at the important contributions made by John Rutsey during his brief tenure as Rush's first drummer.
A woman proudly displayed her Rush fandom on tonight's (July 16) episode of 'Jeopardy!'
Released on June 29, 2004, as part of a celebration of their 30th anniversary, the 'Feedback' EP did a little crate-digging to pay tribute to some of Rush's early influences.
Rush performed 'Losing It' in Concert for the first time ever in June 2015.
Drunken shenanigans in a hotel bar took place between Rush and Van Halen on June 20, 1980.
When Rush rolled into New Orleans on May 22, they had an extra VIP in attendance.
Rush will film both of their Toronto performances this month, returning for a hometown concert recording for the first time since their 'Test for Echo' dates nearly two decades ago.
Rush opened what may be their last major tour on May 8.
Rush have spent more than 40 years charging restlessly ahead, but going out on the road for an anniversary tour is bound to put a fellow in a reflective mood.


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Humberto Ramos
Champions #2 by Humberto Ramos *
Gambit - Humberto Ramos
humberto ramos (@humberto_ramos) | Twitter
Wonder Woman by Humberto Ramos
I like this image because it shows how superheroes do get injured and feel sadness, often after losing their way. I feel as though the blood on X-23's claws represent innocent blood being spilt, which represents how heroes cannot save everyone.
✭ Harley Quinn by Humberto Ramos …
Peter Parker - Spider-Man by Humberto Ramos *
Art by Humberto Ramos* • Blog/Website | (www.humbertoramos.com) ★ || CHARACTER DESIGN REFERENCES™ (https://www.facebook.com/CharacterDesignReferences & https://www.pinterest.com/characterdesigh) • Love Character Design? Join the #CDChallenge (link→ https://www.facebook.com/groups/CharacterDesignChallenge) Share your unique vision of a theme, promote your art in a community of over 50.000 artists! || ★
Jean Grey by Humberto Ramos
Crimson Vol.1 by Humberto Ramos, colours by Edgar Delgado *