text:
|Publication number
|Publication type
|Application number
|Publication date
|May 7, 1991
|Filing date
|Feb 14, 1990
|Priority date
|Jul 29, 1986
|Fee status
|Publication number
|Robert P. L. Absil, Thomas F. Degnan, Scott Han, David O. Marler, Richard F. Socha, Michael R. Stapleton
|Original Assignee
|Mobil Oil Corp.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (28), Referenced by (44), Classifications (47), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
X2 O3 :(n)YO2,
X2 O3 :(n)YO2,
X2 O3 :(n)YO2,
This application is a continuation-in-part of U.S. patent application Ser. No. 254,524, filed Oct. 6, 1988, now U.S. Pat. No. 4,954,325, which is a continuation-in-part of U.S. patent application Ser. No. 98,176, filed Sept. 18, 1987, now abandoned, which is a continuation-in-part of U.S. patent application Ser. No. 890,268, filed July 29, 1986 , now abandoned.
This invention relates to a catalytic hydrocracking process for upgrading hydrocarbon streams.
Zeolitic materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties. Such molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline silicates. These silicates can be described as a rigid three-dimensional framework of SiO4 and Periodic Table Group IIIA element oxide, e.g. AlO4, in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total Group IIIA element, e.g. aluminum, and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedra containing the Group IIIA element, e.g. aluminum, is balanced by the inclusion in the crystal of a cation, e.g. an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of the Group IIA element, e.g. aluminum, to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of cation may be exchanged either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given silicate by suitable selection of the cation. The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.
Prior art techniques have resulted in the formation of a great variety of synthetic zeolites. Many of these zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite Z (U.S. Pat. No. 2,882,243); zeolite X (U.S. Pat. No. 2,882,244); zeolite Y (U.S. Pat. No. 3,130,007); zeolite ZK-5 (U.S. Pat. No. 3,247,195); zeolite ZK-4 (U.S. Pat. No. 3,314,752); zeolite ZSM-5 (U.S. Pat. No. 3,702,886); zeolite ZSM-11 (U.S. Pat. No. 3,709,979); zeolite ZSM-12 (U.S. Pat. No. 3,832,449); zeolite ZSM-20 (U.S. Pat. No. 3,972,983); zeolite ZSM-35 (U.S. Pat. No. 4,016,245); and zeolite ZSM-23 (U.S. Pat. No. 4,076,842), merely to name a few.
The SiO2 /Al2 O3 ratio of a given zeolite is often variable. For example, zeolite X can be synthesized with SiO2 /Al2 O3 ratios of from 2 to 3; zeolite Y, from 3 to about 6. In some zeolites, the upper limit of the SiO2 /Al2 O3 ratio is unbounded. ZSM-5 is one such example wherein the SiO2 /Al2 O3 ratio is at least 5 and up to the limits of present analytical measurement techniques. U.S. Pat. No. 3,941,871 (U.S. Pat. No. Re. 29,948) discloses a porous crystalline silicate made from a reaction mixture containing no deliberately added alumina in the recipe and exhibiting the X-ray diffraction pattern characteristic of ZSM-5. U.S. Pat. Nos. 4,061,724; 4,073,865 and 4,104,294 describe crystalline silicates of varying alumina and metal content.
The hydrocracking of hydrocarbons to produce lower boiling hydrocarbons, and in particular, hydrocarbons boiling in the motor fuel range, is an operation upon which a vast amount of time and effort has been spent in view of its commercial significance. Hydrocracking catalysts usually comprise a hydrogenation-dehydrogenation component deposited on an acidic support such as silica-alumina, silica-magnesia, silica-zirconia, alumina, acid treated clays, zeolites, and the like.
Zeolites have been found to be particularly effective in the catalytic hydrocracking of a gas oil to produce motor fuels and such has been described in many U.S. patents including U.S. Pat. Nos. 3,140,249; 3,140,251; 3,140,252; 3,140,253; and, 3,271,418.
A catalytic hydrocracking process utilizing a catalyst comprising a zeolite dispersed in a matrix of other components such as nickel, tungsten and silica-alumina is described in U.S. Pat. No. 3,617,498.
A hydrocracking catalyst comprising a zeolite and a hydrogenation-dehydrogenation component such as nickel-tungsten sulfide is disclosed in U.S. Pat. No. 4,001,106.
The hydrocracking process described in U.S. Pat. No. 3,758,402 utilizes a catalyst possessing a large pore size zeolite component such as zeolite X or Y and an intermediate pore size zeolite component such as ZSM-5 with a hydrogenation-dehydrogenation component such as nickel-tungsten being associated with at least one of the zeolites.
Hydrocarbon conversion utilizing a catalyst comprising a zeolite, such as ZSM-5, having a zeolite particle diameter in the range of 0.005 micron to 0.1 micron and in some instances containing a hydrogenation-dehydrogenation component is disclosed in U.S. Pat. No. 3,926,782.
The hydrocracking of lube oil stocks employing a catalyst comprising a hydrogenation component and a zeolite such as ZSM-5 is disclosed in U.S. Pat. No. 3,755,145.
Hydrocracking operations featuring the use of dual reaction stages, or zones, and/or two different catalysts are also known.
U.S. Pat. No. 3,535,225 discloses a dual-catalyst hydrocracking process in which a hydrocarbon feedstock is initially contacted with a first catalyst comprising a hydrogenation component and a component selected from the group consisting of alumina and silica-alumina and subsequently with a second catalyst provided as a silica-based gel, a hydrogenation component and a zeolite in the ammonia or hydrogen form and free of any loading metal or metals.
U.S. Pat. No. 3,536,604 discloses a hydrofining-hydrocracking process in which a hydrocarbon feed containing 300 to 10,000 ppm organic nitrogen is contacted with a hydrofining catalyst comprising a Group VI or Group VIII metal on an alumina or silica-alumina support whereby the organic nitrogen content of the feed is reduced to a level of 10 ppm to 200 ppm, a substantial portion of the resulting hydrofined effluent thereafter being contacted with a second catalyst comprising a gel matrix comprising at least 15 wt. % silica, alumina, nickel and/or cobalt, molybdenum and/or tungsten, and a zeolite in the ammonia or hydrogen form and free of any loading metal.
U.S. Pat. No. 3,536,605 discloses a hydrofining-hydrocracking process in which a hydrocarbon feed containing substantial amounts of organic nitrogen is contacted in a hydrofining reaction zone under hydrofining conditions with a catalyst comprising a gel matrix comprising silica and alumina and nickel and/or cobalt and molybdenum and/or tungsten and a zeolite having a silica-to-alumina ratio above about 2.15, a unit cell size below about 24.65 Angstroms (A), and a sodium content below about 3 wt. % to produce a hydrofined product of reduced nitrogen content. The effluent from the hydrofining reaction zone is then hydrocracked in a hydrocracking reaction zone under hydrocracking conditions in the presence of hydrogen and a hydrocracking catalyst.
U.S. Pat. No. 3,558,471 discloses a two-catalyst process wherein a hydrocarbon feedstock is first hydrotreated in the presence of a catalyst comprising a silica-alumina gel matrix containing nickel or cobalt, or both, and molybdenum or tungsten, or both, and a zeolite substantially in the ammonia or hydrogen form free of any catalytic loading metal or metals, the zeolite having a silica-to-alumina ratio above about 2.15, unit cell size below about 24.65 A, and a sodium content belwo about 3 wt. %, calculated as Na2 O, to produce a first effluent which is thereafter hydrocracked in a second reaction zone in the presence of a hydrocracking catalyst which may be the same catalyst used in the first reaction zone or a conventional hydrocracking catalyst.
U.S. Pat. No. 3,788,974 discloses a two-catalyst hydrocracking process wherein a hydrocarbon oil feedstock containing from about 0.01 to 0.5 wt. % nitrogen compounds is contacted in a first hydrocracking zone with a zeolite catalyst of the faujasite type in combination with a nickel/tungsten hydrogenation component to provide an effluent which is contacted in a second separate hydrocracking zone with a hydrocracking catalyst, preferably zeolite X or Y.
In U.S. Pat. Nos. 3,894,930 and 4,054,539, a hydrocracking process is disclosed which employs a catalyst comprising a hydrogenation component, an ultrastable zeolite and a silica-alumina cracking catalyst.
U.S. Pat. No. 4,612,108 discloses a process in which an initial hydrotreating stage employing a conventional hydrotreating catalyst is followed by a hydrocracking stage employing zeolite Beta as the hydrocracking catalyst.
Catalytic hydrocracking of a hydrocarbon feedstock can in certain cases be accompanied by dewaxing, that is selective conversion of straight-chain and slightly branched paraffins, such that the pour point of the product is reduced. See U.S. Pat. No. 3,668,113.
It is known to produce a high quality lube base stock oil by subjecting a waxy crude oil fraction to solvent refining, followed by catalytic dewaxing over ZSM-5, with subsequent hydrotreating of the lube base stock as described in U.S. Pat. No. 4,181,598. Zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 , and ZSM-38 have been proposed for dewaxing processes and their use is described in U.S. Pat. Nos. 3,894,938; 4,176,050; 4,181,598; 4,222,855; 4,229,282; and 4,247,388. A dewaxing process employing synthetic offretite is described in U.S. Pat. No. 4,259,174.
The use of zeolite Beta as catalyst for dewaxing hydrocarbon feedstocks such as distillate fuel oils by isomerization is described in U.S. Pat. Nos. 4,419,220 and 4,501,926. U.S. Pat. No. 4,486,296 teaches hydrodewaxing and hydrocracking of a hydrocarbon feedstock over a three-component catalyst including zeolite Beta. Dewaxing a paraffin-containing hydrocarbon feedstock employing a hydrotreating step prior to the dewaxing step over zeolite Beta catalyst is disclosed in U.S. Pat. Nos. 4,518,485 and 4,612,108. U.S. Pat. No. 4,481,104 discloses distillate-selective hydrocracking using a large pore, high silica, low acidity catalyst, e.g. zeolite Beta catalyst. Hydrocracking C5 + naphthas over a catalyst comprising zeolite Beta is disclosed in U.S. Pat. No. 3,923,641. A dewaxing process using a noble metal/zeolite Beta catalyst followed by a base metal/zeolite Beta catalyst is disclosed in U.S. Pat. No. 4,554,065. U.S. Pat. No. 4,541,919 discloses a dewaxing process using a large pore zeolite catalyst such as zeolite Beta which has been selectively coked. U.S. Pat. No. 4,435,275 describes a moderate pressure hydrocracking process which may use a catalyst comprising zeolite Beta for producing low pour point distillates.
European patent application No. 94,827 discloses the use of zeolite Beta for hydrocracking and compares it for that process with other hydrocracking catalysts such as high silica zeolite Y, zeolite X and ZSM-20 (as described in European patent application No. 98,040). U.S. Pat. No. 4,612,108 describes the hydrocracking and dewaxing of waxy petroleum fractions by passing the fractions over a hydrocracking catalyst comprising zeolite Beta and a matrix material in the presence of hydrogen and under hydrocracking conditions, the proportion of zeolite Beta in the hydrocracking catalyst increasing in the direction in which the fraction is passed.
U.S. Pat. No. 4,601,993 describes the dewaxing of a lubricating oil feedstock by passing the waxy fraction over a catalyst bed containing a mixture of medium-pore size zeolite and large-pore zeolite having a Constraint Index of less than 2 and having hydroisomerization activity in the presence of a hydrogenation component.
U.S. Pat. No. 4,358,362 discloses a dewaxing process in which the feed is subjected to pretreatment with a zeolite sorbent to sorb zeolite poisons present therein.
It is known to produce lubricating oil of improved properties by hydrotreating the lubricating oil base stock in the presence of ZSM-39 containing cobalt and molybdenum, as shown in U.S. Pat. No. 4,395,327.
In accordance with the present invention, there is provided a hydrocracking process which comprises contacting a hydrocarbon stream under hydrocracking conditions and in the presence of hydrogen with a hydrocracking catalyst composition comprising a synthetic porous crystalline zeolite, hereafter referred to as "MCM-22", having an X-ray diffraction pattern including lines set forth in Table I, infra. A particular embodiment of the present invention provides a process for reducing the pour point of a waxy component-containing hyrocarbon oil feed which comprises contacting said feed with a catalyst composition under conditions suitable to effect hydrocracking and dewaxing of said feed to provide a hydrocracked/dewaxed product of reduced pour point, said catalyst composition comprising said synthetic porous crystalline material.
Another embodiment of the present invention provides a dual-stage hydrocracking process which comprises:
(a) contacting a hydrocarbon stream, for example one boiling above a temperature of about 300� F., in a first stage under hydrocracking conditions and in the presence of hydrogen with a first hydrocracking catalyst composition comprising said synthetic porous crystalline material and at least one hydrogenation component to provide a first hydrocracked effluent; and
(b) contacting said first hydrocracked effluent in a second stage under hydrocracking conditions and in the presence of hydrogen with a second hydrocracking catalyst composition comprising (i) a molecular sieve having a larger pore size than the first stage catalyst, e.g. zeolite Beta, and (ii) at least one hydrogenation component to provide a second hydrocracked effluent.
The dual-stage hydrocracking process embodiment of this invention exploits the ability of the first hydrocracking catalyst composition to selectively convert aromatics present in the feedstock introduced to the first stage to paraffins and naphthenes and the ability of the second stage hydrocracking catalyst composition to selectively convert the paraffins to more highly isomerized products having lower pour points.
The terms "hydrocracking" and "hydrocracking conditions" shall be understood herein and in the appended claims to refer to any hydroconversion operation in which a relatively heavy hydrocarbon undergoes mild cracking to hydrocarbon products of lower molecular weight. These terms are to be regarded herein as inclusive not only of hydrocracking per se but such hydroconversion operations as paraffin isomerization.
FIG. 1 is a graphical representation of process performance data relating to a catalytic hydrocracking process over NiW/MCM-22/Al2 O3 catalyst.
FIG. 2 is a graphical representation of process performance data relating to a catalytic hydrocracking process over NiW/zeolite Beta/ As2 O3 catalyst.
FIGS. 3 and 4 are graphical comparisons of process performance data relating to catalytic hydrocracking/dewaxing processes employing NiW/MCM-22, NiW/USY and NiW/zeolite Beta catalysts.
The present process is especially advantageous for hydrocracking heavier waxy fractions, e.g. those having boiling points of 343� C. (650� F.) or higher, e.g. light virgin gas oils, light catalytic cycle oils and light vacuum gas oils, and their mixtures. The present process enables such heavy feedstocks to be converted to distillate range products boiling below 343� C. (650� F.); but in contrast to prior processes which use large-pore catalysts such as zeolite Y, the consumption of hydrogen is less and, for a given rate of conversion, product pour point is lower, that is, the hydrocracking is accompanied by dewaxing. In contrast to dewaxing processes using more shape selective catalysts, bulk conversion, including cracking of aromatic components, takes place, ensuring acceptably low viscosity in the distillate range product. Thus, the present process is capable of effecting bulk conversion together with simultaneous dewaxing. Moreover, this is achieved with a reduced hydrogen consumption as compared to other types of processes. It is also possible to operate at partial conversion, thus, effecting economies in hydrogen consumption while still meeting product pour point and viscosity requirements.
While not intending to be bound by theory, it is believed that during conversion, aromatics and naphthenes which are present in the feedstock undergo hydrocracking reactions such as dealkylation, ring opening and cracking, followed by hydrogenation. The long-chain normal and slightly-branched paraffins which are present in the feedstock, together with the paraffins produced by the hydrocracking of the aromatics are, in addition, converted into products which are less waxy than the straight-chain paraffins, thereby effecting simultaneous dewaxing. The process of the present invention produces not only a reduction in the viscosity of the original feed by hydrocracking but also a simultaneous reduction in its pour point by hydrodewaxing.
Suitable feedstocks for the present invention range from relatively light distillate fractions up to high boiling stocks such as whole crude petroleum, reduced crudes, vacuum tower residua, propane deasphalted residua, e.g. brightstock, cycle oils, FCC tower bottoms, gas oils, vacuum gas oils, deasphalted residua and other heavy oils. The feedstock will normally be a C10 + feedstock, since light oils will usually be free of significant quantities of waxy components. However, the process is also particularly useful with waxy distillate stocks such as gas oils, kerosenes, jet fuels, lubricating oil stocks, heating oils, hydrotreated oil stock, furfural-extracted lubricating oil stock and other distillate fractions whose pour point and viscosity properties need to be maintained within certain specification limits. Lubricating oil stocks, for example, will generally boil above 230� C. (450� F.) and more usually above 315� C. (600� F.). For purposes of this invention, lubricating oil or lube oil is that part of hydrocarbon feedstock having a boiling point of 315� C. (600� F.) or higher, as determined by ASTM D-1160 test method.
The hydrocarbon feedstocks which can be treated by the hydrocracking process of the present invention will typically boil at a temperature above 150� C. (300� F.). Advantageously, the feedstocks will be those which boil within the range of 177� to 538� C. (350� F. to 1000� F.). The feedstocks can contain a substantial amount of nitrogen, e.g. at least 10 ppm nitrogen, and even greater than 500 ppm in the form of organic nitrogen compounds. The feeds can also have a significant sulfur content, ranging from 0.1 wt. % to 3 wt. %, or higher. If desired, the feeds can be treated in a known or conventional manner to reduce the sulfur and/or nitrogen content thereof.
Conveniently, the hydrocracking process of the invention also includes the step of contacting the hydrocarbon feed, either in the same or a separate stage, with a second catalyst composition comprising (i) a molecular sieve having a larger pore size than the zeolite of Table I, e.g. zeolite beta, and (ii) at least one hydrogenation component. Such a two-catalyst scheme exploits the ability of the hydrocracking catalyst composition of the invention to selectively convert aromatics present in the feedstock to paraffins and naphthenes and the ability of the second hydrocracking catalyst composition to selectively convert the paraffins in the first stage effluent to more highly isomerized products having lower pour points.
The feedstocks to be treated by the two-catalyst hydrocracking embodiment of the present invention will ordinarily contain a substantial amount of cyclic hydrocarbons, i.e. aromatic and/or naphthenic hydrocarbons. Advantageously, the feeds can contain 3 wt. % to 40 wt. % aromatics and/or naphthenes. Examples of hydrocarbon streams which can be treated by the two-stage hydrocracking embodiment are light vacuum gas oils, heavy vacuum gas oils, light catalytic cycle oils, heavy catalytic cycle oils, virgin gas oils, and mixtures thereof.
In its calcined form, the zeolite employed in the hydrocracking catalyst composition of the invention has an X-ray diffraction pattern which includes the lines listed in Table I below:
TABLE I______________________________________Interplanar d-Spacing (A) Relative Intensity, I/Io � 100______________________________________30.0 � 2.2 W-M22.1 � 1.3 W12.36 � 0.4 M-VS11.03 � 0.2 M-S8.83 � 0.14 M-VS6.18 � 0.12 M-VS6.00 � 0.10 W-M4.06 � 0.07 W-S3.91 � 0.07 M-VS3.42 � 0.06 VS______________________________________
More specifically, the calcined form may be characterized by an X-ray diffraction pattern including the following lines:
TABLE II______________________________________Interplanar d-Spacing (A) Relative Intensity, I/Io � 100______________________________________30.0 � 2.2 W-M22.1 � 1.3 W12.36 � 0.4 M-VS11.03 � 0.2 M-S8.83 � 0.14 M-VS6.86 � 0.14 W-M6.18 � 0.12 M-VS6.00 � 0.10 W-M5.54 � 0.10 W-M4.92 � 0.09 W4.64 � 0.08 W4.41 � 0.08 W-M4.25 � 0.08 W4.10 � 0.07 W-S4.06 � 0.07 W-S3.91 � 0.07 M-VS3.75 � 0.06 W-M3.56 � 0.06 W-M3.42 � 0.06 VS3.30 � 0.05 W-M3.20 � 0.05 W-M3.14 � 0.05 W-M3.07 � 0.05 W2.99 � 0.05 W2.82 � 0.05 W2.78 � 0.05 W2.68 � 0.05 W2.59 � 0.05 W______________________________________
These values were determined by standard techniques. The radiation was the K-alpha doublet of copper and a diffractometer equipped with a scintillation counter and an associated computer was used. The peak heights, I, and the positions as a function of 2 theta, where theta is the Bragg angle, were determined using algorithms on the computer associated with the diffractometer. From these, the relative intensities, 100 I/Io, where Io is the intensity of the strongest line or peak, and d (obs.) the interplanar spacing in Angstroms Units (A), corresponding to the recorded lines, were determined. In Table I, the relative intensities are given in terms of the symbols W=weak, M=medium, S=strong and VS=very strong. In terms of intensities, these may be generally designated as follows:
It should be understood that these X-ray diffraction patterns are characteristic of all species of the present zeolite. The sodium form as well as other cationic forms reveal substantially the same pattern with some minor shifts in interplanar spacing and variation in relative intensity. Other minor variations can occur depending on the Y to X, e.g. silicon to aluminum, mole ratio of the particular sample, as well as its degree of thermal treatment.
The synthetic porous crystalline zeolite employed in the hydrocracking catalyst composition of the invention has a composition involving the molar relationship:
X2 O3 :(n)YO2,
wherein X is a trivalent element, such as aluminum, boron, iron and/or gallium, preferably aluminum, Y is a tetravalent element such as silicon and/or germanium, preferably silicon, and n is at least 10, usually from 10 to 150, more usually from 10 to 60, and even more usually from 20 to 40. In the as-synthesized form, the zeolite has a formula, on a anhydrous basis and in terms of moles of oxides per n moles of YO2, as follows:
(0.005-0.1)Na2 O:(1-4)R:X2 O3 :nYO2
wherein R is an organic component. The Na and R components are associated with the zeolite as a result of their presence during crystallization, and are easily removed by post-crystallization methods hereinafter more particularly described.
The above zeolite is thermally stable and exhibits high surface area greater than 400 m2 /gm as measured by the BET (Bruenauer, Emmet and Teller) test and unusually large sorption capacity when compared to similar crystal structures. In particular the zeolite exhibits equilibrium adsorption values greater than 4.5 wt. % for cyclohexane vapor and greater than 10 wt. % for n-hexane vapor. As is evident from the above formula, the zeolite is synthesized nearly free of Na cations. It can, therefore, be used as a hydrocracking catalyst with acid activity without an exchange step. To the extent desired, however, the original sodium cations of the as-synthesized material can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations. Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e.g. ammonium, ions and mixtures thereof. Particularly preferred cations are those which tailor its catalytic activity for hydrocracking reactions. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Table of the Elements.
Prior to its use in a hydrocracking catalyst composition, the present zeolite crystals should be subjected to thermal treatment to remove part or all of any organic constituent present therein.
Prior to use, the present zeolite should be dehydrated, at least partially. This can be done by heating the crystals to a temperature in the range of 200� C. to 595� C. in an inert atmosphere, such as air and nitrogen, and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature merely by placing the crystalline material in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
The zeolite employed in the present invention can be prepared from a reaction mixture containing sources of alkali or alkaline earth metal (M), e.g. sodium or potassium, cation, an oxide of trivalent element X, e.g aluminum, an oxide of tetravalent element Y, e.g. silicon, an organic (R) directing agent, hexamethyleneimine, and water, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:
______________________________________Reactants Useful Preferred______________________________________YO2 /X2 O3 10-60 10-40H2 O/YO2 5-100 10-50OH- /YO2 0.01-1.0 0.1-0.5M/YO2 0.01-2.0 0.1-1.0R/YO2 0.05-1.0 0.1-0.5______________________________________
In a preferred synthesis method, the YO2 reactant contains a substantial amount of solid YO2, e.g. at least 30 wt. % solid YO2. Where YO2 is silica, the use of a silica source containing at least 30 wt. % solid silica, e.g. Ultrasil (a precipitated, spray dried silica containing 90 wt. % silica) or HiSil (a precipitated hydrated SiO2 containing 87 wt. % silica, 6 wt. % free H2 O and 4.5 wt. % bound H2 O of hydration and having a particle size of 0.02 micron) favors crystal formation from the above mixture. If another source of oxide of silicon, e.g. Q-Brand (a sodium silicate comprised of 28.8 wt. % of SiO2, 8.9 wt. % Na2 O and 62.3 wt. % H2 O) is used, crystallization may yield little or none of the desired crystalline material. Impurity phases of other crystal structures, e.g. ZSM-12, are prepared in the latter circumstance. Preferably, therefore, the YO2, e.g. silica, source contains at least 30 wt. % solid YO2, e.g. silica, and more preferably at least 40 wt. % solid YO2 e.g., silica.
Crystallization can be carried out at either static or stirred conditions in a suitable reactor vessel such as, e.g. polypropylene jars or teflon lined or stainless steel autoclaves. Generally crystallization is conducted at a temperature of 80� C. to 225� C. for 25 hours to 60 days. Thereafter, the crystals are separated from the liquid and recovered.
Crystallization is facilitated by the presence in the reaction mixture of at least 0.01 percent, preferably 0.10 percent and still more preferably 1 percent, seed crystals (based on total weight) of the crystalline product.
Prior to use in the process of the invention, it may be desirable to incorporate the zeolite described above with another material, or matrix, which is resistant to the temperatures and other conditions employed in the process. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the zeolite, i.e. combined therewith or present during its synthesis, which itself is catalytically active may change the conversion and/or selectivity of the catalyst. Inactive materials suitably serve as diluents to control the amount of conversion so that hydrocracked products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g. bentonite and kaolin, to improve the crush strength of the catalyst under commercial hydrocracking conditions. Said materials, i.e. clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use, it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays which can be composited with the present zeolite include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with the zeolite also include inorganic oxides, notably alumina.
In addition to the foregoing materials, the zeolite can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. It may also be advantageous to provide at least a part of the foregoing matrix materials in colloidal form so as to facilitate extrusion of the bound catalyst component(s).
The relative proportions of zeolite and inorganic oxide matrix vary widely, with the crystal content ranging from 1 to 90 percent by weight and, more usually, particularly when the composite is prepared in the form of beads, in the range 2 to 80 weight percent of the composite.
The hydrocracking catalyst composition also contains a hydrogenation component such as one or more of tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or one or more noble metals such as platinum, palladium where a hydrogenation-dehydrogenation function is to be performed. Such component can be introduced in the catalyst composition by way of co-crystallization, exchanged into the composition to the extent a Group IIA element, e.g. aluminum, is in the structure, impregnated therein or intimately physically admixed therewith. Such component can be impregnated in or on the zeolite such as, for example, by, in the case of platinum, treating the zeolite with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
The stability of hydrocracking catalyst of the invention may be increased by steaming which is conveniently effected by contacting the zeolite with, for example, 5-100% steam at a temperature of at least 300� C. (preferably 300�-650� C.) for at least one hour (preferably 1-200 hours) at a pressure of 101-2,500 kPa. In a more particular embodiment, the catalyst can be made to undergo steaming with 75-100% steam at 315�-500� C. and atmospheric pressure for 2-25 hours.
In general, the hydrocracking process of the invention is conducted at a temperature of 260� C. to 450� C., a pressure of 2860 to 27,680 kPa (400 to 4000 psig), a liquid hourly space velocity (LHSV) of 0.1 hr-1 to 10 hr-1 and a hydrogen circulation rate of 180 to 1780 Nm3 /m3 (1000 to 10,000 standard cubic feet per barrel).
As previously stated, the hydrocracking process of the invention may also include the step of contacting the hydrocarbon feed, either in the same or a separate stage, with a second hydrocracking catalyst composition containing a molecular sieve, such as a zeolite Beta, which has a larger pore size than the zeolite of Table I and (ii) a hydrogenation component such as any of those previously mentioned. Zeolite Beta is described in U.S. Reissue No. 28,341 (of original U.S. Pat. No. 3,308,069) and may be combined with one or more other matrix materials which are resistant to the process conditions, e.g. any of the matrix materials previously identified herein. Where the zeolite beta composition contacts the feed in a separate hydrocracking stage, this is conveniently effected by passing the effluent from a first stage employing the zeolite of Table I, without prior separation of lighter products, over the zeolite Beta composition. The latter operates under hydrocracking conditions which are within the foregoing ranges and effects selective isomerization of paraffinic components in the first stage effluent. Where the feed is subjected to a single hydrocracking stage, the zeolite of Table I may be composited with the zeolite Beta into a single catalyst particle or may be used as a separate particulate catalyst.
Where the feedstock to be hydrocracked according to the process of the invention contains significant quantities of nitrogen and/or sulfur, it may be desirable initially to subject the feedstock to a conventional hydrotreating process. Hydrotreating can be conducted at low to moderate pressures, typically from 3000 kPa to 10,000 kPa, with the temperature maintained at 350� C. to 450� C. Hydrotreating catalysts include those relatively immune to poisoning by the nitrogenous and sulfurous impurities in the feedstock and generally comprise a non-noble metal component supported on an amorphous, porous carrier such as silica, alumina, silica-alumina or silica-magnesia. Other support materials such as zeolite Y or other large-pore zeolites, either alone or in combination with binders such as silica, alumina, or silica-alumina, can also be used for this purpose. Because extensive cracking is not desired in the hydrotreating operation, the acidic functionality of the carrier can be relatively low compared to that of the hydrocracking/dewaxing catalyst described below. The metal component can be a single metal from Groups VIB and VIII of the Periodic Table such as nickel, cobalt, chromium, vanadium, molybdenum, tungsten, or a combination of metals such as nickel-molybdenum, cobalt-nickel, molybdenum, cobalt-molybdenum, nickel-tungsten or nickel-tungsten-titanium. Generally, the metal component will be selected for good hydrogen transfer activity. The catalyst as a whole will have a good hydrogen transfer activity and minimal cracking characteristics. The catalyst should be pre-sulfided in the normal way in order to convert the metal component (usually impregnated into the carrier and converted to oxide) to the corresponding sulfide.
In the hydrotreating operation, nitrogen and sulfur impurities are converted to ammonia and hydrogen sulfide, respectively. At the same time, polycyclic aromatics are more readily cracked in the present process to form alkyl aromatics. The effluent from the hydrotreating step can be passed directly to the present process without conventional interstage separation of ammonia or hydrogen sulfide although hydrogen quenching can be carried out in order to control the effluent temperature and to control the catalyst temperature in the present process. However, if desired, interstage separation of ammonia and hydrogen sulfide may be carried out.
In order to more fully illustrate the present invention, including the embodiments of hydrocracking/dewaxing and dual-stage hydrocracking and the manner of practicing same, the following examples are presented. In examples illustrative of the synthesis of zeolite MCM-22, whenever sorption data are set forth for comparison of sorptive capacities for water, cyclohexane and/or n-hexane, they were Equilibrium Adsorption values determined as follows:
A weighed sample of the calcined adsorbent was contacted with the desired pure adsorbate vapor in an adsorption chamber, evacuated to less than 1 mm Hg and contacted with 12 Torr of water vapor or 40 Torr of n-hexane or 40 Torr of cyclohexane vapor, pressures less than the vapor-liquid equilibrium pressure of the respective adsorbate at 90� C. The pressure was kept constant (within about �0.5 mm Hg) by addition of adsorbate vapor controlled by a manostat during the adsorption perid, which did not exceed about 8 hours. As adsorbate was adsorbed by the MCM-22 crystalline material, the decrease in pressure caused the manostat to open a valve which admitted more adsorbate vapor to the chamber to restore the above control pressures. Sorption was complete when the pressure change was not sufficient to activate the manostat. The increase in weight was calculated as the adsorption capacity of the sample in g/100 g of calcined adsorbant. Zeolite MCM-22 always exhibits Equilibrium Adsorption values of greater than about 10 wt. % for water vapor, greater than about 4.5 wt. %, usually greater than about 7 wt. % for cyclohexane vapor and greater than about 10 wt. % for n-hexane vapor. These vapor sorption capacities are a notable distinguishing feature of zeolite MCM-22.
When Alpha Value is examined, it is noted that the Alpha Value is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst and it gives the relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time). It is based on the activity of the highly active silica-alumina cracking catalyst taken as an Alpha of 1 (Rate Constant=0.016 sec-1). The Alpha Test is described in U.S. Pat. No. 3,354,078, in the Journal of Catalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), each incorporated herein by reference as to that description. The experimental conditions of the test used herein include a constant temperature of 538� C. and a variable flow rate as described in detail in the Journal of Catalysis, Vol. 61, p. 395.
One part of sodium aluminate (43.5% Al2 O3, 32.2% Na2 O, 25.6% H2 O) was dissolved in a solution containing 1 part of 50% NaOH solution and 103.13 parts H2 O. To this was added 4.50 parts hexamethyleneimine. The resulting solution was added to 8.55 parts of Ultrasil, a precipitated, spray-dried silica (about 90% SiO2).
The reaction mixture had the following composition, in mole ratios:
______________________________________ SiO2 /Al2 O3 = 30.0 OH- /SiO2 = 0.18 H2 O/SiO2 = 44.9 Na/SiO2 = 0.18 R/SiO2 = 0.35______________________________________
where R is hexamethyleneimine.
The mixture was crystallized in a stainless steel reactor, with stirring, at 150� C. for 7 days to produce the MCM-22 zeolite of the invention. The crystalline product was filtered, washed with water and dried at 120� C. After a 20 hour calcination at 538� C., the X-ray diffraction pattern contained the major lines listed in Table III. The sorption capacities of the calcined material were measured to be:
______________________________________H2 O 15.2 wt. %Cyclohexane 14.6 wt. %n-Hexane 16.7 wt. %______________________________________
The surface area of the calcined crystalline material was measured to be 4942 /g.
The chemical composition of the uncalcined material was determined to be as follows:
______________________________________Component wt. %______________________________________SiO2 66.9Al2 O3 5.40Na 0.03N 2.27Ash 76.3SiO2 /Al2 O3, mole ratio = 21.1______________________________________
TABLE III______________________________________Degrees Interplanar2-Theta d-Spacing (A) I/Io______________________________________ 2.80 31.55 25 4.02 21.98 10 7.10 12.45 96 7.95 11.12 4710.00 8.85 5112.90 6.86 1114.34 6.18 4214.72 6.02 1515.90 5.57 2017.81 4.98 520.20 4.40 2020.91 4.25 521.59 4.12 2021.92 4.06 1322.67 3.92 3023.70 3.75 1324.97 3.57 1525.01 3.56 2026.00 3.43 10026.69 3.31 1427.75 3.21 1528.52 3.13 1029.01 3.08 529.71 3.01 531.61 2.830 532.21 2.779 533.35 2.687 534.61 2.592 5______________________________________
A portion of the calcined crystalline product of Example 1 was tested in the Alpha Test and was found to have an Alpha Value of 224.
Three separate synthesis reaction mixtures were prepared with compositions indicated in Table IV. The mixtures were prepared with sodium aluminate, sodium hydroxide, Ultrasil, hexamethyleneimine (R) and water. The mixtures were maintained at 150� C., 143� C. and 150� C., respectively, for 7, 8 and 6 days respectively in stainless steel autoclaves at autogenous pressure. Solids were separated from any unreacted components by filtration and then water washed, followed by drying at 120� C. The product MCM-22 crystals were subjected to X-ray diffraction, sorption, surface area and chemical analyses. The results of sorption, surface area and chemical analyses are also presented in Table IV. The sorption and surface area measurements were of the calcined product.
TABLE IV______________________________________Example 3 4 5______________________________________Synthesis Mixture, mole ratiosSiO2 /Al2 O3 30.0 30.0 30.0OH- /SiO2 0.18 0.18 0.18H2 O/SiO2 19.4 19.4 44.9Na/SiO2 0.18 0.18 0.18R/SiO2 0.35 0.35 0.35Product Composition, Wt. %SiO2 64.3 68.5 74.5Al2 O3 4.85 5.58 4.87Na 0.08 0.05 0.01N 2.40 2.33 2.12Ash 77.1 77.3 78.2SiO2 /Al2 O3, mole ratio 22.5 20.9 26.0Adsorption, Wt. %H2 O 14.9 13.6 14.6Cyclohexane 12.5 12.2 13.6n-Hexane 14.6 16.2 19.0Surface Area, m2 /g 481 492 487______________________________________
Quantities of the calcined (538� C. for 3 hours) crystalline silicate products of Examples 3, 4 and 5 were tested in the Alpha Test and found to have Alpha Values of 227, 180 and 187, respectively.
To demonstrate a further preparation of the present zeolite, 4.49 parts of hexamethyleneimine was added to a solution containing 1 part of sodium aluminate, 1 part of 50% NaOH solution and 44.19 parts of H2 O. To the combined solution were added 8.54 parts of Ultrasil silica. The mixture was crystallized with agitation at 145� C. for 59 hours and the resultant product was water washed and dried at 120� C.
Product chemical composition, surface area and adsorption analyses results were set forth in Table V:
TABLE V______________________________________Product Composition (uncalcined)C 12.1 wt. %N 1.98 wt. %Na 640 ppmAl2 O3 5.0 wt.%SiO2 74.9 wt. %SiO2 /Al2 O3, mole ratio 25.4Adsorption, wt. %Cyclohexane 9.1N-Hexane 14.9H2 O 16.8Surface Area, m2 /g 479______________________________________
Twenty-five grams of solid crystal product from Example 7 were calcined in a flowing nitrogen atmospheres at 538� C. for 5 hours, followed by purging with 5% oxygen gas (balance N2) for another 16 hours at 538� C.
Individual 3 g samples of the calcined material were ion-exchanged with 100 ml of 0.1N TEABr, TPABr and LaCl3 solution separately. Each exchange was carried out at ambient temperature for 24 hours and repeated three times. The exchanged samples were collected by filtration, water-washed to be halide-free and dried. The compositions of the exchanged samples are tabulated below demonstrating the exchange capacity of the present crystalline silicate for different ions.
______________________________________Exchange IonsIonic Composition, wt. % TEA TPA La______________________________________Na 0.095 0.089 0.063N 0.30 0.38 0.03C 2.89 3.63 --La -- -- 1.04______________________________________
The La-exchanged sample from Example 8 was sized to 14 to 25 mesh and then calcined in air at 538� C. for 3 hours. The calcined material had an Alpha Value of 173.
The calcined sample La-exchanged material from Example 9 was severely steamed at 649� C. in 100% steam for 2 hours. The steamed sample had an Alpha Value of 22, demonstrating that the zeolite had very good stability under severe hydrothermal treatment.
This example illustrates the preparation of the present zeolite where X in the general formula, supra, is boron. Boric acid, 2.59 parts, was added to a solution containing 1 part of 45% KOH solution and 42.96 parts H2 O. To this was added 8.56 parts of Ultrasil silica, and the mixture was thoroughly homogenized. A 3.88 parts quantity of hexamethyleneimine was added to the mixture. The reaction mixture had the following composition in mole ratios:
______________________________________ SiO2 /B2 O3 = 6.1 OH- /SiO2 = 0.06 H2 O/SiO2 = 19.0 K/SiO2 = 0.06 R/SiO2 = 0.30______________________________________
where R is hexamethyleneimine.
The mixture was crystallized in a stainless steel reactor, with agitation, at 150� C. for 8 days. The crystalline product was filtered, washed with water and dried at 120� C. A portion of the product was calcined for 6 hours at 540� C. and found to have the following sorption capacities:
______________________________________H2 O 11.7 wt. %Cyclohexane 7.5 wt. %n-Hexane 11.4 wt. %______________________________________
The surface area of the calcined crystalline material was measured (BET) to be 405 m2 /g.
The chemical composition of the uncalcined material was determined to be as follows:
______________________________________N 1.94 wt. %Na 175 ppmK 0.60 wt. %Boron 1.04 wt. %Al2 O3 920 ppmSiO2 75.9 wt. %Ash 74.11 wt. %SiO2 /Al2 O3, molar ratio = 1406SiO2 /(Al + B)2 O3, molar ratio = 25.8______________________________________
A portion of the calcined crystalline product of Example 11 was treated with NH4 Cl and again calcined. The final crystalline product was tested in the Alpha Test and found to have an Alpha Value of 1.
This example illustrates another preparation of the zeolite in which X of the general formula, supra, is boron. Boric acid, 2.23 parts, was added to a solution of 1 part of 50% NaOH solution and 73.89 parts H2 O. To this solution was added 15.29 parts of HiSil silica followed by 6.69 parts of hexamethyleneimine. The reaction mixture had the following composition in mole ratios:
______________________________________ SiO2 /B2 O2 = 12.3 OH- /SiO2 = 0.056 H2 O/SiO2 = 18.6 K/SiO2 = 0.056 R/SiO2 = 0.30______________________________________
where R is hexamethyleneimine.
The mixture was crystallized in a stainless steel reactor, with agitation, at 300� C. for 9 days. The crystalline product was filtered, washed with water and dried at 120� C. The sorption capacities of the calcined material (6 hours at 540� C.) were measured:
______________________________________H2 O 14.4 wt. %Cyclohexane 4.6 wt. %n-Hexane 14.0 wt. %______________________________________
The surface area of the calcined crystalline material was measured to be 438 m2 /g.
The chemical compostion of the uncalcined material was determined to be as follows:
______________________________________Component Wt. %______________________________________N 2.48Na 0.06Boron 0.83Al2 O3 0.50SiO2 73.4SiO2 /Al2 O3, molar ratio = 249SiO2 /(Al + B)2 O3, molar ratio = 28.2______________________________________
A portion of the calcined crystalline product of Example 13 was tested in the Alpha Test and found to have an Alpha Value of 5.
This example illustrates the preparation of NiW/MCM-22/Al2 O3 catalyst which provides the first hydrocracking catalyst composition employed in the hydrocracking process illustrated in Example 17, infra.
The zeolite component of the first hydrocracking catalyst composition was synthesized by adding 4.49 parts quantity of hexamethyleneimine to a mixture containing 1.00 part sodium aluminate, 1.00 part 50% NaOH, 8.54 parts Ultrasil VN3 and 44.19 parts deionized H2 O. The reaction mixture was heated to 143� C. (290� F.) and stirred in an autoclave at that temperature for crystallization. After full crystallinity was achieved, the majority of the hexamethyleneimine was removed from the autoclave by controlled distillation and the zeolite crystals separated from the remaining liquid by filtration, washed with deionized water and dried. The product had an X-ray pattern including the lines of Tables I and II.
A portion of the zeolite crystals was combined with Al2 O3 to form a mixture of 65 parts, by weight, zeolite and 35 parts Al2 O3. Water was added to this mixture to allow the resulting catalysts to be formed into extrudates. The catalyst was activated by calcining at 480� C. (900� F.) in 3v/v/min, nitrogen for three hours, then treated with 50 vol. % air/50 vol % N2 at 3v/v/min, also at 480� C. (900� F.) for 1 hour. The calcination was completed by raising the temperature to 540� C. (1000� F.) at 3� C./min and finally switching to 100% air (3v/v/min) and holding at 540� C. (1000� F.) for three hours. The calcined catalyst had an alpha value of 213. This material was then steamed at 480� C. (900� F.) in 100% steam to 12 hours. The resulting catalyst had an alpha value of 35.
The steamed extrudate was impregnated with ammonium metatungstate via a known and conventional incipient wetness technique at room temperature, dried overnight at 120� C. (250� F.), calcined in dry air at 1� C. (1.8� F.)/min to 540� C. (1000� F.) and held at this temperature in flowing air for three hours.
The tungsten-containing catalyst was then impregnated via the incipient wetness technique with nickel nitrate, dried overnight at 120� C. (250� F.), and then calcined in air using the previously described procedure. The finished NiW/zeolite/Al2 O3 catalyst had the properties shown in Table VI as follows:
TABLE VI______________________________________Properties of NiW/zeolite/Al2 O3First Hydrocracking Catalyst Composition______________________________________Density, g/cm3Packed 0.48Particle 0.82Real 2.57Pore Volume, cm3 /g 0.83Surface Area, m2 /g 451Pore Diameter, Angstroms 74Alpha after Steaming 35Sodium, ppm 132Nickel, wt. % 3.12Tungsten, wt. % 7.85______________________________________
This example illustrates the preparation of NiW/zeolite Beta/Al2 O3 used to provide the second hydrocracking catalyst composition employed in the hydrocracking process illustrated in Example 17, infra.
The zeolite Beta component of the second hydrocracking catalyst composition was synthesized substantially as described in U.S. Pat. No. Re. 28,341 (of original U.S. Pat. No. 3,308,069). The zeolite was then ammonium exchanged twice at room temperature with 5 ml/g 1N ammonium nitrate. A 65 wt. % zeolite Beta/35 wt. % Al2 O3 catalyst composition was prepared from this zeolite by extrusion. The material was dried overnight at 120� C. (250� F.), calcined at 540� C. (1000� F.) in 3 v/v/min N2 at a heating rate of 5� F./min, held at 540� C. (1000� F.) for three hours in 3 v/v/min N2, then treated with air for three hours at 3 v/v/min also at 540� C. (1000� F.). The calcined catalyst had an alpha of 380. This material was then steamed at 540� C. (1000� F. ) in 100% steam 10 hours.
The steamed extrudate was impregnated with ammonium metatungstate via the incipient wetness technique at room temperature, dried overnight at 120� C. (250� F.), calcined in dry air at 1� C. (1.8� F.)/min to 540� C. (1000� F.) and held at this temperature in flowing air for three hours.
The tungsten containing catalyst was then impregnated via the incipient wetness technique with nickel nitrate, dried overnight at 120� C. (250� F.), and then calcined in air using the same procedure described above. The finished NiW/zeolite Beta/Al2 O3 catalyst had the properties shown in Table VII as follows:
TABLE VII______________________________________Properties of NiW/zeolite Beta/Al2 O3Second Hydrocracking Catalyst Composition______________________________________Density, g/cm3Packed 0.54Particle 0.96Real 2.64Pore Volume, cm3 /g 0.67Surface Area, m2 /g 384Pore Diameter, Angstroms 69Alpha after Steaming 52Sodium, ppm 105Nickel, wt. % 3.29Tungsten, wt. % 7.39______________________________________
Both the first and second hydrocracking catalyst compositions (Examples 15 and 16, respectively) were individually compared for their activity and selectivity in converting a vacuum gas oil (VGO) having the properties shown in Table VIII as follows:
TABLE VIII______________________________________Properties of Vacuum Gas Oil Distillate______________________________________Viscosity (SUS) 150Distillation, �F.(�C.) 1% 653 (345) 5% 696 (369)50% 784 (418)95% 877 (469)99% 915 (491)Hydrogen, % 13.40Nitrogen, ppm 620Sulfur, % 0.43Paraffins, % 30.7Mononaphthenes, % 16.9Polynaphthenes, % 17.7Aromatics, % 34.7KV 40� C., cs 26.45KV 100� C., cs 4.805Pour Point, �F.(�C.) 95 (35)Cloud Point, �F.(�C.) 112 (44)Flash, COC, �F.(�C.) 421 (216)Reaction conditions were as follows:LHSV, hr-1 0.4 to 0.6Temperature, �F.(�C.) 670 to 750 (350-400)Pressure, psig (kPa) 1400 to 1500 (9750-10440)H2 circulation 3000 to 5000 scf H2 /BBL (534 to 890 Nm3 H2 /m3)______________________________________
Prior to contacting with the vacuum gas oil, both catalyst compositions were presulfided with a mixture of 2% H2 S in H2 at 240-380 kPa (20 to 40 psig.) The presulfiding procedure involved increasing the temperature from 200� to 400� C. (400� F. to 750� F.) over the course of four hours.
The compositions of the 343� C+ (650� F.+) fractions resulting from the hydrocracking of the VGO over the first and second hydrocracking catalyst compositions are shown in Table IX as follows:
TABLE IX______________________________________Hydrocracking of VGO OverCatalyst of InventionConversion, wt. % Feed 44 63 76 82______________________________________Analysis of 343� C.+FractionParaffins 30.7 27.6 35.9 34.4 34.4Naphthenes 34.6 56.0 51.6 55.2 51.4Aromatics 34.7 16.4 12.5 10.4 14.2______________________________________Hydrocracking of VGO OverZeolite Beta CatalystConversion, wt. % Feed 44 54 67 87______________________________________Analysis of 343� C.+FractionParaffins 30.7 34.0 29.1 17.3 10.3Naphthenes 34.6 55.6 59.3 61.9 67.3Aromatics 34.7 10.4 11.6 20.8 22.4______________________________________
The data in Table IX show that the hydrocracking catalyst composition of the invention selectively converts aromatics and concentrates paraffins and naphthenes in the heavy fraction. The zeolite Beta-based hydrocracking catalyst composition, by contrast, primarily converts paraffins while concentrating aromatics. This can also be seen by examining the compositional reaction pathways as shown in FIGS. 1 and 2. These two Figures compare the relative conversions of the paraffin, naphthene, and aromatic fractions in the 343� C.+ fraction versus overall conversion to 343� C.- for both catalysts. Above 50 wt. % conversion, the zeolite beta hydrocracking catalyst composition catalyst is more selective for paraffins conversion and less selective for aromatics conversion. The opposite is true of the first hydrocracking catalyst composition of the invention.
A sample of the zeolite produced as in Example 15 was used to produce a nickel and tungsten-containing catalyst composition for use in the single stage hydrocracking/dewaxing process of Example 20, infra. Initially, the zeolite (65 wt %) was mulled with Kaiser SA alumina (35 wt. %) and the resultant mixture was extruded with sufficient added water to provide a 1.6 mm (1/16 inch) diameter extrudate and the extrudate was dried at 120� C. (250� F.). The dried extrudate was then heated at 3� C. (5� F.)/minute to 480� C. (900� F.) in flowing nitrogen; held at 480� C. (900� F.) for 3 hours in flowing nitrogen; and held at 480� C. (900� F.) for 1 hour in a 50/50 volume ratio of air/nitrogen. The extrudate was then heated to 540� C. (1000� F.) at 3� C. (5� F.)/minute in the 50/50 air nitrogen/mixture, and held at 540� C. (1000� F.) for 3 hours.
The catalyst composition thus prepared was found to have the following physical properties (Table X):
TABLE X______________________________________Alpha Value 213Sodium, ppm 630Density, g/ccPacked 0.48Particle 0.82Real 2.57Pore Volume, cc/g 0.83Surface Area, m2 /g 451Pore Diameter, Angstroms 74Crush, lb/in2 (kg/m2) 77 (5.4 � 104)______________________________________
The final catalyst composition was prepared by first contacting the zeolite/Al2 O3 product with 100% steam for 12 hours at 480� C. (900� F.). The resulting steamed composition was dried for 2 hours at 120� C. (250� F.) and was found to have an alpha value of 30.
The dried composition was then impregnated to incipient wetness at room temperature with a solution of 0.154 g/g of (NH4)6 W12 O39.9H2 O, dried in air at room temperature for 4 hours, then dried at 120� C. (250� F.) overnight.
The dried composition was then calcined in flowing dry air at 19� C. (34� F.)/minute to 540� C. (1000� F.), and held at this temperature for 3 hours in the flowing dry air.
The resulting composition was then impregnated to incipient wetness at room temperature with a solution of 0.206 g/g of Ni(NO3)2.6H2 O, dried in air at room temperature for 4 hours, then dried at 120� C. (250� F.) overnight.
The dried composition was then calcined in flowing dry air at 19� C. (34� F.)/minute to 540� C. (1000� F.) and held at this temperature for 3 hours in the flowing air. The final composition contained 3.3 wt % Ni and 8.6 wt % W.
A nickel and tungsten-containing alumina-bound USY catalyst composition was prepared for comparison with the nickel and tungsten-containing catalyst composition of Example 15 for catalyzing the hydrocracking/dewaxing process illustrated in Example 20, infra.
The USY catalyst composition was prepared by mixing 65 wt% USY zeolite with 35 wt % alumina, extruding, exchanging with NH4 NO3 solution, steaming with 540� C. (1000� F.) steam for 10 hours and co-impregnating with a solution containing nickel and tungsten salts.
The final USY catalyst composition contained 2.0 wt % Ni and 6.0 wt % W.
The catalysts prepared according to Examples 18 and 19 were used simultaneously to hydrocrack/dewax separate samples of the vacuum gas oil employed in Example 17. In each case conversion was carried out at a pressure of 9690 kPa (1400 psig), a temperature of 354�-418� C. (670�-785� F.), and LHSV of 0.5-1.0 and a hydrogen circulation rate of 710-1600 Nm3 /m3 (4000-9000 scf/bbl).
At 75% conversion, the product yield results were as presented in Table XI below. All material balances were between 90-100% recovery, mostly greater than 95%.
TABLE XI______________________________________Product Yields at 75% Conversion______________________________________.sup. 166-343� C. .sup. C5 -166� C.(330-650� F.) (C5 -330� F.)______________________________________ C1 -C4,Catalyst Distillate, wt. % Naptha, wt. % wt. %______________________________________(Example 18) 25 36 14(Example 19) 33 37 5______________________________________
FIG. 3 shows measured pour points of the product at different conversions during the process over each catalyst. The plotted data show that hydrocracking/dewaxing over the zeolite of the invention provides a product having significantly lower pour point for a given rate of conversion.
This example provides a comparison between the catalyst composition of Example 18 (invention) and the Beta catalyst composition of Example 16 for the conversion of the heavy gas oil employed in Example 20.
Presulfiding of the catalysts was accomplished with a mixture of 2% H2 S in H2 mixture at 240-380 kPa (20-40 psig) with a temperature increase of 200�-400� C. (400�-750� F.) over a period of 4 hours. Reaction conditions were varied over the following ranges:
______________________________________Temperature: 670 to 750� F. (350-400� C.)Pressure: 1400 to 1500 psig (9750-10440 kPa)LHSV: 0.4 to 0.6H2 Circulation: 3000 to 5000 scf/bbl (530-890 Nm3 /m3)______________________________________
The reported conversions are based on the 343� C.+ (650� F.+) portion of the feed. The results of the conversion employing the catalyst of the invention (Example 18) are set forth in Table XII and employing the zeolite beta catalyst of Example 16 are set forth in Table XIII as follows:
TABLE XII______________________________________Conversion, % 28 44 63 76 82Pour point, 62 43 47 10 37Herzog, �F.(�C.) (22) (6) (8) (-12) (3)Pour point, �F.(�C.) 65(18) -- 55(13) -- --Cloud point, �F.(�C.) 76(24) -- 74(23) -- --KV at 40� C., cs 27.17 -- 21.91 -- --KV at 100� C., cs 4.799 -- 4.328 -- --VI 94.0 -- 103.9 -- --Hydrogen, wt. % 13.78 13.99 14.11 14.20 --Nitrogen, ppm 28 8 3 9 12Sulfur, wt. % 0.01 0 0.01 0.002 0.002Paraffins, wt. % 27.6 27.6 35.9 34.4 34.4Naphthenes, wt. % 52.0 56.0 51.6 55.2 51.4Aromatics, wt. % 20.4 16.4 12.5 10.4 14.2Simulated Distillation,�F. 5% 683 686 685 685 70350% 774 772 766 764 77195% 868 867 861 859 863______________________________________
TABLE XIII______________________________________Conversion, % 44 54 67 88Pour point, 66(19) 5(-15) -47(-44) -24(-31)Herzog, �F.Pour point, �F.(�C.) 65(18) 25(-4) -40(-40) --Cloud point, �F.(�C.) 80(27) 44(7) -65(18) --KV at 40� C., cs 27.72 34.96 51.31 --KV at 100� C., cs 4.928 5.395 6.219 --VI 100.5 82.3 49.1 --Hydrogen, wt. % 13.93 13.89 -- --Nitrogen, ppm 2 1 -- --Sulfur, wt. % 0.01 0.01 -- --Paraffins, wt. % 34.0 29.1 17.3 10.3Naphthenes, wt. % 55.6 59.3 61.9 67.3Aromatics, wt. % 10.4 11.6 20.8 22.4Simu1ated Distillation,�F. 5% 702 697 679 69350% 774 777 768 78695% 862 866 857 857______________________________________
As shown in Tables XII and XIII, although catalyst compositions achieve pour point reduction, at conversions below 50%, where the catalyst of the invention makes less distillate and more gas than zeolite Beta, the former lowers the pour point to a greater extend (see FIG. 4). At higher conversion levels, zeolite Beta catalyst is superior in this regard. However, the low paraffin/high aromatic content of the zeolite beta producs at high conversion levels results in these products having low viscosity indexes.
The activity of the catalyst compositions including the zeolite of the invention and zeolite beta were compared at 60% conversion of the heavy gas oil of Table VIII (Example 17). At conditions of 9960 kPa (1430 psig), 0.54 LHSV and 800 Nm3 /m3 (4500 scf H2 /bbl) feed, the temperature required to achieve 60% conversion was 377� C. (711� F.) for zeolite Beta and 383� C. (721� F.) for zeolite of the invention. FIG. 4 plots the distillate yield obtained with the two catalysts as a function of conversion. Both zeolite catalysts produced about the same maximum amount of distillate, but the maximum for zeolite of the invention occured at a significantly higher conversion level. Above 70% conversion, zeolite of the invention provides significantly better selectivity than that of the zeolite Beta.
However, when employed in combination, the differences in catalytic properties of the zeolite of the invention and zeolite Beta for the simultaneous hydrocracking and dewaxing of a heavy hydrocarbon feed complement each other and make it possible to improve the viscosity of the product while simultaneously achieving a low pour point.
|Cited Patent
|Filing date
|Publication date
|Jul 12, 1960
|Jul 7, 1964
|Socony Mobil Oil Co Inc
|Catalytic cracking of hydrocarbons with a crystalline zeolite catalyst composite
|Dec 21, 1961
|Jul 7, 1964
|Socony Mobil Oil Co Inc
|Process for cracking hydrocarbons with a crystalline zeolite
|Feb 10, 1964
|Jul 7, 1964
|Socony Mobil Oil Co Inc
|Hydrocarbon conversion with crystalline acid-metal aluminosilicates
|May 1, 1964
|Jul 7, 1964
|Socony Mobil Oil Co Inc
|Catalytic hydrocarbon conversion with a crystalline zeolite composite catalyst
|Jun 22, 1965
|Sep 6, 1966
|Mobil Oil Corp
|Catalytic conversion of hydrocarbons with a crystalline alumino-silicate in a silica-alumina matrix
|Aug 23, 1968
|Oct 20, 1970
|Chevron Res
|Hydrocarbon conversion catalyst and process using said catalyst
|Sep 6, 1968
|Oct 27, 1970
|Chevron Res
|Hydrocarbon conversion process
|Sep 27, 1968
|Oct 27, 1970
|Chevron Res
|Hydrotreating catalyst comprising an ultra-stable crystalline zeolitic molecular sieve component,and methods for making and using said catalyst
|Sep 13, 1968
|Jan 26, 1971
|Chevron Res
|Hydrotreating catalyst comprising an ultrastable crystalline zeolitic molecular sieve component,and methods for making and using said catalyst
|Jun 2, 1969
|Nov 2, 1971
|Chevron Res
|Catalytic hydrocracking process
|Mar 17, 1971
|Aug 28, 1973
|Mobil Oil Corp
|Lube oil hydrocracking with zsm-5 zeolite
|Oct 6, 1970
|Sep 11, 1973
|Mobil Oil Corp
|Catalytic hydrocracking of hydrocarbons
|Jun 13, 1972
|Jan 29, 1974
|Exxon Research Engineering Co
|Hydrocracking process utilizing mixed nonnoble metal catalyst
|Sep 4, 1973
|Jul 15, 1975
|Standard Oil Co
|Catalyst comprising ultrastable aluminosilicates and hydrocarbon conversion processes employing same
|Feb 9, 1973
|Dec 16, 1975
|Mobil Oil Corp
|Hydrocarbon conversion
|Aug 15, 1973
|Jan 4, 1977
|Mobil Oil Corporation
|Catalytic conversion of hydrocarbons
|Nov 28, 1973
|Oct 18, 1977
|Standard Oil Company (Indiana)
|Catalyst comprising ultrastable aluminosilicates and hydrocarbon-conversion processes employing same
|Apr 13, 1982
|Mar 27, 1984
|Bayer Aktiengesellschaft
|Crystalline aluminosilicate PSH-3 and its process of preparation
|Aug 5, 1985
|Sep 16, 1986
|Mobil Oil Corporation
|Hydrocracking process using zeolite beta
|Mar 26, 1984
|Mar 10, 1987
|Union Oil Company Of California
|Process for producing a high quality lube oil stock
|Nov 23, 1987
|Mar 14, 1989
|Amoco Corporation
|Hydrocracking process
|Feb 17, 1987
|May 2, 1989
|Chevron Research Company
|Zeolite SSZ-25
|Nov 10, 1987
|Aug 15, 1989
|Union Oil Company Of California
|Hydrocracking process utilizing a catalyst having a reduced zeolite content
|Mar 27, 1989
|Oct 24, 1989
|Amoco Corporation
|Two-catalyst hydrocracking process
|Oct 6, 1988
|Sep 4, 1990
|Mobil Oil Corp.
|Composition of synthetic porous crystalline material, its synthesis and use
|Feb 14, 1990
|Nov 6, 1990
|Mobil Oil Corp.
|Process for upgrading hydrocarbons
|Jan 27, 1987
|Aug 12, 1987
|Chevron Research And Technology Company
|New zeolite SSZ-25
|May 11, 1988
|Nov 30, 1988
|ENIRICERCHE S.p.A.
|Synthetic, crystalline, porous material containing oxides of silicon and boron
|Citing Patent
|Filing date
|Publication date
|Oct 5, 1992
|Feb 8, 1994
|Mobil Oil Corp.
|Process for the selective hydrocracking of distillates to produce naphta range high octane isoparaffins
|Apr 13, 1993
|Nov 15, 1994
|Shell Oil Company
|Hydrocarbon conversion process
|Jul 6, 1993
|Nov 15, 1994
|Mobil Oil Corporation
|Process for converting multi-branched heavy hydrocarbons to high octane gasoline
|Oct 30, 1996
|Dec 2, 1997
|Chevron U.S.A. Inc.
|Low-Aluminum boron beta zeolite
|Dec 17, 1996
|Jun 15, 1999
|Exxon Research And Engineering Co.
|Raffinate hydroconversion process
|Feb 13, 1998
|Aug 10, 1999
|Exxon Research And Engineering Co.
|Raffinate hydroconversion process
|Feb 13, 1998
|Aug 10, 1999
|Exxon Research And Engineering Co.
|Hydroconversion process for making lubricating oil basestocks
|Jun 28, 1996
|Nov 2, 1999
|Exxon Research And Engineering Co
|Raffinate hydroconversion process (JHT-9601)
|Oct 24, 1997
|Nov 16, 1999
|Uop Llc
|Process for the simultaneous production of lubricating oil base stocks and motor fuel
|Dec 17, 1996
|Aug 1, 2000
|Exxon Research And Engineering Co.
|Hydroconversion process for making lubricating oil basestocks
|Mar 3, 1999
|Oct 9, 2001
|Richmond, Hitchcock, Fish & Dollar
|Method of making a zeolite material
|Mar 21, 2000
|Dec 4, 2001
|Exxonmobile Research And Engineering Company
|Raffinate hydroconversion process
|Jun 26, 2001
|Jul 15, 2003
|Exxonmobil Research And Engineering Company
|Reffinate hydroconversion process
|Mar 14, 2001
|Oct 7, 2003
|Chevron U.S.A. Inc.
|Hydrocracking and hydrotreating separate refinery streams
|Jun 26, 2001
|Dec 13, 2005
|Exxonmobil Research And Engineering Company
|Hydroconversion process for making lubricating oil basestockes
|Mar 6, 2003
|Jun 6, 2006
|Exxonmobil Chemical Patents Inc.
|Hydrocarbon fluids
|Jul 7, 2004
|Oct 16, 2007
|Conocophillips Company
|Optimization of gas-to-liquids hydrocracker
|Mar 6, 2003
|Dec 25, 2007
|Exxonmobil Chemical Patents Inc.
|Process for the production of hydrocarbon fluids
|Oct 1, 2010
|Sep 13, 2011
|Exxonmobil Chemical Patents Inc.
|Method of preparing a molecular sieve composition
|Aug 13, 2010
|Dec 20, 2011
|Exxonmobil Chemical Patents, Inc.
|Process for manufacturing MCM-22 family molecular sieves
|Jul 15, 2009
|Jun 12, 2012
|Exxonmobil Chemical Patents Inc.
|Process of making alkylaromatics using EMM-13
|Jul 15, 2009
|Jul 3, 2012
|Exxonmobil Chemical Patents Inc.
|Hydroalkylation of aromatic compounds using EMM-13
|Jul 15, 2009
|Jul 10, 2012
|Exxonmobil Chemical Patents Inc.
|Hydroalkylation of aromatic compounds using EMM-12
|Jul 15, 2009
|Jun 18, 2013
|Exxonmobil Chemical Patents Inc.
|Process of making alkylaromatics using EMM-12
|Jul 15, 2009
|Apr 22, 2014
|Exxonmobil Chemical Patents Inc.
|Molecular sieve composition EMM-13, a method of making and a process of using the same
|Jul 15, 2009
|Apr 22, 2014
|Exxonmobil Chemical Patents Inc.
|Molecular sieve composition EMM-12, a method of making and a process of using the same
|Mar 6, 2003
|Nov 13, 2003
|Pierre-Yves Guyomar
|Hydrocarbon fluids
|Mar 6, 2003
|Feb 5, 2004
|Pierre-Yves Guyomar
|Process for the production of hydrocarbon fluids
|Jul 7, 2004
|Jan 12, 2006
|Conocophillips Company
|Optimization of gas-to-liquids hydrocracker
|Aug 13, 2010
|Jan 27, 2011
|Wenyih Frank Lai
|Process for Manufacturing MCM-22 Family Molecular Sieves
|Oct 1, 2010
|Jan 27, 2011
|Wenyih Frank Lai
|Method of Preparing a Molecular Sieve Composition
|Jul 15, 2009
|Mar 24, 2011
|Roth Wieslaw J
|Hydroalkylation of Aromatic Compounds Using EMM-12
|Jun 16, 2011
|Johnson Control Technology Company
|Display device, notably for a motor vehicle
|Jul 15, 2009
|Jun 16, 2011
|Helton Terry E
|Process of Making Alkylaromatics Using EMM-13
|Jul 15, 2009
|Jul 7, 2011
|Wieslaw J Roth
|Novel Molecular Sieve Composition EMM-12, A Method of Making and a Process of Using the Same
|Jul 15, 2009
|Jul 7, 2011
|Roth Wieslaw J
|Novel Molecular Sieve Composition EMM-13, A Method of Making and a Process of Using the Same
|Aug 4, 2011
|Roth Wieslaw J
|Molecular Sieve Composition (EMM-10-P), Its Method of Making, and Use for Hydrocarbon Conversions
|Jul 26, 2012
|Omer Refa Koseoglu
|Pressure cascaded two-stage hydrocracking unit
|May 9, 1998
|Dec 2, 1998
|AlSi-PENTA Zeolithe GmbH
|Synthetic cristalline zeolite powder, its preparation and its use
|Feb 28, 2003
|Sep 12, 2003
|Exxonmobil Chemical Patents Inc.
|Improved hydrocarbon fluids
|Feb 28, 2003
|Dec 24, 2003
|Exxonmobil Chem Patents Inc
|Improved hydrocarbon fluids
|Jun 7, 2005
|Feb 16, 2006
|Conocophillips Company
|Optimization of gas-to-liquids hydrocracker
|Jun 27, 2007
|Jan 31, 2008
|Exxonmobil Chemical Patents Inc.
|Molecular sieve composition (emm-10-p), its method of making, and use for hydrocarbon conversions
|Jul 2, 2007
|Feb 7, 2008
|Exxonmobil Chemical Patents Inc.
|Molecular sieve composition (emm-10), its method of making, and use for hydrocarbon conversions
|U.S. Classification
|208/27, 208/18, 208/111.1, 208/59
|International Classification
|Cooperative Classification
|European Classification
|Feb 14, 1990
Owner name: MOBIL OIL CORPORATION, A CORP. OF NY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:ABSIL, ROBERT P. L.;DEGNAN, THOMAS F.;HAN, SCOTT;AND OTHERS;REEL/FRAME:005247/0574;SIGNING DATES FROM 19891212 TO 19900108
|Sep 3, 1991
|Certificate of correction
|Jul 13, 1994
|Fee payment
Year of fee payment: 4
|Dec 1, 1998
|Maintenance fee reminder mailed
|May 9, 1999
|Lapse for failure to pay maintenance fees
|Jul 6, 1999
|Expired due to failure to pay maintenance fee
Effective date: 19990507


text:
Hockenson threw 149.4 feet which was TJ's personal best and beat his qualifying throw by six feet.
This was the 30th Anniversary of the Hershey Track Meet, and the meet included 560 youth athletes from all 50 States, all Canadian Provinces, and China. These athletes were chosen to compete at the National level out of over 500,000 youths initially signed up to compete at the local level from across North America.
TJ represented Region 1, which included Minnesota, Iowa, Missouri, Wisconsin, Illinois, Michigan, Indiana, Ohio and Ontario, Canada.
In celebration of the 30th anniversary, Olympic legends Carl Lewis, Bruce Jenner, Michael Johnson and Rafer Johnson, as well as Team USA stars Monique Henderson, Bershawn Jackson and Hazel Clark met with the youth athletes and performed exhibition races.

subset: commoncrawl


text:
Welcome to Leon Valley Campground LLC!
Nestled in the hills of the Hidden Valley region in Wisconsin
Leon Valley Campground, located near Sparta, WI, is the perfect place to get away from it all. Relax and appreciate nature on Leon Valley's 80 acre wooded campground, while enjoying all of the amenities that make a vacation perfect.
With over 150 campsites available, you will be sure to find what you are looking for. From rustic, secluded sites to semi-private areas to large campsites that will accommodate large RV's, including water and electricity for your convenience. If a cabin is more your style, you won't be disappointed…but reserve early! Group sites are also available for family gatherings.
Leon Valley Campground has something for the entire family
Take in the outdoors and wildlife by hiking the beautiful trails. Or take a dip in Leon Valley's spacious, heated pool. More than just a campground, there are playgrounds, a recreational room with arcade games and a pool table, basketball and volleyball courts, and organized activities throughout the summer.
Make your reservation today at Leon Valley Campground!
The 2016 season is right around the corner..make your plans today!
We have cabin openings due to a cancellation Memorial Weekend. A great chance that doesn't happen often so HURRY!


text:
Top Definition
A skinnyass joint thats as small as a friggin pin. Rolled by dudes who are bogart with thier weed.
"What the fuck...theres more paper than dope in this lameass pin joint..."
by Chipping Woodlet III November 29, 2005
Type your email address below to get our free Urban Word of the Day every morning!
Emails are sent from firstname.lastname@example.com. We'll never spam you.×


text:
Twenty Additions to AWN's Calendar of Events
This week's updates to the Calendar
of Events includes twenty new events,
from animation, short film and visual arts festivals to an advertising arts
competition, to business conferences. The Calendar of Upcoming Events is a
constantly changing reference source for what's happening around the World
of Animation. Use it to stay abreast of animation related activities across
the globe. If you know of animation related events that we don't have
listed, send an email with the pertinent facts to firstname.lastname@example.com. We'd love
to publish your event information for free!


text:
Superb Cajun joint with an incredible array of hot sauces to choose from !!!
Skip their fried calamari and the gator sausage casserole. Everything else I've tried has been fantastic. Really friendly and effective staff, too. Eat here it's good!
Yummy Cosmopolitan's
True Cajun margarita is amazing. If you like jalapenos
Good food... Something different
If you like pain and little heat. Get endorphin rush
Charles Neville live tonight
Gumbo is spot on!
Mac n'cheese with Jalapeño's and grilled Shrimp wrap...delicious!
VooDoo wings are delicious! Great sandwiches too.
The Bayou North , Cajun Restaurant


text:
We regret that due to the technical limitations of our site, we are unable to offer eBooks or Audio Downloads to customers outside of the UK.
For further details please read our eBooks help.
The Runaway Woman (Hardback)Josephine Cox
Hardback Published: 13/02/2014
- In stock
Click & Collect From your local shop
No-one thought she had the courage...Those looking in from the outside think Lucy Lovejoy's life is like any other, but at the centre of her family there is a big empty hole where all the love and warmth should be. Over the years, her children have watched while their father chipped away at Lucy's self-confidence. Now the children are following their own paths, and Lucy has never felt more alone. When tragedy strikes at the heart of the family, it's a wake-up call for Lucy. Everyone has taken a little piece of her, and she isn't sure who she is anymore. So when Lucy faces a betrayal from those she loves deepest, she knows that it's time to make a choice. Is she brave enough to find herself again?
Publisher: HarperCollins Publishers
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text:
E-mail: email@example.com;email@example.com
Original Article
Unit root bootstrap tests under infinite variance
Article first published online: 16 JUN 2011
DOI: 10.1111/j.1467-9892.2011.00737.x
© 2011 Blackwell Publishing Ltd
Journal of Time Series Analysis
Volume 33, Issue 1, pages 32–47, January 2012
Additional Information
How to Cite
Moreno, M. and Romo, J. (2012), Unit root bootstrap tests under infinite variance. Journal of Time Series Analysis, 33: 32–47. doi: 10.1111/j.1467-9892.2011.00737.x
Publication History
- Issue published online: 27 DEC 2011
- Article first published online: 16 JUN 2011
- First version received August 2009
- Abstract
- Article
- References
- Cited By
- Unit root;
- M-estimators;
- bootstrap;
- stable laws
This article presents a family of new tests for unit roots based on M-estimators. Their robustness makes them very appealing when working with distributions that have infinite variance or heavy tails. These tests are completely automatic regardless of the complex distributions of this kind of estimators because the critical values are approximated using bootstrap, no additional parameter has to be estimated and the results obtained are very good in small samples. An exhaustive Monte Carlo study shows the high performance of these tests compared with others proposed in the literature when the variance is infinite.


text:
Last Thursday morning I stopped in at the Jake Fisher Bash, an annual event hosted by the University of Missouri Delta Center and held in Rone Exhibition Hall. It is also sometimes billed as the Delta Center Field Day.
As always there's a little politicking going on, good food, networking between ag producers (formerly known as farmers) and suppliers, and an opportunity for the scientists at the Delta Center to share innovations in crop production.
Local folks were well represented and that's no surprise given the support from around southeast Missouri for the efforts of the center.
James Shannon provided the invocation. A more proper salutation would be Dr. J Grover Shannon, Ph. D. Local folks get to call him Grover. An acknowledged expert in soybean production Grover's stop on the farm tour included a discussion of new soybean varieties. He was particularly pleased to have a group of high school students (future farmers?) as part of the tour.
Judith Haggard, chairwoman of the University of Missouri's Board of Curators, followed her husband, David, chairman of the center's advisory committee, to the podium and delivered an opening speech. A portion of her time included a video of various types of research taking place within the university's statewide system. Local folks get to call her Judy.
Another portion of her talk was about the university's funding, a challenging proposition to be sure.
Dr. Ken Dobbins, president of Southeast Missouri State University, and I had a similar discussion just about 30 minutes prior to hearing Judy's remarks. While the numbers have not yet been set for the next fiscal budget it is fairly certain more cuts from the state are coming. In Southeast's case, it could be as much as $6 million.
That's particularly daunting when you consider the pledge to Gov. Jay Nixon from the state's institutions of higher education not to raise tuition. Over the past couple of years colleges and universities have worked at cutting expenses. Some of those have been difficult calls to make and not without pain. The trick now is to drive revenue and hold costs.
One way Dr. Dobbins said Southeast is doing so is by raising class size from 21 to 26 students. He believes they can do that without dramatically raising the costs of delivering education to those additional 5-6 students.
He said the university is going to look at how it delivers information to the students.
"Just because I've stood up here and lectured for 30 years doesn't mean that's the best way to do it now," he said. "Just because we have 26 or 27 students in a class doesn't mean they will all be in a classroom all the time." I suppose one might think of that as re-educating the educators.
It's innovative thinking like that, taking advantage of current and emerging technology, that shows up in such independent rankings as the U.S. News rankings that indicatet Southeast as being one of the better values when it comes to a college education. The report is published in the magazine's Aug 31 issue.
I also got a little good news at the breakfast from our host.
Jake told me he has instructed his wife, Shelley, to box up all of his ties once he retires and ship them to me. That's quite a bonanza and anyone who has seen Jake all dressed up knows he has quite an assortment of really nice, pretty ties. For the record, though, I'm not in any hurry to receive those ties.
* * *
Thank you
Thanks to Rick and Cathy Bell for the rain last Sunday afternoon. They decided to wash their vehicles and brought us what we vaguely recall as rain. Maybe they'll do it again soon.
* * *
Advantage Walt
Walt Jockety, former Cardinals general manager who basically lost out in a power struggle in St. Louis to current Cards GM, John Mozeliak, had no trouble finding another job. Baseball fans know he landed a similar role in Cincinnati as GM of the Reds.
Heading into the last six weeks of the season it looks like the advantage goes to Jockety. He's made all the right moves while Cards fans are left scratching their heads at what's going on with their team. Many are wondering if the Ryan Ludwick for Jake Westbrook trade will go down as one of the worst in team history. Another interesting note is the number of former, discarded, Cards on the Reds roster. If memory serves, I believe there are about six.
Do you think Jockety is a little motivated?
* * *
More state fair news
"Entries from Kennett's widely-known purebred swine breeders, Jonesway Farms., apparently dominated the Duroc Show Monday at the Missouri State Fair in Sedalia.
"The fair reported a 'good show' for this breed, and said 'quality was pronounced excellent' by Westley Miller of Montpelier, Ohio and C.S. (Fete) Reid of Carrolton, Mo., who awarded the ribbons and supervised the department.
"Jonesway received three ribbons:
"- Jonesway Perfection was first in the Senior Yearling Boar Class and was Reserve Grand Champion.
"- Their Bright Night was first in the Age Board class.
"- Their senior yearling sow was first in her class and was Reserve Grand Champion.
"Their young gilts and young boars took several second and third premiums, to make a total of 15 ribbons won by Jonesway entries, which is understood to be more than any other herd brought home.
"Jonesway had an outstanding offer of about 20 hogs-possibly the largest showing of swine in the fair's history."
The DDD's unofficial, but much appreciated historian, Vivian Helton, sent that timely submission along from the pages of the Friday, Aug. 24, 1951 edition of the Twice-A-Week Dunklin Democrat.
Bud Hunt is
regional vice president,
publisher of the
Daily Dunklin Democrat, Daily Statesman, Delta News-Citizen, Missourian-News and
North Stoddard Countian.


text:
Struggling Families Searching For Options After Fire At Transitional ShelterThe fire on Thursday morning destroyed a home that has been providing emergency housing for families in need for nearly 40 years.
Fire At Transitional Shelter Sends Residents Right Back On The StreetsA transitional shelter apartment building went up in flames Thursday morning in the Five Points neighborhood of Denver, leaving residents struggling for a place to stay.
1 Seriously Injured After Getting Hit By Light Rail Train In Downtown DenverA person has been hospitalized with serious injuries after getting hit by a light rail train in downtown Denver Monday afternoon.
Man Opens Car Door, Punches Driver In FacePolice are searching for a man who walked up to a car, opened the door and punched the driver in the face.
Police Search For Men Responsible For Attack Near Light Rail StationPolice in Denver have released surveillance images of two men they say are responsible for punching a victim.
Shooting Witness: 'He Followed Him In There And Blew Him Away'A man was arrested on Sunday following a deadly shooting in Denver's Five Points neighborhood.
Denver Police Want Help Locating Assault SuspectPolice in Denver would like the public's help locating a suspect in an assault.
Police Searching For Man Seen Masturbating On Light RailPolice are searching for a man a woman saw masturbating on the light rail.
Woman Killed By Light Rail Train In Five Points IdentifiedA woman who was dragged to her death by a light rail train in downtown Denver has been identified as Jessica Lubken, 26, of Denver.
Woman Dragged And Killed By Light Rail In Five PointsPolice in Denver are investigating a fatal accident involving a light rail train and a pedestrian.


text:
<title>Servo Data Base</title>

Info on Servo Data Base

1. Title: Servo Data
2. Sources
(a) Created by: Karl Ulrich (MIT) in 1986
(b) Donor: Ross Quinlan
(c) Date: May 1993
3. Past Usage:
1. Quinlan, J.R., "Learning with continuous classes", Proc. 5th Australian
Joint Conference on AI (eds A. Adams and L. Sterling), Singapore: World
Scientific, 1992
2. Quinlan, J.R., "Combining instance-based and model-based learning",
Proc. ML'93 (ed P.E. Utgoff), San Mateo: Morgan Kaufmann 1993
Results on 10-way cross-validation:
Method Average Relative
------ |Err| Error
------- --------
Guessing mean 1.15 1.00
Instance-based .52 .26
Regression .86 .49
Model trees .45 .29
Neural nets (G. Hinton) .30 .11
Regression+instances .48 .20
Model trees+instances .30 .17
NN+instances .29 .11
4. Relevant Information:
Ross Quinlan:
This data was given to me by Karl Ulrich at MIT in 1986. I didn't
record his description at the time, but here's his subsequent (1992)
"I seem to remember that the data was from a simulation of a servo
system involving a servo amplifier, a motor, a lead screw/nut, and a
sliding carriage of some sort. It may have been on of the
translational axes of a robot on the 9th floor of the AI lab. In any
case, the output value is almost certainly a rise time, or the time
required for the system to respond to a step change in a position set
(Quinlan, ML'93)
"This is an interesting collection of data provided by Karl
Ulrich. It covers an extremely non-linear phenomenon - predicting the
rise time of a servomechanism in terms of two (continuous) gain settings
and two (discrete) choices of mechanical linkages."
5. Number of Instances: 167
6. Number of Attributes: 4 + numeric class attribute
7. Attribute information:
1. motor: A,B,C,D,E
2. screw: A,B,C,D,E
3. pgain: 3,4,5,6
4. vgain: 1,2,3,4,5
5. class: 0.13 to 7.10
8. Missing Attribute Values: None


text:
Rugged Ranch Universal Walk-In Pen METALCOOPDLX$422.97
Standing 6' 4" Tall, the Universal Walk-In Pen gives plenty of room to get inside to spend time with your pets and do all of the weekly maintenance. The welded wire roof and double latch entry add extra security to keep your pets safe from predators. The removable knock-out back panel allows for the addition of Rugged Ranch's large dog house or Wood Nesting Hutch, making it a complete home. Easily houses up to 12 chickens, small dogs, turtles, adult rabbits, cats, baby goats, iguanas, etc. With over a dozen accessory and configuration options, the Universal Walk-In Pen can be used for all of your small animal needs!
**Canvas is sold separately!
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Specifications Product Dimensions 6.5' W x 7.5' L x 6.25' H Product Weight 196 lbs. Shipping Dimensions 44" x 75" x 16" Shipping Weight 316 lbs. Color Black Powder Coat
Great Day Inc. Plot Pro UTV 40 Gallon Boomless Sprayer 15' Nozzle PLP4015-UTV 2"$420.00
Available with either a 2" or 1.25" receiver.
The Plot Pro Spraying System is a revolutionary solution to small-scale spraying—ideal for use around the farm, ranch, business, home or hunting lease! The Plot Pro units are designed to conveniently strap to ATV racks or mount to the cargo beds of UTV's or trucks.
The Plot Pro is a complete system---includes corrosion-proof polyethylene tank, a choice of 1.8 or 2.8 gpm ShurFlo pumps, the amazing Boominator boomless spray tip and a sturdy metal, adjustable handwand. The single boomless tip delivers coverage up to 25' wide—eliminating the need for awkward booms that are difficult to maneuver in close areas.Learn More
Ace Roto Mold 500 Gallon Vertical Flat Top Tank Vt0500-46$430.97
Vertical - Flat Top tanks feature additional flats for fitting installation or mounting. Tank are free standing with a flat bottom for indoor or outdoor installations. Ace Roto-Mold Vertical Tanks conform to the requirements of NSF/ANSI Standard 61. Tanks are manufactured from medium- or high-density polyethylene with U.V. inhibitors. Tank walls are translucent for level viewing and equipped with gallon indicators.
- Capacity - 500 Gallons
- Weight - 118 Pounds
- Lid - 8"
- Fitting - 2"
- Dimensions - 46 x 77
- Specific Gravity - 2.0
Tuthill/FIllrite Sotera SS415BX731 Electric Drum Pump, Diaphragm, 1/4 HP$436.97
TCV1003: In today's agricultural and industrial markets, isn't it good to know that you can rely on one name Sotera to fit your chemical transfer needs? The Sotera 400B Series offers proven technology that combines the attributes of an air operated diaphragm pump with the convenience, portability, and efficiency of an electric driven design. It also uses less power than other conventional chemical pumps for maximum efficiency.Learn More
Taylor Pittsburgh Field General 3-Point Metal Hooper Spreader 233-S-500$445.97
Field General's gives new meaning to the word adaptable. With this one tool you can spread seed, granular fertilizer, crystalline herbicides, pesticides and sand. Plus you can choose from three different spreading patterns; predominately left, predominately right, or left and right. The seamless all steel seeder\spreader is strong enough to endure rough handling and heavy use. The heat treated paint resists corrosion caused by chemicals and moisture. Each unit comes standard with a rotating agitator and gearbox with shielded drive line.
- Fits Category I, 3 Point Hitch Tractors
- Seemless Conical Steel Hopper
- Adjustable Uniform Spreading Rates from 18 to 800lb per acre
- Effective Spreading widths from 39 to 46 feet
- Choice of 3 Spreading Patterns: Full Rear Pattern, Left Side, Right Side
- 900lb Capacity
- Learn More
Swisher 62" Universal Rolled Plow Blade 2850$449.97
Swisher's UTV Plow Blade makes moving snow, dirt, and gravel quick and easy. It has a wide 62-inch rolled blade and 11 gauge steel construction for powerful shoveling and leveling capabilities. It features a heavy-duty swivel with dual engagement and multiple angle adjustments. This plow can be used with a your existing winch. Comes with plow-saving skids and a reversible cutting edge. Use with Swisher's 10260 UTV Universal Mount Kit. Once installed, the plow can be attached and removed in seconds without tools. Includes heavy duty trip springs, indicator markers, and hardware. Made in the USA!Learn More
Ace Roto Mold 345 or 500 Gallons Stand CB052-45ST$405.97
- Capacity - 345 or 500 - 45 Deg
- Weight - 174 Pounds
- Clearance - 13"
Snap Lock Formex Regular Plastic Chicken Coop$439.97
This plastic coop from Snap Lock goes together quickly, is long lasting and easy to clean. With plenty of space for your flock and easy access to your eggs, this chicken coop is for you! Easily houses 4 to 6 average size birds.
- Long lasting with no repainting
- Impervious to rotting
- Easily cleaned by pressure washing
- Water and impact resistant
- Ultraviolet and chemical resistant
- Lightweight for multiple locations
- No tools required for assembly
- Removable litter tray
- Easy access for egg collection
- Predator resistant with lockable access points
- Dual wall construction provides insulation and strength
Speeco 3 Point Post Hole Digger$429.99
SpeeCo's Model 70 Post Hole Digger is a must have for any tractor owner, fast and easy post holes from your tractor seat! Each unit is built with SpeeCo's heavy duty drive lines, heavy duty gear box, high strength 2-7/8" O.D. tubing and shear bolt protection. Augers and weight kit sold separately.Learn More
Howse Implement Single Moldboard Plow 16" Bottom MPH116-R$446.97
Product features
- Plow frame made of 1" x 4" steel bar.
- Category I hitch and lift pins.
- Replaceable share and shin.
- Recommended for tractors with 18-50 hp depending on size.