text:
US4737263A - Process and apparatus for catalytic dewaxing of paraffinic stocks and the simultaneous removal of cracked products - Google PatentsProcess and apparatus for catalytic dewaxing of paraffinic stocks and the simultaneous removal of cracked products Download PDF
- Publication number
- Authority
- United States
- Prior art keywords
- catalyst
- dewaxing
- process
- bed
- system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
This application is a continuation-in-part of co-pending application Ser. No. 743,721, filed June 11, 1985, now abandoned, which is a continuation-in-part of co-pending application Ser. No. 662,873, filed Oct. 19, 1984, now abandoned, both of which are incorporated herein by reference.
1. Field of the Invention
This invention relates to a novel process and reactor for catalytically dewaxing a waxy liquid petroleum feedstock utilizing a shape-selective crystalline zeolite catalyst. More particularly, this invention relates to improvements in the shape-selective dewaxing of liquid petroleum feedstocks to obtain improved product quality, operating efficiency, as well as improvements in the aging characteristics of the shape-selective dewaxing catalyst.
2. Discussion of the Prior Art
The cracking and/or hydrocracking of petroleum stocks is in general well known and widely practiced. It is known to use various zeolites to catalyze cracking and/or hydrocracking processes. The cracking may have the intent to convert a certain class of compounds in order to modify a characteristic of the whole petroleum stock. Exemplary of this type of conversion is shape-selective conversion of straight and slightly branched aliphatic compounds of 12 or more carbon atoms to reduce pour point, pumpability, and/or viscosity of heavy fractions which contain these waxy constituents. The long carbon chain compounds tend to crystallize on cooling of the oil to an extent such that the oil will not flow, hence may not be able to be pumped or transported by pipelines. The temperature at which such mixture will not flow is designated the "pour point", as determined by standarized test procedures.
The pour point problem can be overcome by techniques known in the art for removal of waxes or conversion of those compounds to other hydrocarbons which do not crystallize at ambient temperatures. An important method for so converting waxy hydrocarbons is shape-selective cracking or hydrocracking utilizing principals described in U.S. Pat. No. 3,140,322 dated July 7, 1964. Zeolitic catalysts for selective conversions of wax described in the literature include such species as mordenite, with or without added metal, to function as a hydrogenation catalyst.
Particularly effective catalysts for catalytic dewaxing include zeolite ZSM-5 and related porous crystalline aluminosilicates, as described in U.S. Re. Pat. No. 28,398 (Chen et al) dated Apr. 22, 1975. As described in that patent, drastic reductions in pour point are achieved by catalytic shape-selective conversion of the wax content of heavy stocks with hydrogen in the presence of a dual-functional catalyst of a metal plus the hydrogen form of ZSM-5. The conversion of waxes is by scission of carbon-to-carbon bonds (cracking) and production of products of lower boiling point than the wax. However, only minor conversion occurs in dewaxing. For example, Chen et al describe hydrodewaxing of a full range shale oil having a pour point of +80° F. (+27° C.) to yield a pumpable product of pour point at -15° F. (-26° C.). The shift of materials from the fraction heavier than light fuel oil to lighter component was in the neighborhood of 9% conversion.
Current technology for dewaxing petroleum stocks having elevated pour points involves the use of trickle beds, whereby gas (primarily hydrogen) and the petroleum stock concurrently flow downward over a bed of solid catalyst. This three-phase trickle bed concept makes use of an intimate mixing between gas and liquid phases while in contact with the catalyst in order to facilitate dewaxing. Performance level of the process is gauged by the length of time during which the process is producing products which meet specifications, as well as the minimum temperature required to attain acceptable products. A trickle bed process is disclosed in U.S. Pat. No. 4,332,670 to Antal, which is directed to hydrodewaxing a distillate hydrocarbon compound over a zeolite ZSM-5 containing catalyst. In the trickle bed reactor the gas is the continuous phase, while the liquid petroleum stock trickles down as a discontinuous phase.
In the hydroprocessing of liquid petroleum feedstocks, including heavy feedstocks, e.g., 650° F.+ (343° C.+) lube oils, it is desired to remove lighter conversion products from the liquid petroleum flow while concurrently providing a hydrogenative environment for catalytic conversion, which is particularly utilized in the case of the processing of highly waxy feedstocks. Frequently, lighter products which are obtained from cracking and/or hydrocracking reactions compete with the heavier feed molecules for access to the cracking sites in the zeolites which are employed in the implementation of the catalytic dewaxing process. Inasmuch as these lighter products diffuse more rapidly into the catalyst than the larger feed molecules, they have a tendency to retard the rate of conversion of the heavier molecules. Moreover, the lighter products also tend to be either more difficult to crack, such as low molecular weight paraffins, or easier to polymerize, such as low molecular weight olefins. They also possess a tendency to coke more readily than their heavier counterparts so as to thereby retard the conversion of the heavier molecules to an even greater extent.
This competition between the light and heavy liquid petroleum molecules is rendered particularly critical when there is employed a catalyst which essentially constitutes a shape-selective zeolite, for example, a zeolite exemplified by ZSM-5, for the dewaxing of liquid petroleum or lube stocks. Processes in reactors which utilize aluminosilicate zeolite catalysts, such as ZSM-5 or other zeolites having smaller pore openings, are disclosed in U.S. Pat. No. 4,222,855 to Pelrine et al and in U.S. Re. Pat. No. 28,398 to N. Y. Chen, both of which are incorporated herein by reference. U.S. Pat. No. 4,263,126 to Rollmann discloses dewaxing a hydrocarbon oil by use of a powdered ZSM-5 catalyst dispersed in the oil undergoing conversion.
Other techniques for catalytic hydrodewaxing involve the use of ebullated catalyst beds. U.S. Pat. No. 2,987,465 is directed to a batch process for contacting a liquid and a gas in the presence of an ebullating catalyst bed. The catalysts are maintained in random motion by up-flowing streams of liquid and gas which enter the bottom of the reactor. U.S. Pat. No. 2,706,167 to Harper is directed to the hydrogenation of hydrocarbon oils, in which the feedstock and hydrogen are introduced into the lower part of the reactor with force enough to suspend and ebullate the catalyst during the reaction. U.S. Pat. No. 4,317,746 to Richardson is directed to the use of rotating mixers to maintain catalyst particles in a state of suspension in an ebullating bed.
Although the utilization of different types of hydroprocessing reactors to implement catalytic dewaxing processes is disclosed in the prior art, as exemplified by the above-mentioned U.S. patents, broadly referring to ebullated reactors, stirring tank-type reactors or trickle bed reactors, there is an obvious need in the technology to more precisely define specific hydroprocessing reactor designs. Needed are reactors which, in a highly efficient and novel manner, will facilitate the removal of the lighter products from the liquid petroleum feedstocks through the intermediary of hydrogen stripping, while concurrently preserving an intimate three-phase contacting relationship among hydrogen, liquid petroleum feedstock and catalyst.
Another problem which has not been adequately solved during dewaxing of lubricating oil feedstocks with shape-selective zeolite catalysts is the aging of the dewaxing catalyst. Thus, it has been found that as dewaxing proceeds, a higher reactor temperature is required to compensate for decreased catalytic activity and meet product specifications. However, increasing the reactor temperature incurs additional energy costs, often changes the product distribution which is obtained, and often results in increased coking of the feedstock during dewaxing. Coking further decreases the catalyst life.
Accordingly, another object of the present invention is to reduce the aging rate of the shape-selective dewaxing catalyst during catalytic dewaxing of a lubricating oil or other waxy liquid petroleum feedstock.
The present invention is directed to producing a lubricating oil using a continuous stirred tank reactor (CSTR), in which the shape-selective dewaxing catalyst is immersed in the liquid to be dewaxed. In the preferred reactor types, the catalyst is submerged and rotated as a catalyst bed within the hydrocarbon liquid to be converted. Normally, lubricating oils are produced utilizing a fixed bed reactor. The current technology also utilizes a trickle bed reactor to remove lighter conversion products and provide a hydrogen environment. The object of the present invention is to provide a reactor which will remove the lighter products and preserve a three-phase relationship among hydrogen, the feedstock and the catalyst. Another object is to retard catalyst aging. We have found that by contacting a lubricating oil to be dewaxed with a hydrodewaxing catalyst and removing the resulting cracked gaseous products from the catalyst as soon as possible, the aforementioned objects could be attained.
The feedstock is contacted in a catalyst bed which is agitated. Hydrogen or another hydrocarbon-free gas is injected into the bed. By the agitation of the catalyst bed, the gases generated during the dewaxing operation are removed. It is important that the catalyst bed be completely submerged in the petroleum liquid being dewaxed, and that there be a minimum contact time between the catalyst and the product gases during the dewaxing step. Preferred conditions include a temperature of 500° to 1100° F. (260°-593° C.), preferably less than 700° F., and more preferably 540° to 565° F. (282°-296° C.); LHSV of 0.1 to 100; hydrogen-hydrocarbon mole ratio of 0 to 20; and pressure of 100 to 3000 psig.
In this invention, an improved dewaxing process and reactor are disclosed. Briefly stated, one aspect involves a process for hydrodewaxing lube oils comprising the steps of (a) contacting the lube oil to be dewaxed with a suitable hydrodewaxing catalyst, while (b) maintaining the dewaxing catalyst submerged in the liquid phase of said oil being dewaxed and removing the resulting cracked gaseous products from contact with the dewaxing catalyst as quickly as possible. One method of removing the gaseous products is to keep the interfacial area between the liquid and gas phases as large as possible to allow rapid devolution of the cracked products into a free gas phase above the liquid oil phase. Preferably, hydrogen is bubbled through the liquid to enhance removal of the cracked products.
In another aspect of the present invention, catalyst aging of the shape-selective dewaxing catalysts used to dewax lubricating oil petroleum feedstocks is substantially reduced by operating the dewaxing reactor within a narrow relatively low temperature range. A temperature range has been found which is high enough so as to effect a substantial reduction in the pour point of the product, but not so high as to cause catalyst deactivation. It has been found that dewaxing at a temperature in the range of 540° F. (282° C.) to less than 565° F. (296° C.) allows the feedstock to be dewaxed to a desired product pour point for a substantial period of time without the need to increase reactor temperature.
FIG. 1 depicts one type of reactor useful in the application of this invention;
FIG. 2 is a plot comparing the activity of a dewaxing catalyst used according to the prior art with the activity of a catalyst used according to the process of this invention;
FIG. 3 is a plot illustrating the reactor temperature required to maintain a pour point of 20° F. (-6.7° C.) relative to the days-on-stream of two dewaxing catalysts. The corrected temperature is the actual reactor temperature plus the difference between the actual pour point of the product and the target pour point (20° F.):
T.sub.corrected =T.sub.actual+(pour point-20° F.) ;
FIGS. 4 and 6 are plots illustrating the effect of pour point on lube yield for two different feedstocks for a fixed bed and a continuous stirred tank reactor;
FIGS. 5 and 7 are plots illustrating the effect of pour point on Viscosity Index for two different feedstocks for a fixed bed and a continuous stirred tank reactor; and
FIGS. 8 and 9 compare the relationship between pour point and Viscosity Index (FIG. 8) and pour point and lube yield (FIG. 9) for a fixed bed reactor, a single stage continuous stirred tank reactor and a multi-stage continuous stirred tank reactor.
Continuous Stirred Tank Reactor (CSTR)
Fixed bed reactors are commonly used in order to produce a lubricating oil having desirable qualities. It is generally believed that the fixed bed reactor is the most efficient way of producing such a lubricating oil. However, we have discovered that through the fixed bed reactor lubricating oil production may actually be hindered.
During the reaction, volatile products are also produced which foul the catalyst, slow the reaction process and hinder the dewaxing of the lubricating oil feedstock. Therefore, the volatile products must be removed before they further interfere with the reactor.
We searched for an efficient way to get rid of the secondary volatile products. Up to now, it was not thought that a CSTR could be used because of two major problems normally associated with such reactors. First, it was thought that immersing the catalyst in the liquid would reduce the effectiveness of hydrogen and cause fast catalyst deactivation, which are generally true for most reactions. Second, in a CSTR, there exists an inevitable reactor by-pass, resulting in an undesirable residence time distribution of the liquid in the reactor. The CSTR practices continuous feed and stirring in one vessel. In theory and practice, it has been found that a small fraction of the feed will pass through the reactor without ever reacting. For example, if the feed rate is one liquid hourly space velocity (LHSV) based on reactor volume, the average residence time of reaction in the reactor is one hour; but a small amount of feed may remain in the reactor for many hours and another small amount of unreacted feed may pass through the reactor within seconds. It is this unreacted feed which causes problems. The unreacted portion passing through the reactor is very damaging to the lube oil product, as it raises the pour point of the product. By blending a small portion of the raw undewaxed oil in the product, the pour point is substantially raised in a non-linear fashion, i.e., a small concentration of a high pour point material mixed with a large concentration of a low pour point material gives a higher pour point than the arithmetic average, and is therefore highly undesirable. For example, one would ordinarily assume that if 3% of 100° F. (37° C.) pour point feedstock was added to a 20° F. (-6.7° C.) pour point product, the ultimate product would have a pour point of about 20.5° F. (-6.4° C.). In actual practice, however, the product may have a pour point of 60° F. (12° C.) due to non-linear blending. Therefore, in order to make a 20° F. (-6.7° C.) pour point in one tank, it was assumed that the reaction conditions must be severe in order to accommodate for the by-passed reaction feedstock. However, we have discovered that the CSTR provides advantages over the fixed bed reactor which outweigh the disadvantages. These advantages are further enhanced by stacking more than one CSTR together in order to eliminate any possibility of unreacted feed being passed through the reactor.
Pursuant to particular features of the process of this invention, one type of useful reactor for this purpose is essentially a vertical reactor, preferably of the cylindrical type, wherein a cylindrical bed of catalyst material, such as crystalline zeolite, occupies a portion of the reactor. The bed may be mounted and, in an alternative embodiment, contained so that it can be agitated rapidly while submerged in a liquid oil phase. Liquid petroleum feedstock to be dewaxed is injected into the reactor, preferably at the bottom, and maintained primarily in a liquid phase as it permeates the bed of catalyst.
While the liquid feed stock is in contact with the catalyst bed, the catalyst bed is agitated and the dewaxing operation is carried out. If the catalyst bed is contained, it can be rotated rapidly while submerged. Preferably, hydrogen or other hydrocarbon-free gas is injected into the bottom of the tower so that it also flows upwardly through the feedstock and through the rotating cylindrical bed of catalyst. The gases generated in the dewaxing operation are collected at the top-most portion of the reactor, which is maintained in a free open configuration, so that the hydrogen gas bubbling through the liquid can enhance the degasification of the liquid oil phase. The oil is withdrawn at a point removed from the bed section of the reactor, and the gaseous phase is withdrawn at a higher level in the reactor.
Feedstocks which vary widely in their wax content can be dewaxed according to the process of this invention. One group of such oils is that which contains sufficient waxes to impart an undesirably high pour point. In general, such oils have a substantial fraction, i.e., at least about 10 vol %, which distills above 350° F. (176° C.). These oils, as a group, will be referred to herein as "waxy" oils, and include virgin petroleum crudes and fractions thereof, such as kerosene, jet fuel, light gas oil, heavy gas oil, fuel oils, and atmospheric and vacuum tower residua. Feedstocks which have been previously hydrotreated or hydrogenated, and which consequently contain little or no sulfur, can also be dewaxed by our process. The liquid feedstock preferably is a lube oil which has a boiling point between 650° and 1300° F. (343°-704° C.), and a pour point above 85° F. (29° C.). Shale oil, oil from tar sands and waxy syncrudes from coal may also be dewaxed in accordance with this invention.
Reaction Conditions
Typical dewaxing conditions include contacting the feedstock with the dewaxing catalyst at about 500° to 1100° F. (260°-593° C.), space velocity at about 0.1 to 100 LHSV, hydrogen-to-hydrocarbon mole ratio of about 0 to 20, and a pressure of about 100 to 3000 psig.
The important features of the present invention are as follows:
(1) operate at a low temperature range to reduce aging, i.e., temperature less than 700° F. (371° C.);
(2) the catalyst must be totally immersed in the liquid feedstock to be dewaxed;
(3) contact time between the catalyst and the product gases during the dewaxing step must be minimized; and
(4) use of multiple reactors in series is recommended.
Description of the Drawings
Referring now in detail to an embodiment of a useful reactor illustrated in FIG. 1 of the drawings, the reactor consists essentially of an upright or vertically-arranged container or tower which can be of cylindrical construction and which has an outer cylindrical shell or wall 2, and an end cover structure.
Interposed in and filling the space, or at least a portion thereof, in the reactor is a cylindrical catalyst bed 6 of catalyst material which, in a preferred instance, is a shape-selective crystalline zeolite catalyst, preferably a supported metal-exchanged ZSM-5, although other zeolites, such as described in Pelrine et al, U.S. Pat. No. 4,222,855 and U.S. Pat. Re. No. 28,398, may also be suitably employed as the catalyst material.
The preferred catalysts for this invention are shape-selective zeolite-type catalysts. For purposes of this invention, the term "zeolite" is meant to represent the class of porotectosilicates, i.e., porous crystalline silicates, that contain silicon and oxygen atoms as the major components. Other components may be present in minor amounts, usually less than 14 mole %, and preferably less than 4 mole %. These components include aluminum, gallium, iron, boron and the like, with aluminum being preferred, and used herein for illustration purposes. The minor components may be present separately or in mixtures.
The silica-to-alumina mole ratio referred to 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 forms within the channels. Although zeolites with a silica-to-alumina mole ratio of at least 10 are useful, it is preferred to use zeolites having silica-to-alumina mole ratios of at least 20:1. In addition, zeolites, as otherwise characterized herein but which are substantially free of aluminum, i.e., having silica-to-alumina mole ratios up to and including infinity, are found to be useful and even preferable in some instances. The novel class of zeolites, after activation, acquire an intra-crystalline sorption affinity for normal hexane, which is greater than that for water, i.e., they exhibit "hydrophobic" properties.
A convenient measure of the extent to which a zeolite provides control to molecules of varying sizes to its internal structure is the Constraint Index of the zeolite. Zeolites which provide a highly restricted access to and egress from its internal structure have a high value for the Constraint Index, and zeolites of this kind usually have pores of small size, e.g., less than 5 Angstroms. On the other hand, zeolites which provide relatively free access to the internal zeolite structure have a low value for the Constraint Index, and usually pores of large size, e.g., greater than 8 Angstroms. The method by which Constraint Index is determined is described fully in U.S. Pat. No. 4,016,218, incorporated herein by reference for details of the method.
Constraint Index (CI) values for some typical materials are:
______________________________________ CI (At Test Temperature)______________________________________ZSM-4 0.5 316° C.ZSM-5 6-8.3 (371°-316° C.)ZSM-11 6-8.7 (371°-316° C.)ZSM-12 2.3 (316° C.)ZSM-20 0.5 (371° C.)ZSM-22 7.3 (427° C.)ZSM-23 9.1 (427° C.)ZSM-34 50 (371° C.)ZSM-35 4.5 (454° C.)ZSM-38 2 (510° C.)ZSM-48 3.5 (538° C.)ZSM-50 2.1 (427° C.)TMA Offretite 3.7 (316° C.)TEA Mordenite 0.4 (316° C.)Clinoptilolite 3.4 (510° C.)Mordenite 0.5 (316° C.)REY 0.4 (316° C.)Amorphous Silica-Alumina 0.6 (538° C.)Dealuminized Y (Deal Y) 0.5 (510° C.)Erionite 38 (316° C.)Zeolite Beta 0.6-2 (316°-399° C.)______________________________________
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 exhibit different Constraint Indices. Constraint Index seems to vary somewhat with severity of operation (conversion) and the presence or absence of binders. Likewise, other variables, such as crystal size of the zeolite, the presence of occluded contaminants, etc., may affect the Constraint Index. Therefore, it will be appreciated that it may be possible to so select test conditions, e.g., temperature, as to establish more than one value for the Constraint Index of a particular zeolite. This explains the range of Constraint Indices for zeolites, such as ZSM-5, ZSM-11 and Zeolite Beta.
Zeolite ZSM-4 is taught by U.S. Pat. No. 3,923,639, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-5 is taught by U.S. Pat. No. 3,702,886, and Re. No. 28,847, the disclosures of which are incorporated herein by reference.
Zeolite ZSM-11 is taught by U.S. Pat. No. 3,709,979, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-12 is taught by U.S. Pat. No. 3,832,449, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-18 is taught by U.S. Pat. No. 3,950,496, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-20 is taught by U.S. Pat. No. 3,972,983, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-23 is taught by U.S. Pat. No. 4,076,342, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-34 is taught by U.S. Pat. No. 4,086,186, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-35 is a synthetic ferrierite-type material described by U.S. Pat. No. 4,016,245, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-38 is a synthetic ferrierite-type material described in U.S. Pat. No. 4,046,859, the disclosure of which is incorporated herein by reference.
Zeolite ZSM-48 is described in U.S. Pat. No. 4,397,827, the disclosure of which is incorporated herein by reference.
Zeolite Beta is described in U.S. Pat. Nos. 3,308,069 and Re. No. 28,341, the disclosures of which are incorporated herein by reference.
U.S. Pat. application Ser. No. 386,456 to Valyocsik dated June 8, 1982, which is incorporated herein by reference, discloses a synthetic porous crystalline material designated as zeolite ZSM-50, a method for its preparation and to its use in catalytic conversion of organic compounds.
Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Pat. Nos. 3,293,192 and 3,449,070, the disclosures of which are incorporated herein by reference.
It is to be realized that the above CI values typically characterize the specified zeolites, but that such are the cumulative result of several variables useful in the determination and calculation thereof. Thus, for a given zeolite exhibiting a CI value within the range of 1 to 12, depending on the temperature employed during the test method within the range of 555° F. (290° C.) to 1000° F. (538° C.), with accompanying conversion between 10 and 60%, the CI may vary within the indicated range of 1 to 12. Likewise, other variables such as the crystal size of the zeolite, the presence of possibly occluded contaminants and binders intimately combined with the zeolite may affect the CI. It will accordingly be understood to those skilled in the art that the CI, as utilized herein, while affording a highly useful means for characterizing the zeolites of interest is approximate, taking into consideration the manner of its determination, with the possibility, in some instances, of compounding variable extremes. However, in all instances, at a temperature within the above-specified range of 555° F. (290° C.) to 1000° F. (538° C.), the CI will have a value for any given zeolite of interest herein within the approximate range of 1 to 12.
Zeolites useful in the present invention are termed medium or intermediate pore zeolites and have a Constraint Index generally between 1 and 12, and an effective pore size of generally not greater than about 7 Angstroms, such as to freely sorb normal hexane. In addition, the structure must provide constrained access to larger molecules. It is sometimes possible to judge from a known crystal whether such constrained access exists. For example, if the only pore windows in a crystal are formed by 8-membered rings of silicon and aluminum atoms, then access by molecules of larger cross-section than normal hexane is excluded and the zeolite is not of the desired type. Windows of 10-membered rings are preferred, although, in some instances, excessive puckering of the rings or pore blockage may render these zeolites ineffective.
Although 12-membered rings in theory would not offer sufficient constraint to produce advantageous conversions, it is noted that the puckered 12-ring structure of TMA Offretite does show some constrained access. Other 12-ring structures may exist which may be operative for other reasons, and therefore, it is not the present intention to entirely judge the usefulness of a particular zeolite solely from theoretical structural considerations.
The preferred medium pore zeolites in this invention include those having the structure of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, and other similar materials, with ZSM-5 being particularly preferred.
The zeolites used as catalysts in this invention may be in the hydrogen form or they may be base-exchanged or impregnated to contain ammonium or a metal cation complement. It is desirable to calcine the zeolite after base-exchange. The metal cations that may be present include any of the cations of the metals of Groups I through VIII of the Periodic Table. However, in the case of Group IA metals, the cation content should in no case be so large as to effectively inactivate the catalyst. For example, a completely sodium-exchanged H-ZSM-5 is largely inactive in the present invention.
It is to be understood that the exact configuration of the cylindrical catalyst bed need not be cylindrical. The catalyst bed can be, for example, supported in part on trays arranged along the axis of the reactor, or can be a single continuous body. The important feature of the catalyst bed is that it be completely submerged in the petroleum liquid being dewaxed and that it be designed to minimize the contact time between catalyst and the product gases formed during the dewaxing step. To this end, in the embodiment shown here, the catalyst bed is designed to be rotated rapidly around axial support 8 to effect disengagement of gases on the catalyst. The speed of revolution is easily determined by preliminary testing prior to going on-stream. Inlet line 10 for a liquid petroleum feedstock extends into the reactor so as to allow feedstock to flow through the catalyst bed, thereby completely submerging the catalyst in the oil phase. Also provided is a line 12 for the injection of a gas, preferably hydrogen, which is bubbled up through the catalyst bed and the oil phase permeating therethrough. The effect of the injected gas is to degasify the liquid being treated so that the gases formed during the dewaxing operation are more freely liberated from the oil phase. The oil phase is then carried off at a point 14 through line 16 above the catalyst bed and from the reactor. Gases accumulating in the top of the reactor are removed through exit line 18. Multiple towers may be employed, whereby each tower is a separate stage in which the liquid product from one stage is directed to a successive stage.
The effect of this particular reactor configuration is to achieve removal of cracked products from contact with the catalyst in oil as expeditiously and completely as possible, thereby avoiding further reaction of the cracked products, such as polymerization, or further cracking to lighter, less desirable gases. Details of heat control within the reactor system have not been included, since such does not form part of the invention.
One limitation which has been found during catalytic dewaxing of hydrocarbons using shape-selective zeolite catalysts is the aging rate of the catalyst. It has now been found that by operating a dewaxing reactor within the narrow low temperature range of 540° F. (282° C.) to less than 565° F. (296° C.), it is possible to significantly reduce catalyst aging. The above-defined temperature range is high enough so as to effect a significant reduction in the pour point of the product, typically equal to or less than about 20° F. (-6.7° C.), but not so high as to cause catalyst deactivation and require daily increases of temperature to boost catalyst activity. The exact temperature at which aging stops and the temperature at which aging continues may vary depending on the specific catalyst used. However, regardless of catalyst, within the narrow temperature range defined above, aging of the catalyst stops. This is characterized by meeting product specifications, such as pour point, without the need for daily increase in temperature.
While the embodiment utilizing a rotating bed of catalyst has been illustrated and described, it will be understood by those skilled in the art that changes and modifications, such as use of an agitating or ebullating bed of catalyst, may be resorted to without departing from the spirit and scope of the invention.
To demonstrate the performance of an immersed catalyst dewaxing process, the dewaxing of a bright stock raffinate using an isothermal trickle bed reactor was compared with the dewaxing of the same stock using the identical catalyst in a one-liter, continuous-flow stirred tank reactor. The reactor had the same configuration as described above. Properties of the feedstock are shown in Table 1 below. The catalyst was a 1.6 mm diameter extrudate of nickel-exchanged ZSM-5 zeolite and alumina in a ratio of 65 parts by weight zeolite to 35 parts by weight alumina. Prior to nickel-exchange, the catalyst was steamed for 6 hours at 900° F. (482° C.) to reduce the catalyst alpha to 70. The catalyst was contained in a wire mesh basket which rotated at a speed of 150 rpm in order to provide intimate contact between the bright stock and the catalyst.
The acid activity of zeolite catalysts is conveniently defined by the alpha scale, described in an article published in Journal of Catalysis, Vol. VI, pages 278-287 (1966). In this test, the zeolite catalyst is contacted with hexane under conditions prescribed in the publication and the amount of hexane which is cracked is measured. From this measurement is computed an "alpha" value which characterizes the catalyst for its cracking activity for hexane. The entire article above referred to is incorporated herein by reference. The alpha scale so described will be used herein to define activity levels for cracking n-hexane. And, in particular, for purposes of this invention, a catalyst with an alpha value of less than about 10, and preferably less than about 1, will be considered to have substantially little activity for cracking n-hexane.
Prior to contacting with the bright stock feed, the catalyst was sulfided in 2% H2 S/98% H2 by progressively raising the temperature to 650° F. (343° C.) over the course of 6 hours. The catalyst was then cooled to 540° F. (282° C.) and the bright stock was introduced. The initial product had a very low pour point, i.e., -15° F. (-26° C.). The reactor temperature was maintained at 540° F. (282° C.) for 12 days until the pour point increased to 20° F. (-6.67° C.). For the remaining 34 days, the reactor temperature was adjusted to maintain the desired 20° F. (-6.67° C.) pour point. Catalyst aging rate was 2.2° C./day.
Other operating parameters of the system are given in Table 2. The performance of the immersed catalyst and that of the trickle bed process are compared in FIG. 2. Here, the relative activities and aging rates of the catalysts are compared on the basis of the reactor temperature required to attain a pour point of 20° F. (-6.67° C.). Throughout both the trickle bed and the continuous-flow stirred tank reactor runs a correction of +1° C. reactor temperature equaling -1° C. pour point was applied based on pour point analysis of the 400° C.+ liquid product to produce the adjusted reactor temperature, as shown in FIG. 2. From these data, it is apparent that the immersed catalyst process is superior to the trickle bed process, both in utilizing catalyst activity, as indicated by the lower process starting temperature of 484° F. (251° C.) as compared to 551° F. (288° C.), and the cycle length of the catalyst, as indicated by the number of days-on-stream (46 vs. 30 days-on-stream). Table 3 shows the product distribution comparing the liquid phase and the trickle bed processes.
TABLE 1______________________________________API 25.8ViscosityKV at 100° C. (CS) 27.03KV at 148.9° C. (CS) 8.50Sulfur, Wt % 1.18Nitrogen, ppm 200Hydrogen, Wt % 13.03Aniline Point, °C. 120.6Mass Spec Analysis, Wt %Paraffins 18.3Mononaphthenes 13.4Polynaphthenes 20.9Aromatics 47.4Nickel, ppm 0.18Vanadium, ppm 0.14Iron, ppm 2.3Copper, ppm 0.10Sodium, ppm 4.10Pentane Insolubles, % 2.07DistillationIBP, °C. 4345 47810 49330 51650 55170 582______________________________________
TABLE 2______________________________________Operational Parameters of Trickle Bedand Immersed Catalyst Reactors Trickle Immersed Catalyst Bed______________________________________Reactor R X R R X RVolume 1 LiterID 1.26 cmPressure 500 psi 400 psiLiquid Hourly Space VelocityLHSV, HR.sup.-1 0.65 0.50Catalyst Loading, Grams 18.6 85Volumetric Feed Rate, cc/hr 19.5 170______________________________________
TABLE 3______________________________________Product Distribution, Wt % Trickle Bed Liquid Phase______________________________________Methane 0.04 0.06Ethane/Ethylene 0.09 0.21Propene 0.03 0.22Propane 2.13 2.05Total Dry Gas 2.29 2.54Isobutane 1.37 1.75Butenes 0.03 0.86n-Butane 1.44 0.94Total C.sub.4 's 2.84 3.55Total C.sub.5 's 1.98 --Naphtha, C.sub.6 + 3.20 8.70Lube 89.69 85.20______________________________________ Distributions are given as weight %
The effect of using an unsteamed nickel-free ZSM-5/Al2 O3 catalyst in conjunction with a lower start-up temperature to produce the reduced aging effect described above was demonstrated during the following experiment. The same 1-liter continuous-flow stirred tank reactor used in the above example was used for this run. Thirty cc of an unsteamed nickel-free 65 wt % ZSM-5/35 wt % Al2 O3, having an alpha of approximately 260, was charged to a supported stainless steel basket. The catalyst was then immersed in a bright stock feed having the properties shown in Table 4, and the reactor temperature was raised rapidly to 480° F. (248.9° C.). Conversion of the feed was carried out at 1 LHSV, 2851 to 3196 kPa (400-450 psig), and 2500 Scf/Bbl H2.
After start-up at 480° F. (248.9° C.) resulted in a product that did not meet the 20° F. (-6.67° C.) pour point specification, the temperature was increased to approximately 520° F. (271.1° C.). At this temperature, the pour point easily met specifications, but the catalyst aged. Reactor temperature was increased to 555° F. (290.6° C.), at which point the product pour point remained steady at approximately 20° F. (-6.67° C.) for about 14 days. Partway through this "line-out", however, the temperature was arbitrarily raised to 565° F. (296.1° C.) in an attempt to reduce the pour point below 20° F. (-6.67° C.). Instead, the catalyst responded by resuming to age at a rate approximately equal to that observed prior to the line-out. This is shown in FIG. 3.
TABLE 4______________________________________Properties of Bright Stock______________________________________API Gravity 26.0ViscosityKV at 100° C. 28.19KV at 300° F. 8.865Sulfur, Wt % 1.22Nitrogen, ppm 300Carbon Residue, % 0.76Hydrogen, Wt % 13.00Aniline Point, °F. 247RI at 70° C. 1.47758Furfural, ppm 7Mass Spec., Wt %Paraffins 19.8Mononaphthenes 12.2Polynaphthenes 21.0Aromatics 47.0Metals, ppmNi 0.10V 0.10Fe 1.1Cu 0.10Na 4.4Pentane Insolubles 1.26Distillation, °F.IBP 7675 85010 87330 91950 96070 1012______________________________________
The same feedstock as described in Example 2 was dewaxed with a steamed nickel-containing ZSM-5 catalyst, having an alpha value of 70, at conversion conditions identical with that of Example 2, except space velocity was 0.5 LHSV. Prior to contact with the feed, the catalyst was sulfided as in Example 1. The "line-out", as described in Example 2, was also found in this Example. Here, however, the line-out temperature was 545° F. (285° C.) and aging resumed when the temperature was raised to 550° F. (288° C.). Although the line-out temperature and temperature at which aging resumed are slightly lower than in Example 2, there still is found a narrow temperature range in which catalyst aging is extremely slow.
These examples compare a fixed bed unit with a one-stage CSTR. The experiments were carried out in a 1-liter autoclave equipped with three stainless steel baskets which contained the catalyst and were attached to the stirring shaft of the autoclave. The catalyst is a steamed 1% nickel ZSM-5 containing catalyst, having an alpha of about 70, similar to that disclosed in Example 1. 8.6 grams (15 cm3) of the catalyst was immersed in 130 cm3 of oil, which gave an average residence time in the reactor 8.7 times the space time (1/LHSV) based on the catalyst. The properties of the feedstocks are given in Table 5. The catalyst was sulfided in 2% H2 S in 98% H2, according to the following schedule, at atmospheric pressure: 450° F. (232° C.) for 1 hour, 550° F. (288° C.) for 1 hour, and 650° F. (343° C.) for 2 hours. The temperature was then dropped to 400° F. (204° C.), H2 S flow was stopped, and H2 flow started at 400 psig. The reactor was flooded with oil at no less than 10 LHSV and temperature was raised to 530° F. (277° C.). Flow was reset at 2 LHSV and H2 at 2500 Scf/Bbl. Tables 5 and 6 list the experimental data obtained for the two feeds.
FIGS. 4 and 5 show the relationship between pour point, Viscosity Index and lube yield for feed A in the CSTR and fixed bed reactors. It is clear from this experiment that, for feed A, both yield and Viscosity Index for products from the CSTR are lower than that from the fixed bed reactor. FIGS. 6 and 7, on the other hand, show that, for feed B, there is good agreement between fixed bed and CSTR results. These data are in lower pour point regime than the feed A data, because the target pour for feed B is 50° F. (10° C.) lower than that for feed A. This suggests that the deviation between CSTR and fixed bed results decreases at low pour points. Although not wishing to be held to one theory, it does appear that at very low pour points, or where long-chain paraffins are in low concentration, as in feed B, a type of reactor or the reactor hydrodynamics does not have as significant an effect on product Viscosity Index or lube yield.
Thus, there is a clear difference in the response of different feeds to dewaxing in a CSTR. The product from feed A heavy neutral is lower in yield and Viscosity Index compared to fixed bed, while the product from the severely hydrotreated and previously solvent dewaxed feed B light neutral has the same yield and Viscosity Index from both the CSTR and fixed bed reactor. These results suggest that once the bulk of the long-chain linear paraffins have been removed, i.e., at low pour points, Viscosity Index and lube yield are not are not as sensitive to residence time distribution differences. Therefore, under certain conditions, a one-stage CSTR achieves, at the very least, the same results as a fixed bed reactor. Combined with the other advantages of the CSTR, as disclosed elsewhere in this application, it is apparent that the CSTR is advantageous, at least with certain types of feedstock.
TABLE 5______________________________________Severely Hydrotreated Feedstock Properties Example 4 Example 5 Feed A Feed B______________________________________API Gravity 31.0 32.2Pour Point, °F. 115 5Cloud Point, °F. 120 5Flash Point, °F. 520 425KV at 40° C. 39.74* 30.80KV at 100° C. 10.00 5.348SUS at 100° F. 383 158.8SUS at 210° F. 60.2 44.2Viscosity Index 116 107Sulfur, ppm 64 1Nitrogen, ppm 7 **0.2Hydrogen, Wt % 14.26 14.48Aniline Point, °F. 248 228.5Bromine Number 0.2 0.1Total Acid Number 0.038 **0.01CCR, Wt % **0.01 **0.01Distillation D1160 D1160IBP, °F. 738 6485 851 70810 874 72830 905 76750 918 80070 934 82990 963 86895 971 884______________________________________ *At 130° F. **Less Than
TABLE 6______________________________________Example 4Hydrodewaxing of Feed A in a CSTRMaterial Balance 1 3 4 5 6 7______________________________________Days-on-Stream 1.4 2.3 3.4 4.3 5.8 7.2Temperature, °F. 619 626 579 579 579 579LHSV 0.7 0.6 1.0 1.0 0.9 0.9Lube Yield, % 43 49 63 69 66 69Herzog Pour, °C. *-30 *-30 -17.4 -16.7 -17.8 -18.2D97 Pour, °F. -5 -35 20 20 15 15Cloud Point, °F. 50 -10H 54 54 48 52HKV at 40° C. 92.50 113.9 100.8 103.8 106.7 99.41KV at 100° C. 10.22 11.22 11.13 11.32 11.47 11.02Viscosity Index 89.7 80.5 95.0 94.5 93.5 95.0______________________________________ *Less Than
TABLE 7______________________________________Example 5Hydrodewaxing of Feed B in a CSTR______________________________________Material Balance 1 2 3 4 5______________________________________Days-on-Stream 0.6 1.0 1.6 3.2 4.6Temperature, °F. 531 531 531 540 561LHSV 2.0 1.1 1.2 1.1 1.1Lube Yield, % 65 91 85 83 78Herzog Pour, °C. -44.6 -44.7 -44.0 -43.0 -47.8D97 Pour, °F. -50 -45 -40 -40 -60Cloud Point, °F. -48 -48 -42 -44 -60KV at 40° C. 36.39 35.33 35.06 36.42 36.23KV at 100° C. 5.711 5.592 5.595 5.708 5.664Viscosity Index 94.3 93.3 95.2 93.9 92.4______________________________________Material Balance 6 7 8 9______________________________________Days-on-Stream 5.4 6.6 7.4 8.4Temperature, °F. 595 507 507 509LHSV 1.1 1.1 1.1 1.1Lube Yield, % 72 97 91 94Herzog Pour, °C. *-50 -38.5 -30.9 -29.1D97 Pour, °F. *-65 -40 -25 -20Cloud Point, °F. *-65 -38 -20 -16KV at 40° C. 37.87 35.99 34.66 34.07KV at 100° C. 5.758 5.660 5.600 5.600Viscosity Index 88.6 93.6 97.9 101.3______________________________________ *Less Than
The following example compares a multiple-stage CSTR with a fixed bed reactor. This experiment was conducted utilizing the same equipment described in Examples 4 and 5. The only variable significantly changed was the space velocity, which was varied between 1.5 and 4.0 LHSV. The temperature was maintained between 626° and 631° F. (330° and 333° C.), the pressure was 400 psig, H2 flow was 250 cm3 /min. The feedstock was a light neutral stock, the characteristics of which can be found in Table 8. The catalyst is substantially identical to that described in Examples 4 and 5. The feed was passed over the catalyst in five successive passes. The initial three passes were made at 4.0 LHSV. The fourth and fifth passes were at 2.8 and 1.5 LHSV, respectively, in an attempt to reach a target pour point of 20° F. (-6.7° C.) despite catalyst aging. The lube product (610° F.+) from each pass was recombined with its respective light liquid product (C5 -610° F.), and refed to the charge buret for the next pass. In this way, only the gas was not recycled. Pour points and viscosities were measured on samples of the lube product from each pass, and the data along with the operating conditions are listed in Table 8.
FIG. 8 shows the Viscosity Index/pour point relationship for the products compared to fixed bed results (data results not listed), and the single pass CSTR data for the same feed. As illustrated in FIG. 8, after one or two passes, it can be seen that the Viscosity Index of the product was lower than that of the fixed bed product of the same pour point. However, after three passes, the Viscosity Index reached the fixed bed line and remained there as the pour point decreased. FIG. 9 shows that product yield behaves in a similar fashion, approaching the fixed bed operating line after about three passes.
Thus, two independent measurements, i.e., Viscosity Index and lube yield, all approach the fixed bed results after three passes in the CSTR. It therefore appears that the lower single-pass results in the CSTR were due to the mixing/by-passing characteristics of the CSTR. This supports the hypothesis that by-passing in a CSTR could contribute to both yield and Viscosity Index loss for light neutral products.
TABLE 8______________________________________Multiple-Pass CSTR RunHydrodewaxing at 400 psigPass Feed 1 2 3 4 5______________________________________Temperature, °F. -- 631 631 626 626 626LHSV -- 4.1 3.9 4.0 2.8 1.5Cumulative Lube 100 92 89 85 83 80Yield, %Product PropertiesHerzog Pour, °C. 33.0 27.4.sup.a 29.2.sup.a 11.8 5.9 0.7 -7.2D-97 Pour, °F. 100 90 90 75 45 35 25Cloud Point, °F. 118 100 100 84 76 60 42KV at 40° C. 30.43 33.83 33.28 34.67 36.44 38.88 41.52KV at 100° C. 5.540 5.703 5.509 5.722 5.864 6.050 6.232Viscosity Index 121 108 101 104 102 99 95______________________________________ .sup.a Two samples taken from Pass 1
In summary, the present invention relates to a process for dewaxing a petroleum feedstock which involves reacting a continuous liquid phase with a submerged catalyst contained in the liquid phase. A discontinuous gaseous phase is passed up through the liquid phase to strip the liquid of undesirable secondary reaction products that are more volatile than the feedstock, but which have finite solubility in the liquid phase. It would not have been apparent to use prior art ebullating reactors, because these reactors provide less hydrogen for the reaction than do more conventional trickle bed reactors, and because such reactors are known to have inherent by-passing, which is deleterious to the pour point target required for the product specification. In spite of these theorized shortcomings, it has been found that the continuous liquid phase with submerged catalyst is superior to the conventional three-phase trickle bed or the fixed bed reactors.
Although the invention has been described in conjunction with specific embodiments, it is evident that many alternatives and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, the invention is intended to embrace all of the alternatives and variations that fall within the spirit and scope of the appended claims.
Claims (30)
Priority Applications (2)
|Application Number
|Priority Date
|Filing Date
|US74372185A true
|US06/884,466 US4737263A (en)
|Process and apparatus for catalytic dewaxing of paraffinic stocks and the simultaneous removal of cracked products
Applications Claiming Priority (1)
|Application Number
|Priority Date
|Filing Date
|US06/884,466 US4737263A (en)
|Process and apparatus for catalytic dewaxing of paraffinic stocks and the simultaneous removal of cracked products
Related Parent Applications (1)
|Application Number
|Priority Date
|Filing Date
|US74372185A Continuation-In-Part
Publications (1)
|Publication Number
|Publication Date
|US4737263A true US4737263A (en)
Family Applications (1)
|Application Number
|Priority Date
|Filing Date
|US06/884,466 Expired - Fee Related US4737263A (en)
|Process and apparatus for catalytic dewaxing of paraffinic stocks and the simultaneous removal of cracked products
Country Status (1)
|US4737263A (en)
Cited By (4)
|Publication number
|Priority date
|Publication date
|US5011675A (en) *
|University Of Waterloo
|Conversion efficiency in trickle bed reactors
|US7351385B1 (en) *
|Clearline Systems, Inc.
|System for enabling landfill disposal of kitchen waste oil/grease
|EP2201088A1 (en) *
|Uop Llc
|Hydroisomerization process
|WO2012063253A1 (en) *
|Digambar Pande Dhananjay
|A novel system for adsorbing and separating suspended gaseous impurities from effluent gases and thereby recovery of value added products
Citations (21)
|Publication number
|Priority date
|Publication date
|US28300A (en) *
|US28398A (en) *
|Henry l
|US2231424A (en) *
|Union Oil Co
|Catalytic method
|US2493917A (en) *
|Standard Oil Co
|Catalytic conversion
|US2520424A (en) *
|Procter & Gamble
|Continuous hydrogenator
|US2704741A (en) *
|Sun Oil Co
|Method and apparatus for conversion of organic reactants to other organic products
|US2706167A (en) *
|Sun Oil Co
|Process for hydrogenating hydrocarbon oils
|US2746950A (en) *
|Armour & Co
|Continuous method of extracting animal glue in concentrated aqueous solutions
|US2987465A (en) *
|Hydrocarbon Research Inc
|Gas-liquid contacting process
|US3140322A (en) *
|Socony Mobil Oil Co Inc
|Selective catalytic conversion
|US3297505A (en) *
|Corning Glass Works
|Method of making electrical capacitors
|US3453083A (en) *
|Uster Spindel Motoren Maschf
|Rotary extraction apparatus
|US3489675A (en) *
|Air Prod & Chem
|Fixed bed cracking
|US3761393A (en) *
|Hydrocarbon Research Inc
|High conversion level hydrogenation
|US3969274A (en) *
|National Distillers And Chemical Corporation
|Fixed bed catalyst
|US4158622A (en) *
|Cogas Development Company
|Treatment of hydrocarbons by hydrogenation and fines removal
|US4222855A (en) *
|Mobil Oil Corporation
|Production of high viscosity index lubricating oil stock
|US4263126A (en) *
|Mobil Oil Corporation
|Preparation and use of reactive dispersions
|US4317746A (en) *
|Union Oil Company Of California
|Hydrotreating catalysts
|US4332670A (en) *
|Mobil Oil Corporation
|Catalytic dewaxing of middle distillates
|US4410416A (en) *
|Everman Carl G
|Split hub wheel apparatus and use of same for shale oil retorting
- 1986-07-11 US US06/884,466 patent/US4737263A/en not_active Expired - Fee Related
Patent Citations (21)
|Publication number
|Priority date
|Publication date
|US28300A (en) *
|US28398A (en) *
|Henry l
|US2231424A (en) *
|Union Oil Co
|Catalytic method
|US2493917A (en) *
|Standard Oil Co
|Catalytic conversion
|US2520424A (en) *
|Procter & Gamble
|Continuous hydrogenator
|US2706167A (en) *
|Sun Oil Co
|Process for hydrogenating hydrocarbon oils
|US2746950A (en) *
|Armour & Co
|Continuous method of extracting animal glue in concentrated aqueous solutions
|US2704741A (en) *
|Sun Oil Co
|Method and apparatus for conversion of organic reactants to other organic products
|US2987465A (en) *
|Hydrocarbon Research Inc
|Gas-liquid contacting process
|US3140322A (en) *
|Socony Mobil Oil Co Inc
|Selective catalytic conversion
|US3297505A (en) *
|Corning Glass Works
|Method of making electrical capacitors
|US3453083A (en) *
|Uster Spindel Motoren Maschf
|Rotary extraction apparatus
|US3489675A (en) *
|Air Prod & Chem
|Fixed bed cracking
|US3761393A (en) *
|Hydrocarbon Research Inc
|High conversion level hydrogenation
|US3969274A (en) *
|National Distillers And Chemical Corporation
|Fixed bed catalyst
|US4158622A (en) *
|Cogas Development Company
|Treatment of hydrocarbons by hydrogenation and fines removal
|US4222855A (en) *
|Mobil Oil Corporation
|Production of high viscosity index lubricating oil stock
|US4263126A (en) *
|Mobil Oil Corporation
|Preparation and use of reactive dispersions
|US4317746A (en) *
|Union Oil Company Of California
|Hydrotreating catalysts
|US4332670A (en) *
|Mobil Oil Corporation
|Catalytic dewaxing of middle distillates
|US4410416A (en) *
|Everman Carl G
|Split hub wheel apparatus and use of same for shale oil retorting
Non-Patent Citations (1)
|Chemical Reaction Engineering, Levenspiel, 1972, John Wiley & Sons. *
Cited By (5)
|Publication number
|Priority date
|Publication date
|US5011675A (en) *
|University Of Waterloo
|Conversion efficiency in trickle bed reactors
|US7351385B1 (en) *
|Clearline Systems, Inc.
|System for enabling landfill disposal of kitchen waste oil/grease
|EP2201088A1 (en) *
|Uop Llc
|Hydroisomerization process
|EP2201088A4 (en) *
|Uop Llc
|Hydroisomerization process
|WO2012063253A1 (en) *
|Digambar Pande Dhananjay
|A novel system for adsorbing and separating suspended gaseous impurities from effluent gases and thereby recovery of value added products
Similar Documents
|Publication Date
|US5730858A (en)
|Process for converting wax-containing hydrocarbon feedstocks into high-grade middle distillate products
|US5019665A (en)
|Shape-selective process for concentrating diamondoid-containing hydrocarbon solvents
|US4913797A (en)
|Catalyst hydrotreating and dewaxing process
|US4919788A (en)
|Lubricant production process
|US6190532B1 (en)
|Production of high viscosity index lubricants
|US4463209A (en)
|Aromatics processing
|US5853566A (en)
|Zeolite-beta containing catalyst compositions and their use in hydrocarbon conversion processes for producing low boiling point materials
|US4612108A (en)
|Hydrocracking process using zeolite beta
|US3957621A (en)
|Production of alkyl aromatic hydrocarbons
|US4419220A (en)
|Catalytic dewaxing process
|US5723716A (en)
|Method for upgrading waxy feeds using a catalyst comprising mixed powdered dewaxing catalyst and powdered isomerization catalyst formed into a discrete particle (LAW082)
|US5614079A (en)
|Catalytic dewaxing over silica bound molecular sieve
|US4518485A (en)
|Hydrotreating/isomerization process to produce low pour point distillate fuels and lubricating oil stocks
|US4309279A (en)
|Octane and total yield improvement in catalytic cracking
|US5358628A (en)
|Production of high viscosity index lubricants
|US4309280A (en)
|Promotion of cracking catalyst octane yield performance
|US4908341A (en)
|Method for reactivating spent catalyst by contact with one or more aromatic compounds
|EP0464546A1 (en)
|Production of high viscosity index lubricants
|EP0464547A1 (en)
|Production of high viscosity index lubricants
|US6231749B1 (en)
|Production of high viscosity index lubricants
|US5976351A (en)
|Wax hydroisomerization process employing a boron-free catalyst
|US5865986A (en)
|Hydrocarbon conversion
|US4636299A (en)
|Process for the manufacture of lubricating oils
|US4683050A (en)
|Mild hydrocracking with a catalyst containing an intermediate pore molecular sieve
|US4501926A (en)
|Catalytic dewaxing process with zeolite beta
Legal Events
Owner name: MOBIL OIL CORPORATION, A CORP OF NY.
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CHEN, NAI Y.;DEGNAN, THOMAS F. JR.;PELRINE, BRUCE P.;AND OTHERS;REEL/FRAME:004599/0731
Effective date: 19860708
Owner name: MOBIL OIL CORPORATION, A CORP OF NY.,STATELESS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHEN, NAI Y.;DEGNAN, THOMAS F. JR.;PELRINE, BRUCE P.;ANDOTHERS;REEL/FRAME:004599/0731
Effective date: 19860708
|Fee payment
Year of fee payment: 4
|Maintenance fee reminder mailed
|Lapse for failure to pay maintenance fees
|Expired due to failure to pay maintenance fee
Effective date: 19960417


text:
Australia with Triplets
Free information for parents with triplets
We provide interesting information and are embracing information exchange with parents. Who likes to upload their stories, can decide if they remain anonymous or not.
This site is not for making money or profit, but only to provide a platform to exchange information.
We'll help prospective triplet parents to get ready for parenting triplets.
Read our articles about caring for triplets and send us your feedback so that we can share it on our website with other parents.
Share your triplet experience with us or read our triplet stories! Start your own triplet blog now!
Some Hard Facts About Being a parent of Triplets
So you're having triplets? Scared? Excited? All of the above? Remember the following:
Having the label of a 'triplet parent' means that you will never have your spouse return home to you after their hard day of work and be able to utter the words "This house is a mess, what on earth have you being doing here all day?!"
You will never ever have to leave your home again for the sole purpose of having a playgroup! You have your very own right under your own roof!
Thought you had problems with maths before your birth? Well you will now become an expert in the number 3, and more specifically, dividing everything into equal thirds. No more calculators when it comes to 0.33 again…
Every time you see three of the same thing you will always assume its triplets. True story. Triple the fun, triple your trauma!
It's a very unique experience having triplets, and you will always find yourself thinking differently no matter what the situation! Enjoy it though while you can, it won't be long until they are grown up and you 'miss' the baby days. Really…
Do you have triplets and want to share your story?
Come to us for the opportunity to tell our readers all about raising triplets and what has and hasn't worked for you!
Facts about Triplets in Australia
Finding out you are soon to be a parent is some of the best news you can ever find out, however being told you are going to have triplets or even more babies can be a massive shock for everyone involved!
BEFORE you had your triplets, the idea of a restaurant you could enjoy was a restaurant where you could enjoy some great food with a simple and nice ambience. Some fun facts ... more
Triplets Blog
Come to us for the opportunity to tell our readers all about raising triplets and what has and hasn't worked for you!
Having triplets is an experience that you will know nothing about. In fact it's...
It's a pretty amazing thing when you think about it: having three babies all at once! And if you aren't lucky enough to experience it yourself then you will be amazed when...
Having Triplets
BEFORE you had your triplets, the idea of a restaurant you could enjoy was a restaurant where you could enjoy some great food with a simple and nice ambience.
But AFTER you have your triplets, the idea of a...
Triplets Costs
You've had triplets, you're stressing at the amount of work that you now have to do but have you actually also factored in the cost involved? It's not cheap to have a baby, so try multiplying that by three when it comes...
Nanny or Au Pair
Options for helping you out with triplets
Having triplets is no doubt becoming a very daunting task for you and getting prepared for the caring side of things can be even more daunting. You can always ask as many friends and...
Triplet Prams
So you've found out the news that you're going to be parents! Fantastic! Even better, you find out you're going to be the parents of triplets! Well that brings a whole new level of complication to your situation now doesn't it? Everything...
Having Triplets Changed My Life
Mothers of Triplets
Having triplets is an amazing experience and you will soon find yourself getting comments no matter where you go! I mean look at what you will be having with you: 3 beautiful babies all at once that is something...
Triplets Pregnancy
DO embrace the opportunity at every single turn! As soon as you find out you are having triplets you are going to be scared, nervous and petrified. There are so many different emotions you will experience that we can't...
Triplets Babies
By now you have read the list of potentially good comments you will get about your triplets, and trust us when we say you will get all sorts of positive comments about your babies when you are out in public!
Triplet Babies Routine
When you have triplets you will soon find out the meaning of proper time conservation! Trust us on this! It can be very difficult to properly maintain a good amount of time and effort on many different activities...
Triplets Pregnancy
By now if you have found out you are having triplets, you are no doubt finding yourself asking numerous questions. Well this is not unusual and if anything it is to be expected. Having triplets...
Triplets Australia
Finding out you are soon to be a parent is some of the best news you can ever find out, however being told you are going to have triplets or even more babies can be a massive shock for everyone involved! This is called 'Higher...
Parenting Triplets
If you have found out you are going to be the parent of triplets we are sure you have had a wide variety of emotions! From the pure joy of finding out you are going to be a parent to a bit of panic knowing that you have...
Multiple Discounts for Triplets
One positive thing to come from being the parents of triplets is the fact that you often have the potential to get lots of discounts by buying multiple items all at once! Yes that's right, there are many baby shops...
Paediatricians in Australia
It's always a good idea to have somebody on hand who is a reliable paediatrician so that you will always have a person to go to when your children need medical assistance. This is of course very important...
Traveling with Triplet Babies
You may ask the accommodation provider the following questions:
Can we get 3 cots for the babies? Do we pay for them?
Do you have a twin room available or something like:...

subset: commoncrawl


text:
Sagittarius capability
You share an entrepreneurial nature, but Sagittarius is a gambler while Capricorn only takes extremely calculated risks. To re-balance, the yin sign needs to work on being more open, direct and confident, while the yang sign should cultivate more patience, tolerance and sensitivity. Some are more likely to compliment or complain! Reaching the honeymoon phase is going to be tricky here! Passion resides in the heart and soul of this love match.
There are other planets which also affect someone's personality. Cardinal signs are initiators—they like to lead and direct and manage. Can the Taurus Sagittarius love match go the distance? Passion resides in the heart and soul of this love match. Are you a starter, a doer or a finisher? It is difficult for them to find common ground, but if they do, they can help each other grow different dimensions to their respective personalities. Sagittarius are non-judgmental, helpful, and extroverted individuals who can lift the spirits of any room by just walking into it. Reaching the honeymoon phase is going to be tricky here! The yin sign can be too passive or passive-aggressive and sacrificing, while the yang sign may act domineering, aggressive and selfish. Taurus will bring a semblance of calm and order to the wild and cluttered world of the Sagittarius. It will make the Taurus Sagittarius relationship tick. Of course, all that friction can lead to explosive sexual chemistry, even an obsessive quest to figure each other out you never will. Grounded earth signs seek stability and want to put down roots. While Taurus relies on stability and predictability, Sagittarius shines in a spontaneous and adventurous life. If you would like to explore this further please see the astrology compatibility readings page. But if you learn to appreciate your differences, then you can offer what the other one is missing. Your signs are semisextile , or one sign apart. And the fire sign can help the earth sign take more chances in life. Each one plays an important role in the greater whole of humankind. They will need to tune their frequencies to each other at the start of their relationship, but if they are successful in doing that, the way ahead will be seemingly smoother for the duo. Do you like to take charge and have a plan, or do you prefer to go with the flow? Taurus people enjoy to sit by the fireplace, reading the novel. Comparing sun signs can give a good general idea of compatibility. And the mutable sign should check with the cardinal sign before RSVPing to random events or inviting strangers over for dinner. Your compatibility clicks and clashes Where you click:
That doesn't wish that will be your standard, however you are very hot to recover some inhabitant patterns which can be thoughtful. sagittarius capability Definitely, sagittarius capability should absent on how to get over stories sagittarius capability and find a way to mount closer to each other after every all time. But if you catch to when is flirting cheating your differences, then you can direct what the other one is men. Earth utilizes are looking and matchmaking, and sticky fond couples can benefit from their grounded here. Winning too far based aim on sun requires can therefore be country. But in place to write a fire and with its assessment powers, there must be a keenly ground honestly the great. If you would move to mount this further please see the substantiation compatibility readings page.


text:
Need help with your office search?
Contact one of our property experts for a no obligation consultation.
Call: 020 3053 3882 | Email: email@example.com | Web: www.officebroker.com
This office is no longer available, for alternatives please see offices in Cardiff.
If a first class location is required, this one certainly delivers, being a landmark building, situated within a few hundred yards of Mermaid's Quay and offers a refreshing change from the run of the mill office accommodation, including an inclusive Uniformed Chauffeur Service for all clients. Apart from the bright and airy reception (which features a number of comfortable leather sofas), and the modern communal areas, wide corridors and meeting points help to create an elegant atmosphere unlike any other. Customer choice is important and all occupiers can add a personal touch to their offices, including the type and colour of their furniture.


text:
VISITORS to York Art Gallery can get in for free this weekend, providing they have a National Lottery ticket.
The gallery is one of hundreds of National Lottery-funded attractions across the UK opening their doors for free to anyone with a National Lottery ticket or scratchcard on Saturday or Sunday.
York Art Gallery received £3.5 million from the National Lottery Fund through Arts Council England towards its £8 million transformation in 2015.
Paul Lambert from York Museum Trust, said: "Thanks to National Lottery players we've been able to create a world class gallery that embraces the contemporary, whilst retaining its rich history. It now has 60 per cent more exhibition space, including three galleries with the conditions to bring the most significant art and exhibitions to the city."
For more information, go to yorkartgallery.org.uk


text:
Margaret Kuo was raised in a culture where culinary arts were regarded on a level with music and literature, with recipes treasured as works of art.
Her father was a senator from Manchuria who welcomed some of China's most prominent people into his home for banquets, especially to celebrate the new year. Even after World War II, when the Communists gained power and her family emigrated to Taiwan, Kuo says, the new year was greeted with elaborate meals at which elders and ancestors were honored.
That's one reason Kuo, who had a successful career as a chemist in the United States, eventually went into the restaurant business here. And it explains why she was intent on bringing the Chinese-style banquet to our shores.
Kuo, now with four restaurants under her watchful eyes, is regarded by many as the doyenne of the royal banquet, traditionally held at the Chinese New Year.
The new year holiday, marking 2009 as the Year of the Ox, began Sunday and extends until Feb. 9. But Kuo's banquets will continue through February and some area restaurants from Chinatown to the Main Line will offer banquet menus well into April.
For Kuo, a banquet means an elaborate meal, artfully prepared, using highly prized ingredients served with propriety as a display of respect for honored guests.
A banquet is a departure from some everyday eating customs and an exaggeration of others. At everyday Chinese meals, rice takes center stage and the dishes are served all at once, but a banquet displays the host's generosity and prosperity, so the food is brought in successive bountiful courses.
Guest and host treat each other with great deference. Who enters the room first is as important as where one sits in proximity to the kitchen door, a humble spot.
And all that, the menu and the manners, are bumped up a notch or two for the New Year's celebration.
"New Year's in China," Kuo says, "is like Christmas here."
The house would be scrubbed from top to bottom, to sweep out the old and make way for the new, and then decorated in red for luck and festooned with symbols of good fortune, happiness and longevity.
The children would get red envelopes filled with cash, and everyone had new suits of clothes.
And a table was set with elaborately prepared dishes made with the finest fish, fowl, fruits and spices. It was, she says, a form of Presentation Table laid for the pleasure of one's elders and ancestors whose spirits were said to arrive on the eve of the new year and stay through the entirety of the holiday.
The presence of ancestors in one's home was a blessing and their arrival could not be taken for granted.
So, about a week before the new year, the family would prepare a banquet for the Kitchen God, a spirit akin to a modern-day food critic who traditionally arrives in advance of the ancestors and must be placated.
"If the Kitchen God was not pleased with your cooking, he would say bad things about you to the ancestors and then they might not come. So you make a meal so big that the Kitchen God stuffs his mouth and then he can't say anything bad about you."
Kuo, who arrived in the United States as a college student and met her husband, Warren, at the University of Connecticut, came to Philadelphia to work as a chemist at what was then Women's Medical College in East Falls.
The couple went on to establish four distinguished restaurants and an import/export company called Pearl of the East.
But Kuo's success as a restaurateur was not a certainty from the start. As a child of privilege, she learned to work with master chefs, not become one.
"The only time I cooked with my mother and grandmother was at New Year's," she says.
In 1974, when she opened Peking restaurant in the Granite Run Mall, Americans defined "Chinese food" as cheap chow mein. Instead of egg foo young and wonton soup, Kuo offered authentic Mandarin and Szechuan dishes at prices more typically seen in white-tablecloth eateries.
If not for positive reviews from critics, Kuo says, her business might have gone under. Instead, it has flourished.
Peking restaurant remains happily ensconced in Granite Run, and Kuo's other eateries include Mandarin in Malvern and two restaurants in Media and Wayne that bear her name. She recently turned the second floor of her Wayne restaurant into a Japanese dining room, serving sake, sushi and Tokyo-style cuisine.
The elegant Wayne dining room, where the beef is grass-fed, the shrimp white, and the wine list honored by Wine Spectator magazine, is her home base. This is where she serves her Year of the Ox banquet.
The feast begins with a plate of Four Happiness Appetizers: jumbo shrimp with peppercorn sauce, five-flavored beef, tender asparagus, and thin slices of lotus root to symbolize abundance year after year.
Dumplings are a staple of New Year's banquets because their shape is reminiscent of gold ingots (yuan bao) used during the Ming Dynasty for money; serving them brings the promise of wealth and prosperity.
For the dumpling course at her banquet, Kuo serves one of her signature dishes, Shanghai Steamed Soup Buns, with fist-sized dumplings that, when nipped, exude a gush of delicate soup.
The soup buns are followed by platters of Peking duck, Mandarin cold-water lobster tail, and Kobe beef medallions with baby bok choy.
And there's always room for a traditional dessert - in this case, a sweet chilled soup of fresh lily bulbs, white cloud ear fungi, and Goji berries.
Even a hungry Kitchen God would be satiated.
And here's a money-saving option to consider: The Chinese New Year celebration culminates with the Lantern Festival, which is akin to our Valentine's Day. Take your sweetheart to a Chinese banquet on Feb. 8 and you'll be getting a two-fer.
The Year of the Ox, 4707 in the Chinese zodiac, could be worth watching.
People born under the sign of the ox are said to be unswervingly patient, dependable, tireless, stable, honest, strong and protective.
Feng shui master Lillian Too says the ox "should never be underestimated because of their cool, calm and quiet exterior."
The ox is one who possesses eloquence and an innate ability to achieve great things, and is a born leader.
And this year's most famous ox? Barack Obama, born Aug. 4, 1961.
Obama's lucky elements are metal and earth, which should help him overcome some of the rough patches astrologers say are still to come in 2009.
Chinese astrology master Andy Goh predicts the real estate market will improve (this being an earth year) but not until fall, when Obama enters his peak luck cycle.
Goh advises all earth-metal-oxen to "expect a change in your living environment."
- Dianna Marder
The Chinese New Year celebration started Sunday night and continues until Feb. 9 this year, but some area Year of the Ox banquets will extend through February, March, even into April. Reservations are required at all locations listed below; tax and tip are additional.
Chinese Cultural Center
125 N. 10th St.
firstname.lastname@example.com; www.chinesecc.com
6:30 p.m. now through April 30; 10 courses, $48 per person Friday, Saturday and Sunday; $45 Tuesday, Wednesday, and Thursday; BYOB. Guest chefs from China's Yunnan Province make their first appearance in the United States. See their menu online at www.chinesecc.com.
Margaret Kuo's Restaurants
175 E. Lancaster Ave., Wayne
Year of the Ox Gourmet Dinner, now through Feb. 28, at all locations. Six courses, $45 per person; optional wine pairings extra; see the menu online at www.margaretkuos.com.
Joe's Peking Duck
Chef Joseph Poon
108 Chestnut St.
Banquet menu is 10 courses, $36.50 per person; minimum of six people; seatings at 5:30 and 7:30 p.m. Friday, Saturday and Sunday nights now through March 31. Parties of 10 or more may also arrange weeknight banquets. See the menu online at www.josephpoon.com
Susanna Foo's Gourmet Kitchen
555 E. Lancaster Ave., Radnor
Banquet menu available now through Feb. 28, but not on Feb. 13 and 14. Three courses, $39 per person. See menu online at www.susannafoo.com.
Makes 36 dumplings
1 pound ground pork or beef
1/4 cup thinly sliced green onion
1 tablespoon soy sauce
1 tablespoon Asian sesame oil
2 teaspoons finely chopped fresh ginger
1 teaspoon salt
1/2 teaspoon sugar
1/4 cup frozen chopped spinach, thawed (see note)
36 wonton or round gyoza wrappers (Susanna Foo prefers Twin Dragon brand)
2 tablespoons vegetable oil
1/2 cup water
1. In a large bowl, combine the pork or beef, green onion, soy sauce, sesame oil, ginger, salt and sugar. Squeeze spinach to extract water. Add spinach to bowl and use a large spoon or your hands to mix everything together until the seasonings are incorporated and the spinach and green onion are evenly mixed in.
2. To fold the dumplings: Set up a work space with a dry cutting board, a small bowl of water for sealing the dumplings, the stack of wrappers, and the filling mixture.
3. To shape a dumpling, place a wrapper on the cutting board. Scoop up a generous tablespoon of filling and place it in the center of the wrapper. Dip your index finger into the water, then lightly moisten the outside edge of the wrapper. Fold in half, enclosing the filling and pinching the top edges to make a tight seal. Squeeze out any air bubbles. Create 3 small pleats on one side of the seal, folding toward the center and pressing to seal it well. Form 3 small pleats on the other side and press the entire sealed edge. Press the sealed edge down lightly to plump up the dumpling and make it stand up straight.
4. Continue folding; place folded dumplings in rows on a dry platter so they do not touch.
5. To cook: Heat a 10-inch nonstick skillet over medium high heat. Add the vegetable oil and swirl pan to coat. Carefully place about 12 dumplings in the pan, tucking them to form a circle in one direction (packing them tightly is fine).
6. Let the dumplings cook undisturbed 1 or 2 minutes, until the bottoms are a pale golden brown. Add 1/2 cup water and cover quickly. Let dumplings cook 8 minutes, then uncover the pan.
7. Continue cooking for 1 to 2 minutes more, shaking the pan gently and using a spatula to discourage the dumplings from sticking too much. When the water has evaporated and the dumplings are a crispy brown, turn them out bottom side up onto a serving platter. Serve hot or warm, accompanied by Ginger-Soy Dipping Sauce.
To use blanched fresh spinach: Drop about 4 cups loosely packed spinach into a small pot of boiling water, let cook one minute, drain well, squeeze to extract water, coarsely chop, and measure out 1/4 cup. To use napa or regular cabbage, chop finely and use raw or blanched.
Per serving (based on 12): 202 calories, 9 grams protein, 14 grams carbohydrates, trace sugar, 12 grams fat, 29 milligrams cholesterol, 386 milligrams sodium, trace dietary fiber.
Makes 1/2 cup
1/4 cup soy sauce
3 tablespoons white or apple cider vinegar
1 tablespoon chopped fresh ginger
2 teaspoons sugar
2 teaspoons Asian sesame oil
1/2 teaspoon salt
1. Combine the soy sauce, vinegar, ginger, sugar, sesame oil and salt in a medium bowl.
2. Whisk or stir well to dissolve the sugar and salt and mix everything together into a smooth sauce.
Per tablespoon serving:
21 calories, trace protein, 2 grams carbohydrates, 1 gram sugar, 1 gram fat, trace cholesterol, 341 milligrams sodium, trace dietary fiber
Serves 12
1 cup hoisin sauce
6 tablespoons rice wine or white wine
1/2 cup soy sauce
1 cup sugar
1/2 cup tomato paste
1/4 cup finely minced garlic
2 tablespoons Tabasco
2 pounds pork ribs cut into 1-inch riblets
1. Preheat the oven to 350 degrees.
2. In a medium-size mixing bowl, mix all of the ingredients except the riblets, until smooth. Taste and set aside.
3. Place the riblets in a large roasting pan, and bake, uncovered, for 45 minutes.
4. Remove the pan from the oven, pour the sauce over the riblets and toss to coat.
5. Return the pan to the oven, covered, and bake for another 45 minutes. Toss or baste every 10 minutes so the riblets stay well coated with sauce.
Note: This recipe makes much more sauce than needed. Use only half to two-thirds of the sauce, but do continue basting throughout the cooking time for best results.
Per serving: 194 calories, 11 grams protein, 27 grams carbohydrates, 5 grams fat, 26 milligrams cholesterol.


text:
We use cookies to make your experience better. To comply with the new e-Privacy directive, we need to ask for your consent to set the cookies. Learn more.
University Hospital Limerick tunic for Clinical Nurse Manager 2. Navy tunic with metro blue trim. UHL logo. Matching trousers with metro tag available to buy
|Fabric information


text:
Fans of Take That are celebrating tonight as ex member, Robbie Williams has re-joined the band on tour.
However, he is not going to be joining the group on stage, but will be ensuring that they have ample towels and water behind the scenes.
Robbie in talking to the press this morning described how it all came about - "I talked to Gary about maybe coming Back for Good. He asked me if I was Sure, and I said yes but didn't know if I wanted to go on stage. He said "Do what U want". So, I thought I'd just help out backstage. It's quite fun."
Gary Barlow, later talked about how the fans would take the news - "All the fans we know always said that they would Never Forget the band when it was at full strength and I am Sure that they are going to be happy about this. It make take some time for everyone to get used to the idea, but with some Patience, we will be fine."
Everything Changes, but it seems likely that all the fans that have taken time to Pray for this to happen, have got their wish.


text:
Recspec Sees All Bandanas
Set of six hand-marbled coasters by Stone & Vein
Coasters are a heavyweight paperboard, about 2mm thick and 4" in diameter and come packaged in a cellophane sleeve. The reverse side may have some remnants of the pattern due to the the printing process and handmade nature.
Because they are paperboard, they may become warped or stained over time with excessive moisture. The coasters are both biodegradable and recyclable.


text:
Bidvest company, Konica Minolta South Africa, recently won the bid to assist southern Africa's premier property agency, Pam Golding Properties, in meeting its document output strategy.
In line with the agency's main objectives to increase employee efficiencies, reduce costs, enhance control over its document output environment, leverage the expertise of technology, such as provided by Konica Minolta SA, and improve on its current workflows and business processes, more than 100 bizhub multifunctional (MFD) devices were installed at the group's Bishopscourt, Cape Town head office and its regional offices and branches, replacing the existing fleet of 300 devices.
According to Nicole Marshall, group financial officer at Pam Golding Properties, the group went through a detailed request for proposal process and rated each company that responded on a number of areas, which included understanding the agency's needs, the ability to report on specific usage, quality of print, a national service footprint and, of course, pricing.
"Each criterion was weighted and scored. There were two suppliers that rated highly, but the professionalism of Konica Minolta South Africa was superior and matched our brand image, giving us confidence that the company would be the right choice and be able to deliver," says Marshall.
In addition to the bizhub devices, software by Konica Minolta South Africa will also be utilised by the Pam Golding Property Group.
"This includes our Pagescope Netcare, which enables automated meter readings and service alerts from the devices, and Pagescope Data Administrator, in order to pull user reports from the MFDs for print control purposes and also to add users and scan entries to the devices," explains Wilstan Weichardt, sales manager at Konica Minolta South Africa.
"The print driver packaging utility ensures the customised print drivers were deployed seamlessly and easily; as well as Pagescope Web interface, to remotely access the MFDs and configure these via the Web."
All software supplied is a product of Konica Minolta, which eliminates outsourcing to a third party and enables an exemplary service level resolution in-house.
Konica Minolta South Africa also has a dedicated service desk consultant stationed at Pam Golding Properties IT division, to address and resolve all first line calls from the agency's users and escalate more serious technical/software calls to the Konica Minolta South Africa call centre.
In addition, Konica Minolta South Africa holds monthly service performance meetings with the agency's IT division to both assess the previous month's service results and address any outstanding issues.
"The support received has also been fantastic. Konica Minolta South Africa really goes out of its way to assist us, especially when branches are opening or moving and we require a loan machine for a short period. We feel that we are business partners, rather than Konica Minolta South Africa just being a supplier," says Marshall.
She adds that since implementation, the Pam Golding Property Group has only just begun to appreciate the extent to which process improvement opportunities can be exploited.
"User behaviour patterns have changed in that users are far more cost sensitive and deliberate in their printing processes. Paper workflow processes have also improved significantly with regards to speed and the quality of prints is crisp.
"The standardisation and networking of our printing technology have led to better management and also allowed us to provide useful reporting capabilities to management. Owing to this positive landscape, we will start a new phase shortly, which will look at the more aggressive use of some of the bizhub's capabilities, as we have found the devices to be outstanding and easy to use," she says.
Marshall estimates the cost saving owing to the new output model to be around 20% so far.
"The Konica Minolta South Africa model, all inclusive cost per page, suits the way we do business and helps us monitor our spend as we are able to report by region, by branch, by individual as well as by colour, black and white, print and copy. We have also set up defaults such as printing double sided, meaning that we can save paper and, ultimately, forests.
"In addition, there has been a large saving in personnel's time – as we now have one supplier, one contact person and standard equipment across the company – simplifying the life of the user, the super users (who are responsible for ordering and replacement of toner and paper), the IT support function and the finance team responsible for payments."


text:
|You'll find premium brand paints and supplies which help to provide extra years of longevity to your finish. You'll find sources for replacement hardware.
You'll find a painting process that includes sanding, patching, priming – all before the first coat of paint is applied.What will you not find? When you hire John Psomas Painting to work at your home, you won't find any day laborers or sub-contractors that lack the training required to work for the John Psomas team.
Contact Us:
John Psomas Painting
3174 San Bernadino Street
Clearwater, FL 33759
Click here to contact us


text:
Engineer Electromechanical 1
Avionics and Tactical Networks (ATN) is an operating unit within the Communications business unit of the Airborne C4ISR
Systems division of Northrop Grumman Mission Systems. ATN is located in the Rancho Carmel facility in San Diego, California.
We deliver complex equipment to enable modern battlefields and support aviation missions. Our focus is on the world of avionics, radio and electronic warfare product applications to enable networked communications. As part
of the corporation's business focus area on Communications, we are the equipment providers. Our team of communication systems experts is developing next-generation ground radios for land forces, and our Electronic Warfare subject matter experts are creating the next generation of Improvised Explosive Device (IED) countermeasures to keep our soldiers safe when in harm's way.
Support senior engineers in the mechanical design and packaging of antenna, RF, digital, infrastructure, and test hardware products, including avionics modules, racks, and interface test adapters. Perform thermal and structural analyses, electrical-mechanical tradeoffs, verification testing and qualification testing under the close supervision of a senior engineer. Perform product integrity and reliability calculations; determine MTBF; plan and execute qualification testing, environmental stress screening, reliability demonstration testing, etc.
Basic Qualifications
- Must have at least 0 years of related experience with a Bachelors Degree in STEM field
- Requires a fundamental understanding of heat transfer, mechanics of materials, and vibration.
- Requires attention to detail, self-motivation, and self-regulation.
- Candidate should exhibit strong interpersonal and communication skills, and shall have demonstrated the ability to work
on complex projects with multiple people.
- Experience with CAD and FEM/FEA tools
- Understanding of engineering drawing standards and geometric dimensioning & Tolerancing
- Ability to obtain DoD Secret clearance and SAP/SAR.
Preferred Qualifications:
- Experience using CATIA (CAD), NASTRAN/PATRAN (FEM/FEA), and Flotherm (CFD) is preferred.
- Masters Degree in Mechanical or Aerospace Engineering
- Current DoD Secret clearance is preferred.
Northrop Grumman is committed to hiring and retaining a diverse workforce. We are proud to be an Equal Opportunity/Affirmative Action Employer, making decisions without regard to race, color, religion, creed, sex, sexual orientation, gender identity, marital status, national origin, age, veteran status, disability, or any other protected class. For our complete EEO/AA and Pay Transparency statement, please visit www.northropgrumman.com/EEO . U.S. Citizenship is required for most positions.
Back to top


text:
Sculpture on the Point, Diamond Harbour - free sculpture exhibition all summer. Catch the Black Cat ferry over to DH from Lyttelton and enjoy this exciting inaugural event.
Add a comment
Gift Vouchers | Specials | Stay In Contact
Sitemap | Terms & Conditions | Privacy Policy
Copyright © 2014 Black Cat Cruises | Website design and development by E2 DIGITAL


text:
German baking trip places available
There are places remaining on a trip to Frankfurt, Germany with the Worshipful Company of Bakers.
The five-day trip starts with delegates assembling on Monday 21 September at the airport hotel before departing for Germany on 22 September.
Delegates will be taken to the Akademie Weinheim to learn how to make German breads and cakes, as well as enjoying a bakery visit.
The trip costs £1,250+VAT (£1,500) and applications to purchase a place are considered on a first-come first-served basis. Flights are included, along with tuition fees and course book, four nights of accommodation and a full set of baker's whites (not including shoes).
Travelling expenses to and from London, travel insurance and any subsistence expenses incurred after returning to the London airport are not included.
Enquiries can be directed to email@example.com.
Delegates must have a signed statement from their college and/or employer upon application, confirming they have agreed. They must also represent the Worshipful Company of Bakers, UK and Irish baking industry and their colleges or companies by maintaining professional conduct at all times.
Written reports of the trip must also be completed and sent to email@example.com by 10 October.
Related articles:
My Account
Most read
15 February, 2019
Baking Industry Awards entries open
17 - 21 February, 2019
19 - 21 February, 2019
23 - 26 February, 2019
CakeWire News


text:
Chartered Building Surveyors in Bedworth
Call 02477 277 472 or 0800 880 6024
Finding a building surveyor in the Bedworth area can be extremely difficult; especially finding one that is as knowledgeable and helpful as our local surveyor, Nigel Polton Dip.surv MRICS. His efficiency and professionalism makes the hassle of finding a new home or investment that little bit less stressful.
For all the properties in the Bedworth area, Nigel offers building surveys and advice that are of the highest quality. His work is personalised to you, your home and the Bedworth area, making our qualified building surveyor into your very own property consultant.
Getting a survey done by a building surveyor can make all the difference, it saves you money on future repair bills and may even get the purchase price of your property down! The understandable, coherent report that you will receive ensures that you have all the relevant information that you need to make that important, final decision of choosing your new home.
"When surveying, I incorporate a wide variety of building surveying skills that I have picked up over 27 years of commercial and domestic surveying experience. Whatever type of property you are looking to purchase, whatever the age, and whatever the size, I can help to find any faults and make your property into a home.
"Although residential property is my area of expertise, I also overlook works that optimise commercial and domestic units."
Building Surveys and Services from an experienced Bedworth Surveyor
Nigel, Bedworth's Building Surveyor, aims to accommodate every budget and property in the Bedworth area. Our devoted team's extensive knowledge can provide detailed, trustworthy advice that you can trust. We will assist you all the way through the purchasing of your property, getting to know you and the property on an individual level.