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A process is disclosed wherein a naphtha feed is contacted in a reaction vessel with a dehydrocyclization catalyst comprising a large-pore zeolite containing at least one Group VIII metal to produce an aromatics product and a gaseous stream, the aromatics product is separated from the gaseous stream and is passed through a molecular sieve which adsorbs paraffins present in the aromatics product, then the gaseous stream is used to strip the paraffins from the molecular sieve, and the gaseous stream and the paraffins are recycled to the reaction vessel. Preferably, the dehydrocyclization catalyst comprises a type L zeolite containing from 8% to 15% by weight barium and from 0.6% to 1.0% by weight platinum, wherein at least 80% of the crystals of the type L zeolite are larger than 1000 Angstroms, and an inorganic binder selected from the group consisting of silica, alumina, and aluminosilicates.
1. A dehydrocyclization process comprising:
(a) contacting a naphtha feed in a reaction vessel with a dehydrocyclization catalyst at process conditions which favor dehydrocyclization to produce an aromatics product and a gaseous stream, wherein said dehydrocyclization catalyst is a monofunctional catalyst comprising a large-pore zeolite containing at least one Group VIII metal;
(b) separating said aromatics product from said gaseous stream;
(c) passing said aromatics product through a molecular sieve which adsorbs normal paraffins and a substantial portion of the single-branched isoparaffins present in said aromatics product;
(d) using the gaseous stream to strip said normal paraffins and single-branched isoparaffins from the molecular sieve; and
(e) recycling said gaseous stream and said normal paraffins and single-branched isoparaffins to said reaction vessel.
2. A dehydrocyclization process according to claim 1 wherein said molecular sieve is zeolite A.
3. A dehydrocyclization process according to claim 1 wherein said dehydrocyclization catalyst contains an alkaline earth metal selected from the group consisting of barium, strontium, and calcium.
4. A dehydrocyclization process according to claim 3 wherein said alkaline earth metal is barium and wherein said Group VIII metal is platinum.
5. A dehydrocyclization process according to claim 4 wherein said dehydrocyclization catalyst has from 0.1% to 35% by weight barium and from 0.1% to 5% by weight platinum.
6. A dehydrocyclization process according to claim 5 wherein said dehydrocyclization catalyst has from 8% to 15% by weight barium and from 0.6% to 1.0% by weight platinum.
7. A dehydrocyclization process according to claim 1 wherein said large-pore zeolite has an apparent pore size of from 7 to 9 Angstroms.
8. A dehydrocyclization process according to claim 7 wherein said large-pore zeolite is selected from the group consisting of zeolite X, zeolite Y and type L zeolite.
9. A dehydrocyclization process according to claim 8 wherein said large-pore zeolite is zeolite Y.
10. A dehydrocyclization process according to claim 8 wherein said large-pore zeolite is a type L zeolite.
11. A dehydrocyclization process according to claim 10 wherein the majority of the crystals of said type L zeolite are larger than 500 Angstroms.
12. A dehydrocyclization process according to claim 11 wherein the majority of the crystals of said type L zeolite are larger than 1000 Angstroms.
13. A dehydrocyclization process according to claim 12 wherein at least 80% of the crystals of said type L zeolite are larger than 1000 Angstroms.
14. A dehydrocyclization process accorcing to claim 1 wherein said dehydrocyclization catalyst comprises:
(a) a large-pore zeolite containing barium and platinum; and
(b) an inorganic binder.
15. A dehydrocyclization process according to claim 14 said inorganic binder is selected from the group consisting of silica, alumina, and aluminosilicates.
16. A dehydrocyclization process comprising:
(a) contacting a naphtha feed in a reaction vessel with a dehydrocyclization catalyst at process conditions which favor dehydrocyclization to produce an aromatics product and a gaseous stream;
(b) separating said aromatics product from said gaseous stream;
(c) passing said aromatics product through a molecular sieve which adsorbs normal paraffics and single-branched isoparaffins present in said aromatics product;
(d) using the gaseous stream to strip said normal paraffins and single-branched isoparaffins from the molecular sieve; and
(e) recycling said gaseous stream and said normal paraffins and single-branched isoparaffins to said reaction vessel, wherein said dehydrocyclization catalyst comprises:
(1) a type L zeolite containing from 8% to 15% by weight barium and from 0.6% to 1.0% by weight platinum, wherein at least 80% of the crystals of said type L zeolite are larger than 1000 Angstroms; and
(2) an inorganic binder selected rrom the group consisting of silica, alumina, and aluminosilicates.
The invention relates to a new hydrocarbon conversion process wherein a hydrocarbon feed is contacted with a dehydrocyclization catalyst which has a superior selectivity for dehydrocyclization; then the paraffins in the product stream are extracted and recycled to the reaction vessel.
Catalytic reforming is well known in the petroleum industry and refers to the treatment of naphtha fractions to improve the octane rating by the production of aromatics. The more important hydrocarbon reactions occurring during reforming operation include dehydrogenation of cyclohexanes to aromatics, dehydroisomerization of alkylcyclopentanes to aromatics, and dehydrocyclization of acyclic hydrocarbons to aromatics. A number of other reactions also occur, including the following: dealkylation of alkylbenzenes, isomerization of paraffins, and hydrocracking reactions which produce light gaseous hydrocarbons, e.g., methane, ethane, propane and butane. Hydrocracking reactions are to be particularly minimized during reforming as they decrease the yield of gasoline boiling products and hydrogen.
Because of the demand for high octane gasoline for use as motor fuels, etc., extensive research is being devoted to the development of improved reforming catalysts and catalytic reforming processes. Catalysts for successful reforming processes must possess good selectivity, i.e., be able to produce high yields of liquid products in the gasoline boiling range containing large concentrations of high octane number aromatic hydrocarbons and accordingly, low yields of light gaseous hydrocarbons. The catalysts should possess good activity in order that the temperature required to produce a certain quality product need not be too high. It is also necessary that catalysts either possess good stability in order that the activity and selectivity characteristics can be retained during prolonged periods of operation, or be sufficiently regenerable to allow frequent regeneration without loss of performance.
Catalysts comprising platinum, for example, platinum supported on alumina, are well known and widely used for reforming of naphthas. The most important products of catalytic reforming are benzene and alkylbenzenes. These aromatic hydrocarbons are of great value as high octane number components of gasoline.
Catalytic reforming is also an important process for the chemical industry because of the great and expanding demand for aromatic hydrocarbons for use in the manufacture of various chemical products such as synthetic fibers, insecticides, adhesives, detergents, plastics, synthetic rubbers, pharmaceutical products, high octane gasoline, perfumes, drying oils, ion-exchange resins, and various other products well known to those skilled in the art. One example of this demand is in the manufacture of alkylated aromatics such as ethylbenzene, cumene and dodecylbenzene by using the appropriate mono-olefins to alkylate benzene. Another example of this demand is in the area of chlorination of benzene to give chlorobenzene which is then used to prepare phenol by hydrolysis with sodium hydroxide. The chief use for phenol is in the manufacture of phenol-formaldehyde resins and plastics. Another route to phenol uses cumene as a starting material and involves the oxidation of cumene by air to cumene hydroperoxide which can then be decomposed to phenol and acetone by the action of an appropriate acid. The demand for ethylbenzene is primarily derived from its use to manufacture styrene by selective dehydrogenation; styrene is in turn used to make styrene-butadiene rubber and polystyrene. Ortho-xylene is typically oxidized to phthalic anhydride by reaction in vapor phase with air in the presence of a vanadium pentoxide catalyst. Phthalic anhydride is in turn used for production of plasticizers, polyesters and resins. The demand for para-xylene is caused primarily by its use in the manufacture of terephthalic acid or dimethylterephthalate which in turn is reacted with ethylene glycol and polymerized to yield polyester fibers. Substantial demand for benzene also is associated with its use to produce aniline, nylon, maleic anhydride, solvents and the like petrochemical products. Toluene, on the other hand, is not, at least relative to benzene and the C8 aromatics, in great demand in the petrochemical industry as a basic building block chemical; consequently, substantial quantities of toluene are hydrodealkylated to benzene or disproportionated to benzene and xylene. Another use for toluene is associated with the transalkylation of trimethylbenzene with toluene to yield xylene.
Responsive to this demand for these aromatic products, the art has developed and industry has utilized a number of alternative methods to produce them in commercial quantities. One response has been the construction of a significant number of catalytic reformers dedicated to the production of aromatic hydrocarbons for use as feedstocks for the production of chemicals. As is the case with most catalytic processes, the principal measure of effectiveness for catalytic reforming involves the ability of the process to convert the feedstocks to the desired products over extended periods of time with minimum interference of side reactions.
The dehydrogenation of cyclohexane and alkylcyclohexanes to benzene and alkylbenzenes is the most thermodynamically favorable type of aromatization reaction of catalytic reforming. This means that dehydrogenation of cyclohexanes can yield a higher ratio of (aromatic product/nonaromatic reactant) than either dehydroisomerization or dehydrocyclization at a given reaction temperature and pressure. Moreover, the dehydrogenation of cyclohexanes is the fastest of the three aromatization reactions. As a consequence of these thermodynamic and kinetic considerations, the selectivity for the dehydrogenation of cyclohexanes is higher than that for dehydroisomerization or dehydrocyclization. Dehydroisomerization of alkylcyclopentanes is somewhat less favored, both thermodynamically and kinetically. Its selectivity, although generally high, is lower than that for dehydrogenation. Dehydrocyclization of paraffins is much less favored both thermodynamically and kinetically. In conventional reforming, its selectivity is much lower than that for the other two aromatization reactions.
The selectivity disadvantage of paraffin dehydrocyclization is particularly large for the aromatization of compounds having a small number of carbon atoms per molecule. Dehydrocyclization selectivity in conventional reforming is very low for C6 hydrocarbons. It increases with the number of carbon atoms per molecule, but remains substantially lower than the aromatization selectivity for dehydrogenation or dehydroisomerization of naphthenes having the same number of carbon atoms per molecule. A major improvement in the catalytic reforming process will require, above all else, a drastic improvement in dehydrocyclization selectivity that can be achieved while maintaining adequate catalyst activity and stability.
In the dehydrocyclization reaction, acyclic hydrocarbons are both cyclized and dehydrogenated to produce aromatics. The conventional methods of performing these dehydrocyclization reactions are based on the use of catalysts comprising a noble metal on a carrier. Known catalysts of this kind are based on alumina carrying 0.2% to 0.8% by weight of platinum and preferably a second auxiliary metal.
A disadvantage of conventional naphtha reforming catalysts is that with C6 -C8 paraffins, they are usually more selective for other reactions (such as hydrocracking) than they are for dehydrocyclization. A major advantage of the catalyst used in the present invention is its high selectivity for dehydrocyclization.
The possibility of using carriers other than alumina has also been studied and it was proposed to use certain molecular sieves such as X and Y zeolites, which have pores large enough for hydrocarbons in the gasoline boiling range to pass through. However, catalysts based upon these molecular sieves have not been commercially successful.
In the conventional method of carrying out the aforementioned dehydrocyclization, acyclic hydrocarbons to be converted are passed over the catalyst, in the presence of hydrogen, at temperatures of the order of 500� C. and pressures of from 5 to 30 bars. Part of the hydrocarbons are converted into aromatic hydrocarbons, and the reaction is accompanied by isomerization and cracking reactions which also convert the paraffins into isoparaffins and lighter hydrocarbons.
The rate of conversion of the acyclic hydrocarbons into aromatic hydrocarbons varies with the number of carbon atoms per reactant molecule, reaction conditions and the nature of the catalyst.
The catalysts hitherto used have given moderately satisfactory results with heavy paraffins, but less satisfactory results with C6 -C8 paraffins, particularly C6 paraffins. Catalysts based on a type L zeolite are more selective with regard to the dehydrocyclization reaction; can be used to improve the rate of conversion to aromatic hydrocarbons without requiring substantially higher temperatures than those dictated by thermodynamic considerations (higher temperatures usually have a considerable adverse effect on the stability of the catalyst); and produce excellent results with C6 -C8 paraffins, but catalysts based on type L zeolite have not achieved commercial usage, apparently because of inadequate stability.
In one method of dehydrocyclizing aliphatic hydrocarbons, hydrocarbons are contacted in the presence of hydrogen with a catalyst consisting essentially of a type L zeolite having exchangeable cations of which at least 90% are alkali metal ions selected from the group consisting of ions of lithium, sodium, potassium, rubidium and cesium and containing at least one metal selected from the group which consists of metals of Group VIII of the Periodic Table of Elements, tin and germanium, said metal or metals including at least one metal from Group VIII of said Periodic Table having a dehydrogenating effect, so as to convert at least part of the feedstock into aromatic hydrocarbons.
A particularly advantageous embodiment of this method is a platinum/alkali metal/type L zeolite catalyst containing cesium or rubidium because of its excellent activity and selectivity for converting hexanes and heptanes to aromatics, but stability remains a problem.
A major recent development was the development of a new dehydrocyclization catalyst which comprises a large-pore zeolite, a Group VIII metal, and an alkaline earth metal. This catalyst has a superior selectivity for dehydrocyclization. This selectivity is so high that most of the paraffins that are not dehydrocyclized remain as paraffins in the product stream, and reduce the octane rating of the resulting product.
The present invention overcomes the deficiencies of the prior art by contacting a hydrocarbon feed with a dehydrocyclization catalyst comprising a large-pore zeolite and a Group VIII metal to produce an aromatics product and a gaseous stream; then the paraffins contained in the aromatics product are extracted with a molecular sieve and recycled to the dehydrocyclization zone. The hydrocarbon feed is contacted with a dehydrocyclization catalyst comprising a large-pore zeolite (preferably type L zeolite), at least one Group VIII metal (preferably platinum); and preferably an alkaline earth metal selected from the group consisting of barium, strontium and calcium (preferably barium). The result of the dehydrocyclization is an aromatics product and a gaseous stream. The aromatics product is separated from the gaseous stream and is passed through a molecular sieve which adsorbs the paraffins present in the aromatics product; then the gas stream is used to strip the paraffins from the molecular sieve and both the gaseous product and the paraffins are recycled to the dehydrocyclization zone.
Preferably, the dehydrocyclization catalyst contains: (a) a type L zeolite containing from 0.1% to 5% by weight platinum (preferably from 0.6% to 1.0% by weight platinum) and 0.1% to 40% by weight barium (preferably from 0.1% to 35% by weight barium, more preferably from 8% to 15% by weight barium); and (b) an inorganic binder. The majority of the type L zeolite crystals are preferably greater than 500 Angstoms, more preferably greater than 1000 Angstroms. In the most preferred embodiment, at least 80% of the crystals of type L zeolite are greater than 1000 Angstoms. The inorganic binder is preferably either a silica, alumina, or an aluminosilicate. The hydrocarbons are contacted with the barium-exchanged type zeolite at a temperature of from 400� C. to 600� C. (preferably 450� C. to 550� C.); an LHSV of from 0.1 to 20 (preferably from 0.3 to 5); a pressure of from 1 atmosphere to 500 psig (preferably from 50 to 200 psig); and an H2 /HC ratio of from 0 to 20:1 (preferably from 2:1 to 6:1).
In its broadest aspect, the present invention involves the extraction and recycle of paraffins present in the product stream of a dehydrocyclization process using a dehydrocyclization catalyst having a very high selectivity for dehydrocyclization. This dehydrocyclization is carried out using a dehydrocyclization catalyst comprising a large-pore zeolite and a Group VIII metal.
The term "selectivity" as used in the present invention is defined as the percentage of moles of acyclic hydrocarbons converted to aromatics relative to moles converted to aromatics and cracked products, ##EQU1##
Isomerization of paraffins and interconversion of paraffins and alkylcyclopentanes having the same number of carbon atoms per molecule are not considered in determining selectivity.
The selectivity for converting acyclic hydrocarbons to aromatics is a measure of the efficiency of the process in converting acyclic hydrocarbons to the desired and valuable products: aromatics and hydrogen, as opposed to the less desirable products of hydrocracking.
Highly selective catalysts produce more hydrogen than less selective catalysts because hydrogen is produced when acyclic hydrocarbons are converted to aromatics and hydrogen is consumed when acyclic hydrocarbons are converted to cracked products. Increasing the selectivity of the process increases the amount of hydrogen produced (more aromatization) and decreases the amount of hydrogen consumed (less cracking).
Another advantage of using highly selective catalysts is that the hydrogen produced by highly selective catalysts is purer than that produced by less selective catalysts. This higher purity results because more hydrogen is produced, while less low boiling hydrocarbons (cracked products) are produced. The purity of hydrogen produced in reforming is critical if, as is usually the case in an integrated refinery, the hydrogen produced is utilized in processes such as hydrotreating and hydrocracking, which require at least certain minimum partial pressures of hydrogen. If the purity becomes too low, the hydrogen can no longer be used for this purpose and must be used in a less valuable way, for example as fuel gas.
Regarding the dehydrocyclizable hydrocarbons that are subjected to the method of the present invention, they can in general be any aliphatic hydrocarbon or substituted aliphatic hydrocarbon capable of undergoing ring-closure to produce an aromatic hydrocarbon. That is, it is intended to include within the scope of the present invention, the dehydrocyclization of any organic compound capable of undergoing ring-closure to produce an aromatic hydrocarbon and capable of being vaporized at the dehydrocyclization temperatures used herein. More particularly, suitable dehydrocyclizable hydrocarbons are: aliphatic hydrocarbons containing 6 to 20 carbon atoms per molecule such as C6 -C20 paraffins, C6 -C20 olefins and C6 -C20 polyolefins. Specific examples of suitable dehydrocyclizable hydrocarbons are: (1) paraffins such as n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, n-heptane, 2-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, n-octane, 2-methylheptane, 3-ethylhexane, 2,2-dimethylhexane, 2-methyl-3-ethylpentane, 2,2,3-trimethylpentane, n-nonane, 2-methyloctane, 2,2-dimethylheptane, n-decane and the like compounds; (2) olefins such as 1-hexene, 2-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene and the like compounds; and (3) diolefins such as 1,5-hexadiene, 2-methyl-2,4-hexadiene, 2,6-octadiene and the like diolefins.
In a preferred embodiment, the dehydrocyclizable hydrocarbon is a paraffin hydrocarbon having about 6 to 12 carbon atoms per molecule. For example, paraffin hydrocarbons containing about 6 to 10 carbon atoms per molecule are dehydrocyclized by the subject method to produce the corresponding aromatic hydrocarbon. It is to be understood that the specific dehydrocyclizable hydrocarbons mentioned above can be charged to the present method individually, in admixture with one or more of the other dehydrocyclizable hydrocarbons, or in admixture with other hydrocarbons such as naphthenes, aromatics and the like. Thus, mixed hydrocarbon fractions, containing significant quantities of dehydrocyclizable hydrocarbons that are commonly available in a typical refinery, are suitable charge stocks for the instant method; for example, highly paraffinic straight-run naphthas, paraffinic raffinates from aromatic extraction or adsorption, C6 -C12 paraffin-rich streams and the like refinery streams. An especially preferred embodiment involves a charge stock which is a paraffin-rich naphtha fraction boiling in the range of about 140� F. to about 400� F. Generally, best results are obtained with a charge stock comprising a mixture of C6 -C12 paraffins.
Preferably, the feedstock is substantially free of sulfur, nitrogen, metals, and other known poisons for reforming catalysts. This catalyst is especially sensitive to sulfur. The feedstock can be made substantially free of sulfur, nitrogen, metals, and other known poisons by conventional hydrofining techniques plus sorbers that remove sulfur compounds.
In the case of a feedstock which is not already low in sulfur, acceptable levels can be reached by hydrofining the feedstock in a pretreatment zone where the naphtha is contacted with a hydrofining catalyst which is resistant to sulfur poisoning. A suitable catalyst for this hydrodesulfurization process is, for example, an alumina-containing support and a minor proportion of molybdenum oxide, cobalt oxide and/or nickel oxide. Hydrodesulfurization is ordinarily conducted at 315� C. to 455� C., at 200 to 2000 psig, and at a liquid hourly space velocity of 1 to 5. The sulfur and nitrogen contained in the naphtha are converted to hydrogen sulfide and ammonia, respectively, which can be removed prior to reforming by suitable conventional processes.
According to the present invention, the hydrocarbon feedstock is contacted with the catalyst in a dehydrocyclization zone maintained at dehydrocyclization conditions. This contacting may be accomplished by using the catalyst in a fixed bed system, a moving bed system, a fluidized system, or in a batch-type operation; however, in view of the danger of attrition losses of the valuable catalyst and of well-known operational advantages, it is preferred to use either a fixed bed system or a densephase moving bed system. It is also contemplated that the contacting step can be performed in the presence of a physical mixture of particles of a conventional dual-function catalyst of the prior art. In a fixed bed system, the hydrocarbons in the C6 to C14 range are preheated by any suitable heating means to the desired reaction temperature and then passed into a dehydrocyclization zone containing a fixed bed of the catalyst. It is, of course, understood that the dehydrocyclization zone may be one or more separate reactors with suitable means therebetween to ensure that the desired conversion temperature is maintained at the entrance to each reactor. It is also important to note that the reactants may be contacted with the catalyst bed in either upward, downward, or radial flow fashion. In addition, the reactants may be in a liquid phase, a mixed liquid-vapor phase, or a vapor phase when they contact the catalyst, with best results obtained in the vapor phase. The dehydrocyclization system then preferably comprises a dehydrocyclization zone containing one or more fixed beds or dense-phase moving beds of the catalyst. In a multiple bed system, it is, of course, within the scope of the present invention to use the present catalyst in less than all of the beds with a conventional dual-function catalyst being used in the remainder of the beds. The dehydrocyclization zone may be one or more separate reactors with suitable heating means therebetween to compensate for the endothermic nature of the dehydrocyclization reaction that takes place in each catalyst bed.
Although hydrogen is the preferred diluent for use in the subject dehydrocyclization method, in some cases other art-recognized diluents may be advantageously utilized, either individually or in admixture with hydrogen, such as C1 to C5 paraffins such as methane, ethane, propane, butane and pentane; the like diluents, and mixtures thereof. Hydrogen is preferred because it serves the dual function of not only lowering the partial pressure of the acyclic hydrocarbon, but also of suppressing the formation of hydrogen-deficient, carbonaceous deposits (commonly called coke) on the catalytic composite. Ordinarily, hydrogen is utilized in amounts sufficient to insure a hydrogen to hydrocarbon mole ratio of about 0 to about 20:1, with best results obtained in the range of about 2:1 to about 6:1. The hydrogen charged to the dehydrocyclization zone will typically be contained in a hydrogen-rich gas stream recycled from the effluent stream from this zone after a suitable gas/liquid separation step.
The hydrocarbon dehydrocyclization conditions used in the present method include a reactor pressure which is selected from the range of about 1 atmosphere to about 500 psig, with the preferred pressure being about 50 psig to about 200 psig. The temperature of the dehydrocyclization is preferably about 450� C. to about 550� C. As is well known to those skilled in the dehydrocyclization art, the initial selection of the temperature within this broad range is made primarily as a function of the desired conversion level of the acyclic hydrocarbon considering the characteristics of the charge stock and of the catalyst. Ordinarily, the temperature then is thereafter slowly increased during the run to compensate for the inevitable deactivation that occurs to provide a relatively constant value for conversion.
The liquid hourly space velocity (LHSV) used in the instant dehydrocyclization method is selected from the range of about 0.1 to about 20 hr.-1, with a value in the range of about 0.3 to about 5 hr.-1 being preferred.
Reforming generally results in the production of hydrogen. Thus, exogenous hydrogen need not necessarily be added to the reforming system except for pre-reduction of the catalyst and when the feed is first introduced. Generally, once reforming is underway, part of the hydrogen produced is recirculated over the catalyst. The presence of hydrogen serves to reduce the formation of coke which tends to poison the catalyst. Hydrogen is preferably introduced into the reforming reactor at a rate varying from 0 to about 20 moles of hydrogen per mole of feed. The hydrogen can be in admixture with light gaseous hydrocarbons.
If, after a period of operation, the catalyst has become deactivated by the presence of carbonaceous deposits, said deposits can be removed from the catalyst by passing an oxygen-containing gas, such as dilute air, into contact with the catalyst at an elevated temperature in order to burn the carbonaceous deposits from the catalyst. The regeneration can be performed either in the semiregenerative mode in which the reforming operation is interrupted after a more or less long period of time and catalyst regeneration is carried out, or in the onstream regenerative mode, in which a portion of the catalyst is regenerated while the reforming operation is continued over the remainder of the catalyst. Two types of onstream regeneration are known in the prior art, cyclic and continuous reforming. In cyclic reforming, the catalyst in one of a series of reactors is regenerated while reforming is continued in the rest of the plant. In continuous reforming, a portion of deactivated catalyst is removed from the plant, regenerated in a separate regeneration system while reforming is continued in the plant, and the regenerated catalyst is returned to the plant. The method of regenerating the catalyst will depend on whether there is a fixed bed, moving bed, or fluidized bed operation. Regeneration methods and conditions are well known in the art.
The dehydrocyclization catalyst according to the invention is a large-pore zeolite charged with one or more dehydrogenating constituents. The term "large-pore zeolite" is defined as a zeolite having an effective pore diameter of 6 to 15 Angstroms.
Among the large-pored crystalline zeolites which have been found to be useful in the practice of the present invention, type L zeolite, zeolite X, zeolite Y and faujasite are the most important and have apparent pore sizes on the order of 7 to 9 Angstroms.
The chemical formula for zeolite Y expressed in terms of mole oxides may be written as:
(0.7-1.1)Na2 O:Al2 O3 :xSiO2 :yH2 O
wherein x is a value greater than 3 up to about 6 and y may be a value up to about 9. Zeolite Y has a characteristic X-ray powder diffraction pattern which may be employed with the above formula for identification. Zeolite Y is described in more detail in U.S. Pat. No. 3,130,007. U.S. Pat. No. 3,130,007 is hereby incorporated by reference to show a zeolite useful in the present invention.
Zeolite X is a synthetic crystalline zeolitic molecular sieve which may be represented by the formula:
(0.7-1.1)M2/n O:Al2 O3 :(2.0-3.0)SiO2 :yH2 O
wherein M represents a metal, particularly alkali and alkaline earth metals, n is the valence of M, and y may have any value up to about 8 depending on the identity of M and the degree of hydration of the crystalline zeolite. Zeolite X, its X-ray diffraction pattern, its properties, and method for its preparation are described in detail in U.S. Pat. No. 2,882,244. U.S. Pat. No. 2,882,244 is hereby incorporated by reference to show a zeolite useful in the present invention.
The preferred catalyst according to the invention is a type L zeolite charged with one or more dehydrogenating constituents.
Type L zeolites are synthetic zeolites. A theoretical formula is M9 /n [(AlO2)9 (SiO2)27 ] in which M is a cation having the valency n.
The real formula may vary without changing the crystalline structure; for example, the mole ratio of silicon to aluminum (Si/Al) may vary from 1.0 to 3.5.
Although there are a number of cations that may be present in zeolite L, in one embodiment, it is preferred to synthesize the potassium form of the zeolite, i.e., the form in which the exchangeable cations present are substantially all potassium ions. The reactants accordingly employed are readily available and generally water soluble. The exchangeable cations present in the zeolite may then conveniently be replaced by other exchangeable cations, as will be shown below, thereby yielding isomorphic form of zeolite L.
In one method of making zeolite L, the potassium form of zeolite L is prepared by suitably heating an aqueous metal aluminosilicate mixture whose composition, expressed in terms of the mole ratios of oxides, falls within the range:
______________________________________K2 O/(K2 O + Na2 O) From about 0.33 to about 1(K2 O + Na2 O)/SiO2 From about 0.35 to about 0.5SiO2 /Al2 O3 From about 10 to about 28H2 O/(K2 O + Na2 O) From about 15 to about 41______________________________________
The desired product is hereby crystallized out relatively free from zeolites of dissimilar crystal structure.
The potassium form of zeolite L may also be prepared in another method along with other zeolitic compounds by employing a reaction mixture whose composition, expressed in terms of mole ratios of oxides, falls within the following range:
______________________________________K2 O/(K2 O + Na2 O) From about 0.26 to about 1(K2 O + Na2 O)/SiO2 From about 0.34 to about 0.5SiO2 /Al2 O3 From about 15 to about 28H2 O/(K2 O + Na2 O) From about 15 to about 51______________________________________
It is to be noted that the presence of sodium in the reaction mixture is not critical to the present invention.
When the zeolite is prepared from reaction mixtures containing sodium, sodium ions are generally also included within the product as part of the exchangeable cations together with the potassium ions. The product obtained from the above ranges has a composition, expressed in terms of moles of oxides, corresponding to the formula:
0.9-1.3[(1-x)K2 O, xNa2 O]:Al2 O3 :5.2-6.9SiO2 :yH2 O
wherein "x" may be any value from 0 to about 0.75 and "y" may be any value from 0 to about 9.
In making zeolite L, representative reactants are activated alumina, gamma alumina, alumina trihydrate and sodium aluminate as a source of alumina. Silica may be obtained from sodium or potassium silicate, silica gels, silicic acid, aqueous colloidal silica sols and reactive amorphous solid silicas. The preparation of typical silica sols which are suitable for use in the process of the present invention are described in U.S. Pat. No. 2,574,902 and U.S. Pat. No. 2,597,872. Typical of the group of reactive amorphous solid silicas, preferably having an ultimate particle size of less than 1 micron, are such materials as fume silicas, chemically precipitated and precipitated silica sols. Potassium and sodium hydroxide may supply the metal cation and assist in controlling pH.
In making zeolite L, the usual method comprises dissolving potassium or sodium aluminate and alkali, viz., potassium or sodium hydroxide, in water. This solution is admixed with a water solution of sodium silicate, or preferably with a water-silicate mixture derived at least in part from an aqueous colloidal silica sol. The resultant reaction mixture is placed in a container made, for example, of metal or glass. The container should be closed to prevent loss of water. The reaction mixture is then stirred to insure homogeneity.
The zeolite may be satisfactorily prepared at temperatures of from about 90� C. to 200� C. the pressure being atmospheric or at least that corresponding to the vapor pressure of water in equilibrium with the mixture of reactants at the higher temperature. Any suitable heating apparatus, e.g., an oven, sand bath, oil bath or jacketed autoclave, may be used. Heating is continued until the desired crystalline zeolite product is formed. The zeolite crystals are then filtered off and washed to separate them from the reactant mother liquor. The zeolite crystals should be washed, preferably with distillated water, until the effluent wash water, in equilibrium with the product, has a pH of between about 9 and 12. As the zeolite crystals are washed, the exchangeable cation of the zeolite may be partially removed and is believed to be replaced by hydrogen cations. If the washing is discontinued when the pH of the effluent wash water is between about 10 and 11, the (K2 O+Na2 O)/Al2 O3 molar ratio of the crystalline product will be approximately 1.0. Thereafter, the zeolite crystals may be dried, conveniently in a vented oven.
Zeolite L has been characterized in "Zeolite Molecular Sieves" by Donald W. Breck, John Wiley & Sons, 1974, as having a framework comprising 18 tetrahedra unit cancrinite-type cages linked by double 6-rings in columns and crosslinked by single oxygen bridges to form planar 12-membered rings. These 12-membered rings produce wide channels parallel to the c-axis with no stacking faults. Unlike erionite and cancrinite, the cancrinite cages are symmetrically placed across the double 6-ring units. There are four types of cation locations: A in the double 6-rings, B in the cancrinite-type cages, C between the cancrinite-type cages, and D on the channel wall. The cations in site D appear to be the only exchangeable cations at room temperature. During dehydration, cations in site D probably withdraw from the channel walls to a fifth site, site E, which is located between the A sites. The hydrocarbon sorption pores are approximately 7 to 8 Angstroms in diameter.
A more complete description of these zeolites is given, e.g., in U.S. Pat. No. 3,216,789 which, more particularly, gives a conventional description of these zeolites. U.S. Pat. No. 3,216,789 is hereby incorporated by reference to show a type L zeolite useful in the present invention.
Zeolite L differs from other large pore zeolites in a variety of ways, besides X-ray diffraction pattern.
One of the most pronounced differences is in the channel system of zeolite L. Zeolite L has a one-dimensional channel system parallel to the c-axis, while most other zeolites have either two-dimensional or three-dimensional channel systems. Zeolite A, X and Y all have three-dimensional channel systems. Mordenite (Large Port) has a major channel system parallel to the c-axis, and another very restricted channel system parallel to the b-axis. Omega zeolite has a one-dimensional channel system.
Another pronounced difference is in the framework of the various zeolites. Only zeolite L has cancrinite-type cages linked by double-six rings in columns and crosslinked by oxygen bridges to form planar 12-rings. Zeolite A has a cubic array of truncated octahedra, beta-cages linked by double-four ring units. Zeolites X and Y both have truncated octahedra, beta-cages, linked tetrahedrally through double-six rings in an arrangement like carbon atoms in a diamond. Mordenite has complex chains of five-rings crosslinked by four-ring 25 chains. Omega has a fourteen-hedron of gmelinite-type linked by oxygen bridges in columns parallel to the c-axis.
Presently, it is not known which of these differences, or other differences, is responsible for the high selectivity for dehydrocyclization of catalysts made from zeolite L, but it is known that catalysts made of zeolite L do react differently than catalysts made of other zeolites.
Various factors have an effect on the X-ray diffraction pattern of a zeolite. Such factors include temperature, pressure, crystal size, impurities, and type of cations present. For instance, as the crystal size of the type L zeolite becomes smaller, the X-ray diffraction pattern becomes broader and less precise. Thus, the term "zeolite L" includes any zeolites made up of cancrinite cages having an X-ray diffraction pattern substantially similar to the X-ray diffraction patterns shown in U.S. Pat. No. 3,216,789.
Crystal size also has an effect on the stability of the catalyst. For reasons not yet fully understood, catalysts having at least 80% of the crystals of the type L zeolite larger than 1000 Angstroms give longer run length than catalysts having substantially all of the crystals of the type L zeolite between 200 and 500 Angstroms. Thus, the larger of these crystallite sizes of type L zeolite is the preferred support.
Type L zeolites are conventionally synthesized largely in the potassium form, i.e., in the theoretical formula given previously, most of the M cations are potassium. The M cations are exchangeable, so that a given type L zeolite, e.g., a type L zeolite in the potassium form, can be used to obtain type L zeolites containing other cations, by subjecting the type L zeolite to ion exchange treatment in an aqueous solution of appropriate salts. However, it is difficult to exchange all of the original cations, e.g., potassium, since some exchangeable cations in the zeolite are in sites which are difficult for the reagents to reach.
A preferred element of the present invention is the presence of an alkaline earth metal in the dehydrocyclization catalyst. That alkaline earth metal must be either barium, strontium or calcium. Preferably the alkaline earth metal is barium. The alkaline earth metal can be incorporated into the zeolite by synthesis, impregnation or ion exchange. Barium is preferred to the other alkaline earths because the resulting catalyst has high activity, high selectivity and high stability.
In one embodiment, at least part of the alkali metal is exchanged with barium, using techniques known for ion exchange of zeolites. This involves contacting the zeolite with a solution containing excess Ba++ ions. The barium should preferably constitute from 0.1% to 35% of the weight of the zeolite, more preferably from 8% to 15% by weight.
The dehydrocyclization catalysts according to the invention are charged with one or more Group VIII metals, e.g., nickel, ruthenium, rhodium, palladium, iridium or platinum.
The preferred Group VIII metals are iridium and particularly platinum, which are more selective with regard to dehydrocyclization and are also more stable under the dehydrocyclization reaction conditions than other Group VIII metals.
The preferred percentage of platinum in the catalyst is between 0.1% and 5%, more preferably from 0.6% to 1.0%.
Group VIII metals are introduced into the zeolite by synthesis, impregnation or exchange in an aqueous solution of an appropriate salt. When it is desired to introduce two Group VIII metals into the zeolite, the operation may be carried out simultaneously or sequentially.
By way of example, platinum can be introduced by impregnating the zeolite with an aqueous solution of tetrammineplatinum (II) nitrate, tetrammineplatinum (II) hydroxide, dinitrodiamino-platinum or tetrammineplatinum (II) chloride. In an ion exchange process, platinum can be introduced by using cationic platinum complexes such as tetrammineplatinum (II) nitrate.
An inorganic oxide can be used as a carrier to bind the zeolite containing the Group VIII metal and alkaline earth metal and give the dehydrocyclization catalyst additional strength. The carrier can be a natural or a synthetically produced inorganic oxide or combination of inorganic oxides. Preferred loadings of inorganic oxide are from 5% to 25% by weight of the catalyst. Typical inorganic oxide supports which can be used include aluminosilicates (such as clays), alumina, and silica, in which acidic sites are preferably exchanged by cations which do not impart strong acidity.
One preferred inorganic oxide support is attapulgite. Another preferred inorganic oxide support is "Ludox", which is a colloidal suspension of silica in water, stabilized with a small amount of alkali.
When an inorganic oxide is used as a carrier, there are two preferred methods in which the catalyst can be made, although other embodiments could be used.
In the first preferred embodiment, the zeolite is made, then the zeolite is ion exchanged with a barium solution, separated from the barium solution, dried and calcined, impregnated with platinum, calcined, and then mixed with the inorganic oxide and extruded through a die to form cylindrical pellets. Advantageous methods of separating the zeolite from the barium and platinum solutions are by a batch centrifuge or a pressed filter. This embodiment has the advantage that all the barium and platinum are incorporated on the zeolite and none are incorporated on the inorganic oxide. It has the disadvantage that the large-pore zeolite is of small size, which is hard to separate from the barium solution and the platinum solution.
In the second preferred embodiment, the large-pore zeolite is mixed with the inorganic oxide and extruded through the die to form cylindrical pellets, then these pellets are ion exchanged with a barium solution, separated from the barium solution, impregnated with platinum, separated from the platinum solution, and calcined. This embodiment has the advantage that the pellets are easy to separate from the barium and platinum solutions, but it has the disadvantage that barium and platinum may be also deposited on the inorganic oxide carrier which could catalyze undesirable reactions. Thus, the choice of which embodiment is used depends on the trade-off between catalyst selectivity and ease of separation of the catalyst from the barium and platinum solutions.
In the extrusion of large-pore zeolite, various extrusion aids and pore formers can be added. Examples of suitable extrusion aids are ethylene glycol and stearic acid. Examples of suitable pore formers are wood flour, cellulose and polyethylene fibers.
After the desired Group VIII metal or metals have been introduced, the catalyst is treated in air at about 260� C. and then reduced in hydrogen at temperatures of from 200� C. to 700� C., preferably 300� C. to 620� C.
At this stage the dehydrocyclization catalyst is ready for use in the dehydrocyclization process. In some cases however, for example when the metal or metals have been introduced by an ion exchange process, it is preferable to eliminate any residual acidity of the zeolite by treating the catalyst with an aqueous solution of a salt of a suitable alkali or alkaline earth element in order to neutralize any hydrogen ions formed during the reduction of metal ions by hydrogen.
In order to obtain optimum selectivity, temperature should be adjusted so that reaction rate is appreciable, but conversion is less than 80%, as excessive temperature and excess reaction can have an adverse affect on selectivity. Pressure should also be adjusted within a proper range. Too high a pressure will place a thermodynamic (equilibrium) limit on the desired reaction, especially for hexane aromatization.
Since the selectivity of this dehydrocyclization catalyst is high, the product stream from the dehydrocyclization is comprised predominantly of aromatics and paraffins, plus a small gaseous stream. The aromatics and paraffins are then separated from the gaseous stream using a high pressure separator or other conventional separation technology.
Most of the paraffins are extracted from the aromatics by passing the aromatics and paraffins through a molecular sieve which adsorbs the normal paraffins and some of the isoparaffins present, but not the aromatics. To cause such a separation, the molecular sieve should have an effective pore diameter of from 4.5 to 5.5 Angstroms. Examples of such molecular sieves are A, X, Y, offretite and ZSM, with cations properly used to tailor the size of zeolite opening to accommodate the desired separation.
The gaseous stream is then used to strip the paraffins from the molecular sieve. Then both the gaseous stream and the paraffins stripped from the molecular sieve are recycled to the dehydrocyclization zone. Since both the gaseous stream and the paraffins are recycled, there is no need to separate the paraffins from the gaseous stream.
Thus, by this process, a highly selective dehydrocyclization catalyst can be used without the octane penalty resulting from the presence of excess paraffins. Instead, these paraffins are converted to high octane aromatics.
Another major advantage of this process is that, since the paraffins are recycled, the severity of the dehydrocyclization reaction can be reduced and still achieve the same yields and octane numbers as when a higher severity dehydrocyclization is used without recycle. This means that the reaction can be operated at lower temperatures, which will result in longer run times.
While the present invention has been described with reference to specific embodiments, this application is intended to cover those various changes and substitutions which may be made by those skilled in the art without departing from the spirit and scope of the appended claims.
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Homemade Dairy Products to Be Legally Offered in Restaurants
Amendments to the regulation for the direct sale of homemade products would allow Bulgaria's restaurants to legally offer homemade dairy products to their clients.
The amendments allow the use of mobile dairies to produce white and yellow cheese of goat, sheep and buffalo milk directly at the pasture itself, reports the daily 24 Chasa. Such dairies are a novelty in Bulgaria, but are already widely used in Switzerland.
Now some restaurants offer homemade cheese, in violation of the food safety regulations, which strictly forbid the sale of such products from unlicensed small dairy producers.
Experts expect great interest from dairy producers in the mountain regions in Bulgaria, as those dairies can be driven straight to the pasture. The control will be carried out by the regional food safety departments.
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I'm conceding defeat. California is not in my future come January. I'd hoped to celebrate my 35th birthday there but it turns out paying my bills and affording to eat is more of a priority. Ho hum.
My cousins have lived in San Francisco at least 15 years now and each of those years I've expressed my hope to visit soon. I hardly ever get to see Clara and Emily because of the distance and I suppose I have romanticized this future visit as a result. Still, they're my only girl cousins on my mom's side of the family and I like the idea of us having time together, just us three.
I especially liked the idea of celebrating my birthday with them and a few friends who also live in San Francisco. I hoped 2015 would be the year I finally made it out to California for the first time
I'm putting my birthday dream back on a shelf.
This is my third post as the Pilgrim in Residence at A Sacred Journey. Head over to read the rest.
The hopes and fears of all my years met in the living room that night. A few years back I sat beside my two best friends and their husbands, reunited for the weekend. We watched a Nicholas Sparks movie but that wasn't the reason I wanted to cry.
I had prepared myself for inevitable disconnect. They moved on to be wives and mothers, while I have not. This difference does not divide us but it's there. I knew at some point I would feel sad our lives are not all on the same page. But that wasn't quite it either.
I was surrounded by the people who have known me best and longest but I felt alone, suddenly catapulted back to 16, self-hating and desperate to be accepted and loved by my peers. All I could see was them in their respective couplings and me, the consistent fifth wheel. Was this how it would be for the rest of our lives? Did they really want me there? Surely they only kept me around out of pity. The unexpected nature of those insecurities crept into my present and threw me.
After the movie ended, I quietly put my shoes on, said goodnight, and then fell apart as I walked to my car.
I'm sharing about how I've had to learn to be vulnerable, even with my best friends, at A Deeper Story today. Read the rest over there.
I owe a good deal to Preston Yancey. When I first happened upon his blog a few years back, I had little idea how much his words would come to mean to me.
Last spring I took his Sacramental Baking e-course. The combination of baking and spiritual disciplines was impossible to resist. We learned about sourdough starter and Lectio Divina, Rosemary Remembrance Bread and Praying in Color. By practicing different forms of prayer as we baked, the mundane became a way of centering ourselves.
Each Saturday we would put a new spiritual discipline into practice. The Visual Lectio Divina exercise allowed me to see I needed a therapy tune-up. I had proof on the page before me of how stuck and overwhelmed I felt. I still see my counselor at least once a month nearly a year and a half later. Though I no longer feel stuck, regular visits are an act of self-care.
Preston and I Skyped before the e-course ended as part of the class.
We talked about what I'd been learning through the e-course and how the different recipes had turned out. (Everything worked but the sourdough starter. Someday I will prevail!) And then I filled him in on how hard it had been to go to church for the last 6 or so months. Every week I'd psych myself up to go and every Sunday morning I'd be very sure about not going. I battled between the expectations I'd grown up with and the angst courtesy of accumulated church baggage.
Preston listened intently and then he asked me the question that changed everything.
"What if you took yourself off the hook and saw this as a sabbatical from church instead of beating yourself up every Sunday for not following through?"
Preston loves the Church so I didn't expect to hear this from him but it was just what I needed. My relationship with God grew stronger than ever, as I experienced Him through conversations with friends, song lyrics, books, and the great outdoors. My church sabbatical gave me the space to heal and to figure out what I was looking for. It lasted 5 months.
I don't think Preston was surprised when I landed in an Episcopal church. He made the transition from evangelical upbringing to Anglicanism himself. I often marvel at the way he discusses God and the Church and theology.
I tell you all this so you'll have a glimpse of how I felt when Tables in the Wilderness: A Memoir of God Found, Lost, and Found Again arrived in the mail this past June. I held the ARC in my hands and I cried. I am so proud of what my friend has accomplished and have no doubt it will speak to many.
This spiritual memoir resonated with me in ways big and small. Though our lives look very different, I related to the ways Preston looked to hear from and experience God. God went silent while Preston attended Baylor University and this loss ultimately teaches Preston what it is to hear.
This called to mind a dark night of the soul that happened in my early 20s, a season where I did not hear from God and had to grasp every bit of faith to believe He was still present in spite of His perceived absence. I wish I would have had this book then.
When I read Tables in the Wilderness, my summer of transitions was about to begin. In the months since, I have referred to starred and underlined passages on a regular basis. Passages that speak to my situation and remind me of God's presence in the midst of uncertainties.
Wisdom and grace permeate the pages of this beautifully written book.
We can find God and lose Him in many ways throughout our lives. We are worn down by life at times and this can make it that much harder to sense Godhead in the mundane. We may trust He is there, even if we no longer sense Him, but when the days turn into weeks turn into months, the longing turns into an ache. And then what?
"You don't always get to know when you set out on the journey. In fact, Abraham will wander in a circle before he is sent out to where he is eventually to be." -Preston Yancey, p. 205
Each time I've set out into the unknown, I have eventually landed where I was meant to be all along. It never looks like what I imagined and very rarely do I have anything to do with the result. I am changed by the process and more aware of my smallness and God's vast mystery.
I suppose this then is why I recommend Preston's memoir. Tables in the Wilderness serves as a guide through the unknown. Through Preston's story, we see ourselves. We remember our smallness and God's vast mystery.
We remember what it is to be lost and then found. We remember what it is to be welcomed at the Table.
Full disclosure: I received an advance copy of this book but all thoughts and opinions are my own. I was not paid to provide a positive review. Amazon affiliate links have been included. If you click through to Amazon, your purchase helps support this site.


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Amanda peterson - imdb, Amanda peterson was born on july 8, in greeley, colorado. with a natural beauty, powerful charm and a strong personality this talented and truly gifted actress began. Whatever happened to: amanda peterson - weht.net: the, Amanda peterson played opposite patrick dempsey in the 80' smash hit movie: can't buy me love as the beautiful cindy mancini. before that she was a child actor. We find stars! where are they now?: where is amanda peterson?, Now the "kr" stands for kasha-ryan. ryan is the photographer for the site. he has stated that he didn't even plan on taking those pictures of amanda.
Amanda peterson - biography - imdb, Amanda peterson was born on july 8, in greeley, colorado. with a natural beauty, powerful charm and a strong personality this talented and truly. Amanda peterson - listen to me (douglas day stewart, 1989, A group of college debaters learn about the world, friendships, love, dreams and family in this warm, endearing drama. copyright disclaimer under section. Statement analysis: scott peterson interview, Skeptical said after reading this post, i am thinking the training of all forensic psychiatrists should include statement analysis. march 6, 2013 at 8:51 am.
2013 emerging leaders | gopac | education and electing a, State senator bob peterson (oh) bob peterson is a farmer, business owner and former county official. peterson is an eighth generation farmer and raises corn, soybeans. Cleveland missing women news, photos and videos - abc news, Browse cleveland missing women latest news and updates, watch videos and view all photos and more. join the discussion and find more about cleveland missing women at. Amanda bearse - rotten tomatoes: movies | tv shows | movie, Amanda bearse celebrity profile - check out the latest amanda bearse photo gallery, biography, pics, pictures, interviews, news, forums and blogs at rotten tomatoes!.


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Louisiana tax extensions must be electronically filed
Updated On: Mar 26 2013 09:32:25 AM CDT
Louisiana taxpayers who require more time to file their 2012 income taxes must submit their extension requests electronically.
The Louisiana Department of Revenue implemented the requirement beginning with returns due in 2013. Filing extension requests must be submitted no later than the tax filing deadline.
2012 Louisiana Corporation Income and Franchise tax returns are due April 15, while 2012 Louisiana Individual Income tax returns are due May 15. Failure to file returns on time, or to submit an extension request by the filing deadline, will incur late-filing penalties.
A filing extension grants only additional time to file a return. It does not grant an extension of time to pay taxes due.
The department says paper requests will not be accepted.
Copyright 2013 by The Associated Press. All rights reserved. This material may not be published, broadcast, rewritten or redistributed.
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Modest Mouse — The Waydown Lyrics
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And if you asked them how, they couldn't say how they got there
And if you want them now you could just pull on the lever
And say, "i'm hung up on gravity."
You move your mouth and you start to talk
You close your eyes and then lose the thought
What's mine is mine and what's yours you probably got
And we all fall
On the waydown they saw a lot they don't remember
And if you asked them how, they'd say gravity's how they got there
And if you want them now you could just pull on the lever
And say, "i'm hung up on this decade."
They found some shelves on a school's sand house
They created pagers to collect all their calls
What's mine is mine and what's yours and we all always fall
And we fall


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Ghouls in BOO-dies Podcast: Halloween Movies, American Horror Story, and Kanye WestLions Gate
On this week's podghast, we start off getting into the Halloween spirit by discussing our Halloween costume hopes and fears. At what age is it appropriate to ask your parents to play the Castevets in a Rosemary's Baby group costume? Then it's time to recap our weeks in live music — Molly and Tess's evening of girl power with Katy Perry, Tegan and Sara, and Ellie Goulding; Emily's pilgrimage to the church of Yeezus. We also check back in with American Horror Story: Coven and compare notes on its success thus far, both as a TV show and as a season of American Horror Story. Finally, we wrap up with some Halloween movie recommendations for this evening. They were supposed to be scary movies, but if you're more in the documentary mood on this night of spooks, Molly has got you covered. Happy Halloween!
Listen to the podcast here: ESPN.com Podcenter.
Subscribe to the Grantland Pop Culture podcasts on iTunes, and check out our podcasts page.
Filed Under: American Horror Story, Grantland Network, Kanye West, Katy Perry
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Turkish governor apologizes to Chief Rabbi for saying synagogue would be turned into museum
Report: Number of ISIS recruits grows as group relaxes strict admission requirements
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Israel's just war and 'purity of arms'
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On the volcano's edge
Knowledge, power and abuse
Q&A with a Colombian lone soldier
European Press: Dividing line
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Book Review: Written from his heart
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Who is your God?
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Upscale dining in Neveh Tzedek
Obama: Helping terror go nuclear
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דְיוֹקְנְאוֹת תַרְבּוּת
מָה הַסִיפּוּר?
הָאַרְכִיוֹן שֶל רוֹמַן וִישְנִיָאק
Har Nof in flames
Genome of lowly centipede sequenced, adding a piece to puzzle of how life started on Earth
A creative twist on Italian in the heart of Tel Aviv
'Game of Thrones', 'Breaking Bad' director MacLaren to oversee Gal Gadot in 'Wonder Woman'
A First Look: Gal Gadot as Wonder Woman
Bennett announces Water City for Israeli technologies in Shougang, China
Tempête au sein de la coalition
Crise de confiance
Qui prendra la relève de Mahmoud Abbas ?
Arafat, Abbas, même combat ?
L'unité : notre seule planche de salut
Daniel Oren, maestro d'Israël, d'Italie et d'ailleurs !
Nos plus belles années ?
De Berlin à New York, 1920-1975
Le pot de chocolat liégeois par qui le scandale arrive
Le dernier kibboutz
La course aux étoiles
Les mordus du français
On n'invite pas un pyromane à éteindre un incendie
Tuer l'EI dans l'œuf
Le mont du Temple et la guerre sainte de l'islam
Les attentats du lundi 10 novembre vus par la presse française
L'Europe, nouvelle alliée d'Abbas ?
Ces enseignants-éclaireurs
Christian priest speaks out strongly in favor of Jewish state law
Hispanic Evangelicals among Israel's greatest supporters
Christians United for Israel Chairman John Hagee says Obama is anti-Semitic
Temple Mount: Common ground between Jews and Christians
Pope Francis condemns Palestinian violence
KKL Belgium Donates Portable Bomb Shelter to Kiryat Gat
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11.26.2014 | 4 Kislev, 5775
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Diplomacy & Politics
04/30/2013 16:39
Pope and Peres 370.
(photo credit:Courtesy Spokesman of the President's Residence)
Pope Francis accepted a personal invitation to visit Israel during his meeting
with President Shimon Peres – one of the first world leaders to be granted an
audience – in the Vatican's Apostolic Palace on Tuesday."The citizens of
Israel see in you a leader of peace and good will. The sooner you visit the
better, as in these days a new opportunity is being created for peace, and your
arrival could contribute significantly to increasing the trust and belief in
peace," said Peres.The pope accepted the invitation "with willingness
and joy," a Vatican spokesman said, but there was no indication when a trip
would be made.Peres was also granted an audience with the previous pope,
Benedict XVI, who like his predecessor John Paul II, visited Israel and in his
case, planted an olive tree in the presidential garden in 2009.The
president told the pope that his leadership created "a new spirit of hope for
peace" at a time when religious leaders in the Middle East were advocating
terror and bloodshed."We all have an obligation to stand up and say, in
a loud and clear voice, that the Lord did not give anyone the authority to
murder and carry out bloodshed," Peres said.The pope shared his plan for
an international peace convocation, with spiritual leaders of many faiths, which
will call for an end to violence, "in a loud, clear voice.""I turn to
you and ask that within your sermons in front of millions of believers in the
world you include the hope for peace in the Middle East and the whole world,"
Peres said.The pope had already made an appeal for peace between
Israelis and Palestinians in his Easter address last month.He also spoke
out strongly on the need to combat anti-Semitism.A Vatican statement
said the two discussed prospects for a resumption of negotiations for a solution
that would respect "the legitimate aspirations of the two peoples, thus
decisively contributing to the peace and stability of the region."They
agreed on the need for a political solution to the civil war in neighboring
Syria. Peres also updated the pope on recent developments in the Middle East,
saying the region's greatest problems are hunger and poverty, political
instability and unemployment.At the conclusion of the meeting, Peres
presented the pope with a specially bound Bible with a passage from the Book of
Kings on the cover: "So that you may prosper in all you do and wherever you
go."Prior to leaving for Rome on Monday, Peres said one of the purposes
of his meeting with the pontiff was to strengthen the existing good relations
between Israel and the Vatican – which he said, has an important role to play in
the stability of the Middle East in endeavors towards peace.On the day
of Peres's departure, Palestinian Christians from Beit Jala, near Bethlehem,
published an open letter entreating the pope to intercede on their behalf and
prevent the construction of a separation wall which would isolate them from
Jerusalem.Peres also met with Cardinal Tarcisio Bertone, the prime
minister of the Holy See, and with Italy's Prime Minister Enrico Lette. The
president wished the new premier success and drew his attention to the dangers
posed by a nuclear Iran and Syria's chemical weapons.Lette told Peres
that good relations between Israel and Italy were important to him and that he
would invite Israel's government ministers to a joint meeting in Rome later in
the year.Reuters contributed to this report.
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text:
WBZ TV & Radio political analyst
When is the best time to hit the road for the holiday? Advice from the state's top transportation official at 6 on WBZ news
RT @billjanovitz: Congrats to my own Harvard beating Yale today. When I say my own, I mean the school next to which I drank many pints during and after UMass.
In WBZ interview, Lt. Gov-elect Karyn Polito says state budget deficit is "probably closing in on a billion dollars." Full intvw Sun. 8:30am
RT @LaurenWBZ: DC reporter @TishaOnTV on how tough it can be to get PUBLIC records from the govt. Her 6 year ordeal! #FOIA nbcwashington.com/investigations…"
RT @bostonjonas: @kelleratlarge Or only at certain times, certain issues. Like alternate side parking in NYC.
AKA failure to lead MT @bostonjonas: On #education policy, Gov. Patrick has had a split personality.#mapoli commonwealthmagazine.org/Voices/Back-St…
RT @PetesWire: BREAKING: From @KenMacWBZ at Walden Pond, #Concord. Woman waded into water, ended up in distress & a man nearby jumped in to…
Jimmy Ruffin of "What Becomes of the Brokenhearted" fame has died. What a voice. rollingstone.com/music/news/jim…
Has your trip to work been plagued by commuter rail delays lately? The man in charge explains why at 6 on WBZ News
RT @PolitiFact: Obama: #Gruber was "some adviser who never worked on our staff." Mostly False. bit.ly/11ikj0c pic.twitter.com/3gcivCEgxV


text:
World Bulletin / News Desk
Israeli supermarkets have been boycotting Turkish products in protest against Turkey's support for the Palestinians of the Gaza Strip, amid Israeli deadly bombardment of civilian-packed areas.
Rami Levi and Blue Square and emptied their shelves of Turkish products, and said that they will not renew their stock of Israeli brand names that base their production in Turkey.
Israel's Channel 10 reported that the boycotts would lead to a loss of $93 million from the markets.
Brand For You CEO Rafi Sheffer also said that his firm has not yet decided on whether or not to boycott Turkish products.
Super Sol, one of Israel's biggest supermarkets, is also expected to join the boycott, despite Turkish products costing much less than other brands.
On Sunday, Turkey's Prime Minister Recep Tayyip Erdogan fiercely criticized Israel's offensive in Gaza, comparing it to atrocities carried out by Adolf Hitler during World War Two.
Erdogan said: "Israelis curse and swear about Hitler day and night for the Holocaust, but now the terrorist state of Israel has surpassed Hitler with its atrocities in Gaza."
"Turkey will not remain silent on the ongoing cruelty because a great state does not remain silent and unmoved, but mediates and strives for peace," he warned.
Israeli Prime Minister Benjamin Netanyahu meanwhile said the remarks by his Turkish counterpart Recep Tayyip Erdogan were "anti-Semitic," Israeli media reported.
Israeli daily The Jerusalem Post quoted diplomatic officials as saying that Netanyahu spoke to U.S. Secretary of State John Kerry overnight on Sunday about the ongoing military operation against the Gaza Strip, and said that "Erdogan's anti-Semitic comments profaned the memory of the Holocaust."
However, Netanyahu's office did not officially confirm the remarks, which were also reported by Israeli daily Haaretz.
"I cannot officially confirm what the two leaders spoke on the phone," Netanyahu's spokesman Mark Regev told Anadolu Agency on Sunday.
Since July 7, Israel has been pounding the besieged Gaza Strip with air and naval bombardments with the stated aim of halting rocket attacks.
At least At least 509 Palestinians have been killed and more than 3000 injured since the Israeli assault began.
Israel's military operation, dubbed operation "Protective Edge," is the self-proclaimed Jewish state's third major offensive against Gaza in the last six years.
This is the third time the Israeli police stop Hamdallah's convoy since he assumed office in June
Tunisians head to cast their ballots to elect a new president in a vote billed as the first free presidential election in the country that sparked the Arab Spring uprisings three years ago.
Diplomats said a framework accord was still possible, but that weeks or months would then be needed to agree on the all-important details of how it would be implemented.
Thailand's lese-majeste law is the world's harshest and makes it a crime to defame, insult or threaten the king, queen or heir to the throne or regent.
Palestinian villages in the West Bank, especially those near Israeli settlements, have recently been subject to repeated assaults by Jewish settlers
Authorities warn historic snow levels are ready to melt in upstate New York as temperatures rise
Adverse weather conditions are hampering efforts to rescue around 300 migrants stranded on a vessel that broke down near Northern Cyprus' coast
The U.S. planned to admit close to 7,000 refugees from Turkey in the coming year, including Iraqis, Iranians, and a growing number of Syrians, the statement said
Sarkozy pressed on with increasingly Eurosceptic proposals rare among the country's mainstream politicians.
A senior ally of Merkel has warned the foreign minister and his fellow Social Democrats against pursuing a more friendly approach
Remi Fraisse, 21, was killed last month by a so-called "offensive grenade" during a standoff between police and opponents of a dam project in wetlands near Toulouse
Netanyahu's office said following discussions last week, the Israeli Prime Minister was expected to propose the bill against those who commit "terrorist" attacks with national ramifications
Armenia announced that they launched operation in order to transfer dead pilots' bodies and collect helicopter wreckage.
The militants attacked the fishing town of Doron Baga near the Chad borders
Around 800 far-right extremists protested the construction of a refugee hostel by shouting racist slogans.
Mohamed al-Maghrabi said the civilian protesters seized the ship as soon as it had anchored at the port on Friday in protest against Qatar's policies


text:
The 100km Tribute organizing team has announced that award winning documentarian Peter Musurlian will be producing a short movie about the walkers, bicyclists, and motorcycle riders who will be honoring the martyrs of the Armenian Genocide on Thanksgiving weekend through a 100km tribute.
Home » CommunityYou are browsing entries filed in "Community"
Award Winner to Document 100km Tribute
Pilibos Students Become the Teachers
The old adage of see one, do one, teach one rings true at Rose and Alex Pilibos Armenian School. During Armenian Cultural month, Pilibos students have been busy with many activities and learning opportunities where they could further explore what it means to be an Armenian living in the diaspora, to embrace their heritage, and celebrate their identity.
100 Km Tribute to Benefit Book Series on Armenian Architecture
Cyclists, Hye Riders, AHS Join 100 Km Tribute
Zareh & Lucik Misserlian donate $250,000 to KZV School in San Francisco
Burbank Homenetmen Participates in South American Navasartian Games
East San Fernando Valley ANCA to Host Community Reception
Encino's Holy Martyrs Church Celebrates 51 Years of Service
New Honorary Consul General to Fresno Appointed
Armenian-American community members and elected officials came together on October 20 for a ceremony marking the opening of the office of the first Honorary Consul General to Armenia to Frenso. On October 15, Armenia's Foreign Minister Edward Nalbandian appointed Berj Apkarian as the Honorary Consul.


text:
Arizona Wildcats
Arizona football linebacker Scooby Wright emerges onto radar
TUCSON, Ariz. -- Three months ago, the name Scooby Wright meant nothing to Arizona football fans. Flash-forward to the second week of the season, and the Wildcats' linebacker is being swarmed by the media.
Bring up the name Scooby around any of the Arizona football players and their faces light up. This isn't about their favorite childhood cartoon -- they're animated because of how hard their true freshman linebacker plays. His relentless motor has earned him a starting spot at linebacker and could someday make him one of the best in the conference.
"He'll be an all-Pac-12 linebacker someday," senior linebacker Jake Fischer said after the Wildcats' 35-0 victory over NAU last Friday.
Wright finished his first college game with six tackles, tied for second-most on the team, and has only continued to gain praise from his teammates and coaches in the days following the victory.
Wright's birth name is Phillip Wright III, while "Scooby" is a nickname his dad gave him when he was young.
Despite his attention-grabbing name, the Wildcats' starting outside linebacker wasn't a top Arizona recruit from the 2013 class. Rivals.com only gave the 6-foot-1,230-pound Wright a two-star ranking, putting him as one of the lower-ranked recruits for the class.
California was the only other Pac-12 school that showed any interest at all in the Santa Rosa, Calif., native.
Scouts were impressed by his athleticism, strength and instincts but were worried that he couldn't play in space and expected him to redshirt before making any kind of impact at the Division I level.
But what the scouts didn't see was Wright's drive and effort.
"Man, Scooby just gives you 110 percent," junior safety Tra'Mayne Bondurant said. "He never stops moving. He's constantly hustling, chasing down the ball and making plays."
Coming into fall camp, Wright didn't let his unknown status stop him from giving his full effort. His father, a coach, taught Wright at an early age that if he worked hard, in time his exertion would help him overcome any failures.
"My dad has always told me if you're going to mess up, do it 110 percent," Wright said.
But this time, Wright profited quickly.
During Arizona's first defensive series, Wright said he felt like he was flying around a little too fast and was out of control. But he said that after a break on the sideline, he remembered that this was the same sport he excelled at in high school, and calmed down.
Relaxing might have helped Wright to focus, but his drive is who he is as a player. Head coach Rich Rodriguez has said he's amazed at his freshman's natural instincts and believes he could put Wright at any position on the field and watch him succeed.
However, Wright said he's not interested in playing other positions. Now that he is finally starting to grasp that he is a Division I starting linebacker as a freshman, he wants to take it slow -- but that doesn't mean he'll play slow.
"Giving it my all is just in my nature," Wright said. "I don't see any reason not to go out and give my 110 percent -- it's got me pretty far."
This story was courtesy of the Arizona Daily Wildcat.
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Relevant offers
Parts of rural New Zealand are struggling and are at risk of becoming migrant "ghettos" while the nation's two biggest cities roar ahead, an economist warns.
Shamubeel Eaqub, chief economist at New Zealand Institute of Economic Research (NZIER), this week said growing inequality between regions was the "elephant in the room" being ignored by policymakers.
The inequality spanned geographical, race and education lines, creating the risk of even affluent farming regions like Southland producing European-style migrant "ghettos".
Pay and job prospects were fragile in some of these pastoral strongholds.
In the deep south, migrants bridging gaps in dairying were at risk of becoming socially and economically marginalised, Eaqub said.
Reserve Bank Governor Graeme Wheeler last week raised the official cash rate (OCR) 25 basis points to 3.25 per cent, the third increase since March, when he started lifting the rate from its low of 2.5 per cent.
Eaqub said New Zealand's growth in the first half of this year was being driven mostly by Auckland and Canterbury, and many other areas were stagnating or going backwards.
Raising the OCR was a "huge mistake" that would punish the provinces, many of which were struggling, he said.
Regions like Northland and the East Coast had relatively high unemployment, while the growth of wages and employment was "flat or falling" in other rural regions.
ANZ chief economist Cameron Bagrie said many regional centres were doing exceptionally well, to the extent that mid-sized cities like Dunedin were being propped up by outlying areas.
He suggested Eaqub was "grandstanding" on the economics, given that he only recently suggested the provinces were being hurt by speculative investment in Auckland housing.
Eaqub was now blaming structural weakness linked to OCR policy, Bagrie said.
"You can't have it both ways."
It was wrong for NZIER's expert to claim New Zealand was a "two or three-shot economy" dependent on Auckland housing, the Christchurch rebuild and strong dairy commodity prices, Bagrie said.
In the South Island, places like Queenstown and Wanaka had overtaken centres like Rotorua and Taupo as wealth generators on the back of tourism, farming and related industries.
It was a similar story in Canterbury, where parts of Mid and South Canterbury were "absolutely flying".
"Now, that's not Auckland overflow stuff. That's a result of the irrigation development we're seeing on the Canterbury Plains."
In fact, rural pay rises had encouraged people to quit some of our biggest cities.
Between 2006-2013, Auckland had a slight net outflow to other parts of the country, Bagrie said.
Outside the obvious irrigation zones, areas like Marlborough, which had just had a record grape harvest, were improving, he said.
The "good vibe" Bagrie felt in Blenheim this week was significantly better than during the Global Financial Crisis (GFC), when wine prices slumped and land values crashed in sympathy.
It was true that pockets of rural New Zealand, including Northland and the East Coast, were struggling with "deep-rooted" economic weakness, he said.
Dunedin was "really struggling", and looking to spinoff from Central Otago for its prosperity.
Nationally, rural incomes were generally rising, as employers were forced to pay more for well-qualified staff.
Agricultural wages had jumped massively in the past decade, to a point where good university graduates could expect to start on the same salary as a new lawyer or accountant.
"You go call a farmer and ask what the starting salary is. She's a long way above minimum wage," Bagrie said.
"There's all this hocus-pocus out there about agricultural staff not getting paid.
"The real problem is getting the bloody staff in there."
The urgent need for overseas migrants to fill rural jobs was a commentary on New Zealanders' attitudes to agricultural work, not a sign that the regions were doing it tough, he said.
Bagrie spent his university holidays picking fruit in Central Otago but understood this long-running supply of Kiwi workers dried up during the GFC, forcing employers to look overseas for staff.
It was only now that the local labour force was returning to that seasonal work in good numbers.
Eaqub had earlier argued that structural economic problems were making it harder for provincial New Zealand to keep pace with cities.
House prices in Auckland had risen 20 per cent in real terms since 2007, with prices up 13 per cent in Canterbury and seven per cent in Wellington.
However, prices in the rest of the country fell 21 per cent in real terms during the same period.
While Auckland had had the fastest jobs growth over that time at 4 per cent, some areas, such as Whanganui, had more than 10 per cent fewer jobs now than in 2007.
In Kawerau, the country's poorest location, the median income was about $25,000 a household. In Auckland's eastern suburbs, the median income was $120,000. Eaqub blamed the gap between haves and have-nots on structural rather than cyclical factors.
There were demographic and economic factors in the regions to consider, such as the ageing population and the loss of manufacturing jobs. Manufacturing had been in decline since 1966, and there were fewer manufacturing jobs than in 1946 in absolute terms.
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text: Justin Bieber vs. Slipknot By Marcie Pink March 24, 2011 12:52 PM Share on Facebook Share on Twitter - Psychosocial Baby – I bet you were surprised! Pretty good video, 'ey? Filed Under: justin beiber, slipknot Category: Videos Share on Facebook Share on Twitter More Leave a comment Send to a friend! Print this page Pin it! Reddit This! Share on Tumblr! More from Classic Rock 96.1 Hottest Natalie Dormer GIFs 45 Years Ago: John Lennon Returns His MBE to the Queen 'Jurassic Park 4' Trailer: Welcome to Jurassic World! Madison Welch — Babe of the Day Best of the Web


text:
CLAP 3 - Pictograms
Put down your hog dog burrito, it time to learn the Chinese.4.56 / 5.00 7,324 Views
Hoenn Confirmed
Hoenn Intro Animated4.27 / 5.00 5,749 Views
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i like how the ending is the title!
Great work
The derp faces were hilarious and the sound effects worked perfectly.
The movement of the main demon's face was a bit choppy though. Maybe it just moved too quick for me to see, but it looked like it just skipped from one face to another with no animation.
That wasn't so funny. I admit I smiled a little but still...
that was kinda short but funny as hell! :D
thanks i loled!


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