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text: United States Patent: 4072475 ( 1 of 1 ) United States Patent 4,072,475 Schlosberg , et al. February 7, 1978 Method for improving gasification process rates and yields by means of electrophilic aromatic substitution pretreatment of coal Abstract Coal is electrophilically aromatically substituted (i.e., alkylated or acylated) in the presence of an alkylating or acylating agent with or without a catalyst under mild conditions to give a treated coal product. This treated coal product may then be solvent extracted to give an extract and an upgraded coal residue, with this residue being subjected to a gasification process procedure or the treated coal product may be subjected to gasification process procedures without any prior extraction being performed. By means of either technique, a material is prepared for which the rate of gasification and the yield of desired product upon gasification is dramatically increased when compared with nonelectrophilically aromatically substituted material (i.e., raw coal). An improved gasification process is disclosed comprising the steps of electrophilically aromatically substituting coal and subjecting such pretreated coal, either extracted or unextracted to gasification process techniques. Inventors: Schlosberg; Richard H. (New Providence, NJ), Wright; Franklin J. (Plainfield, NJ), Hartgerink; Ronald L. (Edison, NJ) Assignee: Exxon Research & Engineering Co. (Linden, NJ) Appl. No.: 05/720,144 Filed: September 3, 1976 Current U.S. Class: 48/210 ; 208/403; 208/435; 44/620; 44/905; 48/202 Current International Class: C10J 3/00 (20060101); C10L 9/02 (20060101); C10B 57/00 (20060101); C10L 9/00 (20060101); C10B 57/08 (20060101); C10J 003/00 () Field of Search: 48/210,202,206,197R,214A 44/1R 208/8 References Cited [Referenced By] U.S. Patent Documents 3888043 June 1975 Child et al. 3920418 November 1975 Rice 3940190 February 1976 Hayes 3970541 July 1976 Williams et al. 3996026 December 1976 Cole Primary Examiner: Lindsay, Jr.; Robert L. Assistant Examiner: Yeung; George C. Attorney, Agent or Firm: Allocca; Joseph J. Claims What is claimed is: 1. A process for the gasification of coal which comprises: (1) treating the coal with a reagent selected from the group consisting of alkylating agents and acylating agents and thereby introducing into the coal a radical selected from the group consisting of aliphatic hydrocarbon radicals and acyl radicals respectively to yield a treated coal; (2) subjecting the treated coal to gasification conditions. 2. The process of claim 1 wherein the gasification reaction practiced on the treated coal comprises using materials selected from the group consisting of CO.sub.2, H.sub.2 O, steam, H.sub.2, air, O.sub.2, CO, H.sub.2 S, SO.sub.2, NH.sub.3 and mixtures thereof at pressures ranging from atmospheric to 2000 psi and at temperatures ranging from about 300.degree. to about 1000.degree. C. 3. The process of claim 1 wherein the reagent is an alkylating agent and is selected from the group consisting of olefins, paraffins, organo halides, wherein the organo group is an alkyl, cycloalkyl, arylcycloalkyl or aryl alkyl radical, the halogen is selected from the group consisting of fluorine, chlorine, bromine and iodine, and organo hydroxyls wherein the organo group is as defined previously. 4. The process of claim 1 wherein the reagent is an acylating agent and is selected from the group consisting of CO, haloacyls and compounds having the formula ##STR9## wherein R is an alkyl, cycloalkyl, arylcycloalkyl or aryl alkyl radical and X is a halogen or anhydride derivative. 5. The process of claim 1 wherein the treating step of step (1) practiced on the coal further comprises the use of a catalyst. 6. The process of claim 4 wherein the acylation step is practiced on coal using carbon monoxide as the acylating agent in the presence of a hydrogen halide catalyst. 7. The process of claim 1 wherein step (1) comprises treating the coal under appropriate conditions to an alkylation reagent selected from the group consisting of organo halides and organo hydroxyls, wherein the organo group is selected from the group consisting of C.sub.2 -C.sub.20 alkyl, cycloalkyl, arylcycloalkyl and aryl alkyl radical and halogen is selected from the group consisting of chlorine and bromine in the presence of a catalyst. 8. The process of claim 5 wherein the catalyst is selected from the group consisting of Lewis acids. 9. The process of claim 8 wherein the Lewis acid catalyst is selected from the group consisting of aluminum chloride, aluminum bromide, zinc chloride, ferric chloride, boron trifluoride. 10. The process of claim 1 wherein step (1) practiced on the coal comprises: (1) treating the coal with a reagent selected from the group consisting of alkylating agents and acylating agents at a pressure and for a time sufficient to cause the coal to react with the reagent; (2) working the treated coal to remove substantially all of the unreacted reagents; (3) repeating steps (1) and (2). 11. The process of claim 1 step (1) wherein the coal being treated is a higher rank coal. 12. The process of claim 11 wherein the coal is selected from the group consisting of bituminous and anthracite. 13. The process of claim 11 wherein the coal is selected from the group consisting of Illinois #6 and Kentucky HVB coals. 14. The process of claim 1 wherein the alkylating agent is a C.sub.2 -C.sub.8 alkyl halide. 15. The process of claim 1 wherein the alkylating agent is a C.sub.2 -C.sub.8 olefin. 16. The process of claim 1 wherein the acylating agent is a C.sub.2 -C.sub.20 acyl halide. 17. The process of claim 1 further characterized by the step of extracting the treated coal of step (1) with a solvent before subjecting it to gasification conditions. 18. The process of claim 17 wherein the solvent of the extraction step is selected from the group consisting of benzene, toluene, xylene, paraffins, alcohols, ethers, hydrocarbon halides, amines, phenols and ketones. 19. The process of claim 1 further characterized by the step of slowly pyrolyzing the treated coal of step 1 resulting in a volatile product make and a char make and subjecting the char make to the gasification conditions of step (2). 20. The process of claim 19 wherein the slow pyrolysis step comprises heating the treated coal at a rate of from 0.1.degree. C/min to 10.degree. C/min to a temperature of from 200.degree. to 1200.degree. C in a flowing inert gas atmosphere. 21. The process of claim 3 wherein the alkylation step practiced on the coal further comprises the use of a catalyst. 22. The process of claim 4 wherein the acylation step practiced on the coal further comprises the use of a catalyst. 23. The process of claim 21 wherein the catalyst is selected from the group consisting of Lewis acids. 24. The process of claim 23 wherein the Lewis acid catalyst is selected from the group consisting of aluminum chloride, aluminum bromide, zinc chloride, ferris chloride, and boron trifluoride. 25. The process of claim 22 wherein the catalyst is a hydrogen halide. 26. The process of claim 7 wherein the catalyst is selected from the group consisting of Lewis acids. Description Much of the world's needs for liquid fuels are and will continue to be supplied by crude oil production, but this supply cannot meet the added growth indefinitely. In the last 20 years of this century, the needs for clean automotive, aviation, residential, and commercial liquid fuels will exceed the availability of such fuels from conventional sources. Large deposits of coal are available to help fill the gap and could be converted to clean liquids as commercial technology emerges. It appears that one of the preferred ways to use coal in industry and electric power generation while meeting acceptable environmental standards will be coal conversion to clean liquid fuels. Thus, coal conversion processes will be important factors in meeting the world's energy needs for the remainder of this century. COMPOSITION OF COAL Chemically, coal has a much lower ratio of hydrogen to carbon than natural petroleum and contains larger amounts of impurities as illustrated in Table I. TABLE I ______________________________________ Elemental Composition of Some Coals and Hydrocarbons (1) Wt % of Element in Fuel Form C H O S N Other ______________________________________ Methane (CH.sub.4) Gas 75 25 -- -- -- -- Naphtha Liq. 85 15 -- -- -- -- Fuel Oil Liq. 86 12 0.5 0.4 0.5 0.6 Bituminous Coal Solid 73 5 9.0 3.0 1.5 8.5 (Dry) Subbit. Coal (Dry) Solid 71 5 16.0 0.5 1.5 6.0 Lignite (Dry) Solid 64 4.6 18.0 0.5 1.5 11.4 ______________________________________ (1) Federal Power Commission, "Synthetic Gas-Coal", prepared by the Synthetic Gas-Coal Task Force for the Supply-Technical Advisory Committee of the National Gas Survey, Issued April, 1973. While the structure of coal is not completely understood, over 70% of the carbon atoms are thought to be in aromatic rings. It is generally believed that much of the carbon is present in condensed ring structures such as pyrene or phenanthrene. Numerous authors have proposed molecular structures for coals, exemplified by Given's picture of a typical (Vitrain of 82% C) bituminous-type coal. The key features of the Given model include a 9,10-dihydrophenanthrene prototype, a minimum of alkyl side chains, a non-planar structure, and a value of 70% for the aromatic carbons versus 30% aliphatic carbons. The empirical formula for the Given model is C.sub.102 H.sub.77 O.sub.10 N.sub.2. It is possible, however, to state that coal contains aromatic rings which are highly substituted (i.e., fused to other aromatics, fused to hydroaromatics, or attached to alkyl, ether, hydroxyl, etc. groups.) Furthermore, it is believed that analogously to proteins, coal exhibits secondary structural characteristics. Thus there seem to be hydrogen bonds, interaromatic ring bonds, etc., which generate the three dimensional structure of coal. PRIOR ART There are three general schemes used to derive liquid and gaseous products from coal. The simplest approach is pyrolysis. Heat is used to drive off or "distill" the volatile portions of the coal without adding hydrogen. This results in substantial quantities of by-product char. A second scheme involves both heat and the addition of H under pressure. This is the approach usually described as coal liquefaction. Volatile matter is driven off and portions of the coal molecule are broken down. Hydrogen is added by chemical reaction with some of the coal to form hydrocarbons with molecular weights lower than the original coal moieties. A third scheme is conversion of the coal to gaseous products, e.g. hydrogen and carbon oxides, through very high temperature processing. Subsequently, this gas mixture may be reacted catalytically to form hydrocarbons. This approach incorporates coal gasification with steam and oxygen followed by the Fischer-Tropsch synthesis reaction or other analogous processes to produce the liquid or gaseous (e.g. methane, ethane) hydrocarbons. Gasification involves reacting coal with steam or another convenient small molecule such as CO.sub.2, etc., at 1500.degree. F. and above, (catalytically at 1200.degree. F) and at pressures of up to 1500 psi. This makes a mixture of methane, hydrogen, and carbon oxides. In upgrading steps, this mixture is converted to hydrogen or to synthetic natural gas (SNG). The upgrading steps are based on commercial technology and are essentially the same in the various processes. Differences in approach mainly concern the gasification reactor configuration and method of heat input. Some processes can make either high Btu SNG or 150-500 Btu/SCF gas which is preferred economically in some cases. Another option involves gasification by partial oxidation, i.e., reaction of coal with oxygen (or air) instead of with steam. The Koppers-Totzek partial oxidation process is developed and commercially available. Raw gas upgrading to high Btu gas is common to all gasification processes. The raw gas (CO + H.sub.2) produced in the gasification reactions must thus undergo shift (CO + H.sub.2 O .fwdarw. CO.sub.2 + H.sub.2), acid gas removal (CO.sub.2 and H.sub.2 S) and methanation (CO + 3H.sub.2 .fwdarw. CH.sub.4 + H.sub.2 O) to produce high-Btu or pipeline quality gas. Moreover, the same basic chemical reactions are involved in gasification reactions, to wit: ##STR1## Some methane is therefore formed directly from coal and some by carbon-hydrogen interaction. Carbon also reacts with steam and some of the coal is burned to provide heat for the gasification. BRIEF DESCRIPTION OF THE DRAWINGS FIG. I presents the reactivity of alkylated coal as compared to the reactivity of unalkylated coal based on the rate of reaction with CO.sub.2 at 850.degree. C. FIG. II presents the instantaneous rate in mg/g/min against % burn off of alkylated Wyodak coal subjected to CO.sub.2 at 850.degree. C. PRESENT INVENTION It is an object of the instant invention to produce an upgraded coal for use in coal processes which features greater product yields with reduced waste generation. It is another object of the instant invention to demonstrate a multistep process for upgrading coal and utilizing the coal, thereby obtaining increased yields of useful products. The instant invention teaches a multistep process for the production of synthetic fuels. Briefly, the process involves the alkylation or acylation of coal to produce an upgraded product which product in its turn is subjected to coal gasification process conditions to yield desirable synthetic fuel precursors and products. It has been unexpectedly discovered that pretreatment of coal via alkylation or acylation yields a product which, when subjected to coal gasification conditions displays enhanced activity as compared to raw coal. It has also been surprisingly discovered that using alkylated or acylated coal as starting material in coal gasification reactions permits such processes to give equivalent or even higher yields of desired product vis-a-vis raw coal; or similar yields at less severe reaction conditions. It has also been surprisingly discovered that alkylated or acylated higher rank coals show superior gasification product yields than do alkylated or acylated low rank (i.e. sub-bituminous) coals. Further, the rate of gasification of the upgraded material is markedly improved in addition to exhibiting superior weight loss characteristics upon slow pyrolysis (i.e. greatly enhanced product yield upon slow pyrolysis). The coals which may be utilized in electrophilic aromatic substitution reaction (i.e. alkylation or acylation) to give a product with enhanced gasification characteristics are higher rank coals, i.e. anthracite, and bituminous as exemplified by Illinois #6 and Kentucky HVB coals. This invention relates to a method whereby coal is pretreated via electrophilic aromatic substitution reactions to yield an upgraded product which product is then utilized is gasification process procedures and is marked by improved yield and rate characteristics in such procedures. The upgraded product may be used either extracted with a solvent before gasification or used directly in such gasification processes without extraction. Two typical electrophilic aromatic substitution reactions are alkylation and acylation. Imposition of big alkyl or acyl groups into the coal structure presumably disrupts the secondary structural features, e.g. hydrogen bonds, interaromatic ring bonds, etc., of coal. Literature on coal pretreatment and especially alkylation is relatively meager. What work has been done has generally been conducted with the overriding purpose of increasing the solubility of the coal in various solvents so as to facilitate the gathering of analytical data which can lead to a better understanding of coal structure and chemical makeup. Such work was conducted by Frank Meyer and presented in his doctoral thesis "Reaktionen von Steinkohlen und Modellsubstanzen im System Fluorwasserstoff-Bortrifluorid" at the University of Munich, 1969. In the course of his study, Meyer conducted what he characterized as depolymerization of coals by means of Friedel-Crafts catalysis, the classic method used for alkylation. Meyer demonstrated how, by Friedel-Crafts alkylation, the solubility of coals in various solvents can be increased. The acid catalyst system he employed was HF-BF.sub.3 while the alkylating agents were generally alkenes containing two to twenty carbon atoms. Solubility in pyridine, chloroform and benzene exhibited a tendency to increase with increasing size of the alkyl group. Analysis conducted to determine the hydrogen to carbon ratio in the alkylated coal material disclosed that the hydrogen/carbon (H/C) ratio went from 0.674 with untreated coal to 0.828 for C.sub.12 1-dodecene alkylated coal to 1.15 for 1-eicosene alkylated coal. After extraction, hard coal, which normally had a pyridine soluble constituent having a H/C ratio of 0.622 demonstrated that such pyridine soluble constituent rose to an H/C of 0.937 when the coal was alkylated with 1-dodecene and rose to 1.25 when 1-eicosene was used. However, analysis of the residue remaining after extraction of the alkylated material demonstrated a marked reduction in the H/C ratio. That portion of untreated coal which is insoluble in pyridine had a H/C (atomic) of 0.560. When 1-dodecene was used the H/C ratio went to 0.555. Resort to 1-eicosene yielded a pyridine insoluble residue which had H/C of 0.555. The work of Meyer therefore tends to demonstrate that alkylation of coal yields a product which exhibits improved solubility in a variety of solvents, which has a pyridine soluble constituent having markedly improved H/C ratio but which produces a residue decidedly inferior in H to C ratio which would lead one to the conclusion that coal alkylation followed by extraction results in the production of a degraded residue possessing inferior characteristics when compared to normal raw coal. Werner Hodek and George Kolling in Fuel, 1973, Vol. 52, "Increase in Extractability of Bituminous Coals Caused by Friedel-Crafts Acylation" examined the effect of acylation on coal chemistry. Again, these experiments were undertaken with an eye toward clarifying and expanding current understanding of the structure of coal. Hodek and Kolling indicate that other researchers reacted coal with BF.sub.3 and phenol (Heredy and Neuworth) so as to improve extractability in various solvents. Hodek and Kolling, in the course of their work determined the extractability of coals in pyridine both before and after treatment with acylating agents in the presence of aluminum chloride. They used, as acylating agents, the chlorides of acetic acid, propionic acid, butyric acid, isoovaleric acid, caproic acid, sebacic acid (C.sub.7), caprylic acid (C.sub.8), capric acid (C.sub.10) stearic acid (C.sub.12), palmitic acid (C.sub.16) and determined that acylation increased the extractability in pyridine of all but low rank coals. THE ELECTROPHILIC AROMATIC SUBSTITUTION STEP OF THE INVENTION Alkylation and acylation can be broadly characterized as electrophilic substitution reactions. More particularly, the alkylation or acylation of coal can be characterized as an electrophilic substitution wherein the aromatic carbon-hydrogen bond, e.g., aromatic C--H of the coal molecule, is the site of primary attack by the alkylating or acylating agent. Alkylation and acylation are well known and well documented reactions. The use of coal as the material to be alkylated or acylated does not change the chemistry of the reaction or the manner in which the reaction proceeds. Consequently, coal can be alkylated or acylated at conditions amenable to alkylation or acylation of many other materials, particularly those of an aromatic nature. Nevertheless, the coal should be in a finely ground state, further elaborated upon hereinbelow, to facilitate contact with the alkylating or acylating reagent which may be either a liquid or a gas at reaction conditions. Generally, any compound capable of being an acylating agent or an alkylating agent can be employed. In the case of acylation, the reagent may be any compound containing an acyl group, that is, ##STR2## Thus, acyl halides, e.g., iodide, bromide, chloride, or fluoride, can be employed as well as haloacyls, e.g., phosgene, and compounds generally of the formula ##STR3## wherein X may be a halogen (i.e., iodine, bromine, chlorine, fluorine), ##STR4## (as in anhydride), and R may be alkyl, cycloalkyl, aryl cycloalkyl, or arylalkyl. Acylation also includes the reaction of CO in the presence of a Friedel-Crafts catalyst to synthesize aldehydes, i.e., formylation. By this method CO is introduced into aromatic molecules under the influence of typical Friedel-Crafts catalysts. The number of carbon atoms in the acyl containing compound can vary widely, such as C.sub.2 or larger, preferably C.sub.2 to C.sub.20. Examples of acyl containing compounds are acetyl chloride, lauroyl chloride, benzoyl chloride, etc. Additionally, carbon monoxide, although not an acyl compound, per se, can be employed, as previously mentioned, in the formylation reaction. In the case of alkylation, the reagent can be olefinic, paraffinic, cycloparaffinic, or an alkyl halide. The size of the reagent is not critical although the larger the chain the greater the benefit per reaction site insofar as subsequent conversion of the coal via gasification is concerned. Preferably C.sub.2 -C.sub.20 olefins are employed, C.sub.2 -C.sub.20 paraffins, and compounds having the general formula R.sub.2 --X wherein X is any halogen and R.sub.2 can be alkyl, cycloalkyl, aryl cycloalkyl, or arylalkyl and more preferably having from 1-20 carbon atoms. Still more preferably are C.sub.2 -C.sub.8 alkyl halides and C.sub.2 -C.sub.8 olefins, e.g., ethylene, propylene, butylene, pentylene, butyl chloride, propyl bromide, ethyl chloride, ethyl iodide, etc. Alcohols can also be employed as alkylating agents although a greater than stoichiometric amount of catalyst is usually required when an alcohol is the alkylating reagent. C.sub.1 -C.sub.20 straight chain or branched compounds can be employed. Thus, in the formula R.sub.2 --X, X can also be an OH (hydroxyl) group. The use of acyl halides or alkyl halides requires the use of an acid catalyst to promote the desired reaction. Catalysts that can be employed are broadly characterized as electron acceptors and may be commonly referred to as Friedel-Crafts catalysts. Examples of such catalysts are as follows. (1) Acidic halides such as Lewis acids, typified by metal halides of the formula MX.sub.n wherein M is metal selected from Groups IIB,IIIA,IIIb,IVA,IVB,VA,VB,VIB,or VIII of the Periodic Chart of the Elements, X is a halide from Group VIIA, and n is an integer from 2 to 6. Further examples of these materials are the fluorides, chlorides, or bromides, preferably fluorides, chlorides, or bromides of aluminum, beryllium, cadmium, zinc, boron, gallium, titanium, zirconium, tin, lead, bismuth, iron, uranium, molybdenum, tungsten, tantalum, niobium, etc. Preferably, preferred materials are aluminum chloride, aluminum bromide, zinc chloride, ferric chloride, antimony pentafluoride, tantalum pentafluoride, boron trifluoride, etc. Additionally, these materials may be promoted with cocatalysts that are proton releasing substances, e.g., hydrogen halides, such as hydrogen chloride. Thus, a particularly preferred catalyst is HCl or AlCl.sub.3 /HCl. (2) Metal alkyls and halides of aluminum, boron, or zinc, e.g., triethyl aluminum, diethyl aluminum halide, and the like. (3) Protonic acids commonly referred to as Bronsted acids and typified by sulfuric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, fluorosulfuric acid, phosphoric acid, alkane sulfonic acids, e.g., trimethane sulfonic acid, trifluoroacetic acid, aromatic sulfonic acids such as para-toluene sulfonic acid, and the like, preferably HF or HCl. (4) Acidic oxides and sulfides (acidic chalcides) and modified zeolites, e.g., SiO.sub.2 /Al.sub.2 O.sub.3. Additionally, these materials may be promoted with cocatalysts that are proton releasing substances, e.g., hydrogen halides such as hydrogen chloride and hydrogen fluoride. Since eastern and western American sub-bituminous coals, bituminous coals, and lignite contain significant amounts (as much as 7% by weight) of clays and acidic oxides, the use of clays and acidic oxides either by promotion with acids (e.g., HCl, HF) or alone is particularly preferred. (5) Cation exchange resins. (6) Metathetic cation forming agents. Preferred catalysts are Lewis acids, Bronsted acids and acidic oxides. These catalysts may be mixed together in the presence or absence of a liquid diluent. The components may be mixed separately or in the presence of the substrate coal. Generally, the order of mixing of the reaction components is not critical, but in the case of alkene alkylation the unsaturated moiety should be added in such a way as to minimize polymerization and other side reactions. When the metal halides are employed normal precautions should be taken to avoid preferential reaction and consequently catalyst deactivation, by combination with water. Thus, the coal is normally dried and should be substantially moisture free, that is, less than 4 wt. % moisture, based on coal, preferably less than 2 wt. % moisture. Alternatively, the acyl halide or alkyl halide can be mixed with the metal halide catalyst prior to contacting with the coal and thereby inhibit any deactivation of the metal halide catalyst due to reaction with water. The metal halide catalyst must be present in greater than stoichiometric amounts, based on the acylating agent. Thus, about 100 to 150 mol. % metal halide, preferably 100 to 120 mol. %, and more preferably 100 to 105 mol. % metal halide can be employed. Acylation conditions are not critical and temperatures may range from about -20.degree. to 200.degree. C, preferably 0 to 150.degree. C, while pressures may range from 0 to 2000 psig, preferably atmospheric to 1500 psig. Contact times may also vary widely, e.g., a few seconds to several days, preferably about 10 seconds to 300 minutes, most preferably 1 minute to 2 hours. Alkylation is similarly accomplished by the use of known techniques. Thus, alkylation of the coal can be effected either with or without the addition of an extraneous catalyst. Normally, alkylation is effected either catalytically or thermally. However, in the case of coal, it is believed that the mineral matter present in coal may also act as a catalyst for alkylation. Again, moisture should be avoided and the presence of water should be kept below the amounts mentioned above. Additionally, when olefins are employed, care should be taken to avoid conditions that could lead to olefin polymerization, e.g., lower temperatures. Preferably C.sub.2 and terminal olefins are used and preferred catalysts are HF, BF.sub.3, phosphoric acid, or acid promoted coal mineral matter or no extraneous catalyst. Generally, however, temperatures may range from about 0.degree. to 300.degree. C, preferably 25.degree. to 250.degree. C with pressures ranging from about 0 to 2000 psig, preferably 0 to 1500 psig and contact times again ranging from a few seconds to several days, preferably about 10 seconds to about 300 minutes, most preferably 1 minute to 2 hours. When no extraneous catalyst is employed, temperatures should be raised within the ranges shown to facilitate the process. A variety of alkylation catalysts can be employed and these can be known and reported catalysts such as the Friedel-Crafts catalysts mentioned above, particularly the Lewis acids, or strong acids such as hydrofluoric acid, hydrochloric acid, sulfuric acid, fluorosulfuric acid, trifluoracetic acid, methane sulfonic acid, and the like as well as mixtures of Lewis acids with Bronsted acids for example as shown in the U.S. Pat. No. 3,708,583. The amount of catalyst, if any, employed can range from 0.05 to 50 wt. % based on coal, preferably 0.05 to 10 wt. %. The substitution reactions may be carried out in the presence of an inert diluent. Such diluents suitable for use in the process are solvents such as normal paraffins, preferably C.sub.2 to C.sub.12, halogenated solvents such as carbon tetrachloride, chloroform, ethylene dichloride, and other typical Friedel-Crafts alkylation solvents including nitromethane, nitrobenzene, carbon disulfide, etc. Solvents which may be used to extract the activated coal product, when such extraction is desired, are solvents such as aromatics including benzene, toluene, xylene; paraffins, preferably C.sub.4 to C.sub.12, alcohols, ethers such as ethyl ether, tetrahydrofuran, halogenated solvents such as CCl.sub.4, CHCL.sub.3, ethylene dichloride, amines such as pyridine quinoline, morpholine, piperidine, etc. and phenols such as phenol, cresol, xylenols, etc., and acetones such as acetone, 2-butanone, etc. At the conclusion of the alkylation or acylation reaction, the activated coal is separated from the reaction mixture by conventional techniques and made free of any acid catalyst, as by washing. As mentioned above, the alkylation or acylation step can then be repeated to maximize the amount of reagent taken up by the coal and further reduce, insofar as possible, the presence of secondary structural characteristics in the coal. Generally, any type of higher rank coal can be utilized in the process of this invention, such as bituminous, anthracite, etc., preferably bituminous, the coal is generally ground to a finely divided state and will contain particles less than about 1/4 inch in size, preferably less than about 8 mesh, more preferably less than about 100 mesh. It is believed that the degree of alkylation and/or acylation of the coal may be a function of coal surface area. Consequently, it is desirable to expose as much coal surface area as possible without losing coal as dust or fines or as the economics of coal grinding may dictate. Thus, particle sizes of less than about 8 mesh to greater than about 325 mesh are preferred and particle sizes of less than about 100 mesh to greater than about 325 mesh are more preferred. The coal can be dried by conventional drying techniques, for example, by heating to about 100.degree. to 110.degree. C, but below temperatures that might cause other reactions when susceptible coals are employed. The dried coal can then be fed to the alkylation or acylation zone either as a solid or slurried in a suitable solvent, e.g., paraffins such as heptane, hexane, cyclohexane, carbon disulfide, halogenated paraffins such as carbon tetrachloride, CHCl.sub.3, etc., although a solid feed is preferred since solvents tend to reduce the activity of catalysts employed in alkylation or acylation. Subsequent to the alkylation/acylation reaction, the product, hereafter referred to as "activated coal," is subjected to gasification. Examples 1-3 are presented to demonstrate that the materials used to alkylate coal, when used separately effect essentially no change in the coal and cannot therefore, be viewed as contributing independently to the result finally observed when used in combination. EXAMPLE 1 ______________________________________ EXTRACTION OF RAW ILLINOIS #6 COAL WITH BENZENE ______________________________________ Reactants 30.0 g Illinois #6 (<200 Mesh) refluxed in 500 ml benzene under nitrogen. Reaction Conditions T, .degree. C 78 Pressure, (kPa) 101 (1 atm) Time, hr 8 Extract Yield = 0.4 g Recovered Coal = 29.0 g ##STR5## ##STR6## Coal Recovered Coal ______________________________________ % H 5.08 4.69 % C 69.07 65.86 H/C 0.876 0.849 ______________________________________ EXAMPLE 2 ______________________________________ REACTION OF ILLINOIS #6 WITH ALUMINUM CHLORIDE ______________________________________ REACTANTS 10.0 g Illinois #6 (<200 Mesh) added to 3.0 g AlCl.sub.3 in a 120 ml Paar autoclave at 25.degree. C. Reaction Conditions T, .degree. C140 Pressure, Total (kPa), 25.degree. C 276 40 psi Time, hr24 Mixture quenched, filtered and vacuum oven dried 12 hr at 80.degree. C. Recovered Coal = 9.5 g Material Balance = 9.5 g .times. 100% = 95% 10.0 g Recovered Coal Benzene Extraction Before Extraction After Extraction ______________________________________ % H 4.59 4.65 % C 66.60 66.23 H/C 0.821 0.837 ______________________________________ EXAMPLE 3 ______________________________________ EFFECT OF 2-CHLOROPROPANE ON COAL ______________________________________ Reactants 2.0 g Illinois #6 (<200 mesh) covered in a capped jar with 2-chloropropane. Reaction Conditions T, .degree. C25 25 Pressure, kPa 101.353 Time, Hr12 Mixture washed with water, separated by filtration and the coal vacuum oven dried for 16 hrs. at 80.degree. C. Treated Coal ______________________________________ % H 4.61 % C 66.47 H/C 0.826 No Reaction Observed. ______________________________________ GENERAL PROCEDURE - ALKYLATION A 128 ml Paar autoclave (316 stainless steel) is charged with vacuum-oven dried coal, alkylating agent and catalyst at either 0.degree. or room temperature. If either or both the alkylating agent and catalyst are gases, the gaseous reactant(s) is added last to the evacuated autoclave. When a reaction temperature above room temperature was required, the heat was supplied by an external steam bath or by an oil bath. All reactions were cooled to ambient prior to venting or collecting the gases and opening the autoclave. The solid reaction product is treated with enough water or dilute caustic to destroy the strong Lewis acid catalyst and the aqueous material is separated either by filtration or extraction with a suitable organic solvent. EXAMPLE 4 ______________________________________ To demonstrate the results obtained by realkylation of the coal (i.e. multiple alkylation). Reactants 28.13 g <100 mesh Illinois #6, 41.6 g, 2- chloropropane, 5.9 g aluminum chloride in a 128-ml Paar autoclave. Reaction Conditions T, .degree. C Initial 0 Maximum 100 Pressure, MPa, Maximum 2.90 420 psig Final 1.86 270 psig Time Hr 1.7 Vessel vented, the reaction mixture quenched with 20 ml water, filtered, and the coal product taken up in 300 ml benzene. Extraction 0.17 hr in hot (75.degree. C) benzene gave 3.46 g extract ##STR7## Realkylation Recovered coal (30.26 g), 59 g 2-chloro- propane and 6.0 g aluminum chloride in a 128 ml Paar autoclave. Reaction Conditions T, .degree. C 160 Pressure, MPa, Max 340 psig Pressure, Final 80 psig Time, Hr 12 Vessel vented, quench filtered, and extracted with pentane (0.10 g), cold benzene and hot (75.degree. C) benzene (1.52 g). Solid recovered was 30.48 g. Total Extract = 5.1 g ##STR8## Analyses Coal Product Extract ______________________________________ % H 5.29 4.88 8.65 % C 68.58 58.04 86.32 H/C 0.926 1.01 1.20 % Cl 0.18 6.20 -- % N 1.35 0.93 0.092 % STotal 4.01 2.80 0.28 % Spyritic 1.12 -- -- % Ash 8.20 13.0 -- % O -- -- 2.0 Mol. Wt. 280.0 (GPC, Hydrocarbon Standard) ______________________________________ ALKYLATION WITH OLEFINS-GENERAL In general the chief difference between alkyl halide and olefin alkylations are: the olefins used are gaseous and side reactions and especially polymerizations are far more prevalent with olefin alkylations. When an olefin polymerizes the product has the molecular formula (CH.sub.2).sub.n. In those alkylations where a liquid product or liquid extract has an H/C atomic ratio of 1.9.fwdarw.2.0 we consider this product to be essentially polymeric olefin with some small amount of coal possibly dissolved in the polymer. EXAMPLE 5 ______________________________________ ALKYLATIONS WITH ETHYLENE ______________________________________ Reactants 10.0 g Illinois #6 (<200 Mesh), 0.758 Mpa (110 psi) HCl, 0.793 MPa (115 psi) ethylene. Reaction Conditions T, .degree. C100 Pressure, MPa 2.65 385 psi Time, Hr2 Vessel vented, product water washed and dried overnight at 80.degree. C on house vacuum. No extraction run. Analyses on Product ______________________________________ % H 4.69 % C 65.98 H/C 0.854 % ASH 9.38 ______________________________________ EXAMPLE 6 Alkylated Illinois coal vs. raw Illinois coal gives improved volatile matter make and improved carbon dioxide gasification rate. There is no change in steam gasification rate. REACTANTS 10.0g Illinois #6 (< 100 mesh), 3.0g aluminum chloride and 10.0g of 2-chloropropane were mixed together at 0.degree. C in a 128 cc autoclave which was then sealed at 0.degree. C. ______________________________________ REACTION CONDITIONS ______________________________________ T, .degree. C 155 Pressure (Kpa) 2275 827 at 25.degree. Time, Hr. 1 ______________________________________ Mixture was cooled to room temperature, the autoclave was vented and the reaction products were water washed, filtered and vacuum oven dried to give 11.73 g of product: 69.04% C, 6.17% H, H/C = 1.06. EXAMPLE 7 Alkylated Kentucky HVB coal vs. raw Kentucky HVB coal gives improved volatile matter make and improved carbon dioxide gasification rate. There is no change in steam gasification rate. REACTANTS 10.0g Kentucky HVB (dry, <100 mesh) 2g aluminum chloride and 8.6g of 2-chloropropane were mixed together at 0.degree. C in a 365 cc autoclave which was then sealed at 0.degree. C. ______________________________________ REACTION CONDITIONS: ______________________________________ T, .degree. C 176 Pressure (Kpa) 1896 690 at 25.degree. Time, Hr. 1.5 ______________________________________ Mixture was cooled to room temperature, the autoclave was vented and the reaction products were water washed, filtered and vacuum oven dried to give 11.7g of product. EXAMPLE 8 Alkylated Wyodak coal vs. raw Wyodak coal gives no improvement in volatile matter make and marked decreases in the rate of carbon dioxide and steam gasification vs. the untreated coal. REACTANTS 20.0g Wyodak (dry, <100 mesh), 5.0g aluminum chloride and 20.0g of 2-chloropropane were mixed together at 0.degree. C in a 128cc autoclave which was then sealed at 0.degree. C. ______________________________________ REACTION CONDITIONS: ______________________________________ T, .degree. C 150 Pressure (Kpa) 2551 1310 at 25.degree. Time, Hr. 1 ______________________________________ Mixture was cooled to room temperature, the autoclave was vented and the reaction products were water washed, filtered and vacuum oven dried to give 17.0g of product. EXAMPLE 9 ______________________________________ Reactants 5.0 g Illinois #6 coal (<200 Mesh) 1.0 g aluminum chloride, 2.5 ml 1-octadecene and 15 ml carbon tetrachloride charged to autoclave. Reaction Conditions T,.degree. C 80 Pressure, MPa -- Time, Hr .about. 16 Vessel was vented, product filtered, CCl.sub.4 layer water washed, dried and evaporated to give 1.8 g extract (A) residue, after washing with dilute HCl, dilute caustic, and water and drying overnight in a vacuum oven at 80.degree. C, was 5.06 g (B). Analyses ______________________________________ % H 5.15 % C 67.98 H/C 0.908 ______________________________________ Changes in the reactivity of Illinois #6 Kentucky and Wyodak coals which result from alkylation have been measured. GASIFICATION It is difficult to give an all-encompassing and unambiguous definition of reactivity when referring to coal or coke. However, the rate of gasification by CO.sub.2 is often taken as a measure of activity and generally as a measure of ease and facility of gasification in general and therefore this approach has been used. Using a sensitive recording balance, the rates of reaction with carbon dioxide of the alkylated coal sample as a function of burn-off, i.e., of the extent of reaction at 850.degree. C, have been measured. These were then compared with the rates obtained under identical conditions for an untreated sample. Extracted and unextracted alkylated coals were also compared. (See Table II). These experiments were performed on samples which initially weighed .about. 50 mg. They were heated at a rate of from 5.degree. to 10.degree. C/min to 850.degree. C and maintained at that temperature for 45 min. in an atmosphere of argon flowing through the reactor at a rate of 2 liter/min. This pyrolysis resulted in a substantial loss of weight due to volatilization of easily removed material. In the case of the untreated sample, this loss amounted to 49.7%, the weight decreasing from 50.90 mg to 25.60 mg. The alkylated sample lost an almost identical weight, i.e., 50.9%. When the weight of the sample reached a steady value, the argon atmosphere was replaced by CO.sub.2 at 1 atmosphere flowing at the rate of 2 L/min also and the weight loss which occurred as a result of gasification due to the reaction: C + CO.sub.2 .fwdarw. 2 CO was continuously recorded. From these curves both the rates dm/dt and the actual weight of the sample (m) could be calculated. In the attached Figures the rate of gasification expressed as (1/m) dm/dt against percent burn-off has been plotted. These experiments resulted in the following conclusions: 1. The amount of volatile materials lost upon pyrolysis is greater for alkylated than nonalkylated coal samples in all reported instances with the exception of Wyodak coal; 2. The rate of gasification increases with increased burn-off. At .about. 80% burn-off, for example, (see FIG. I), the rate is almost 3 times the initial rate of gasification. This acceleration of the gasification process is likely due to an increase in the surface area of the solid and to an enlargement of pore diameters so as to make them more accessible to reaction. 3. The rate of gasification of the alkylated extracted sample is higher than that of the untreated coal. Initially, this increase amounts to about 40-45% although the average increase is probably more like 25%. This improvement is significant. From this it can be seen that alkylated coal (Illinois #6) whether extracted or not extracted, gasifies more rapidly than does nonalkylated coal. Alkylated Illinois #6 and Kentucky coals exhibit greater weight loss upon pyrolysis (on the order of 25 to 100% increase) as compared to nonalkylated Illinois #6 and Kentucky coals. The reactivity of alkylated Wyodak coals with that of the corresponding untreated sample have also been compared. As previously indicated, the rate of gasification of the coals by CO.sub.2 at 850.degree. C and 1 atm pressure has been taken as a measure of reactivity. The instantaneous rates increase with burn-off. The rate of gasification of the untreated Wyodak coal is over 10 times faster than that of the alkylated sample. This is in contradistinction with the behavior which we have observed with the Illinois coal which, upon alkylation, had somewhat higher reactivities (40-50% higher) and indicates that all coals are not equivalent insofar as their ability to benefit from electrophilic aromatic substitution pretreatment in the case of gasification. This is more easily seen in the table below. Untreated Wyodak gasifies 5-10 times faster than does alkylated Illinois. The results of these various experiments are summarized in Table II below. TABLE II __________________________________________________________________________ GASIFICATION WITH CO.sub.2 AND H.sub.2 O SHOWS ALKYLATION CAN AFFECT THE COAL CHAR* % Wt. Loss % Burn-Off (CO.sub.2)** % Wt. Loss % Burn-Off (H.sub.2 O)** Coal Type Treatment Pyrolysis to 850.degree. C. 20 40 60 Pyrolysis to 850.degree. C 20 40 60 __________________________________________________________________________ Wyodak Alkylated 52.3 3.8 4.2 4.6 54.3 52.0 53.5 55.0 Raw 55.3 55.0 61.0 65.0 50.4 218 240 270 Illinois Alkylated 65.1 7.8 8.8 9.8 50.9 43.2 38.0 36.0 Raw 50.2 5.5 6.2 7.0 41.8 39.0 40.9 36.2 Alkylated 50.9 9.9 13.0 15.7 Extracted Raw 49.7 7.7 10.7 13.8 Kentucky Alkylated 43.3 5.6 5.8 5.9 42.6 37.0 39.0 30.4 Raw 26.6 3.4 3.3 3.3 32.5 35.5 37.7 28.8 __________________________________________________________________________ *850.degree. C **Instantaneous burn-off rate mg/min./g. carbon.? This increase of the gasification rate in the case of alkylated Illinois #6 and Kentucky coals as compared with identical unalkylated coals indicates that the gasification process is beneficially affected by electrophilic aromatic substitution pretreatment of certain coals and results in an improved gasification process which is markedly superior to standard gasification processes utilizing unpretreated coals. The increased weight loss upon slow pyrolysis of the alkylated coals coupled with the enhanced rate of gasification of the pretreated coals demonstrate that the coal is being more efficiently utilized on a per ton basis by pretreating the coal with an electrophilic aromatic substitution step and consequently results in production of an increased volume of desired end products as compared with identical pyrolysis-gasification techniques practiced on unpretreated coal. In general, the gasification procedures practical in the instant invention utilizing the superior characteristics of electrophilically substituted coal may include procedures wherein the small molecule gas used to gasify mau be CO.sub.2, H.sub.2 O (steam), H.sub.2, air, O.sub.2, CO, H.sub.2 S, SO.sub.2, NH.sub.3 or mixtures thereof, especially H.sub.2 O/H.sub.2. The gasification procedures which may be practiced using the above small molecule gases may be run at pressures ranging from atmospheric to 2000 psi, preferably 50 psi to 500 psi. The temperatures at which such procedures may be run range from 200.degree. to 1200.degree. C, preferably 425.degree. to 900.degree. C. The electrophilically aromatically substituted coal is heated to the desired maximum temperature (from the starting point of ambient room temperature) at a rate of from 0.1.degree. C/min to 10.degree. C/min. The heating rate is selected in order to alter aspects of the pyrolysis process other than the total weight loss such as for example, the fluidity of the coal, gas versus liquid make, heat transfer limitation, etc. Once the electrophilically aromatically substituted coal is heated to the desired maximum temperature, it may be held at that temperature for a period of time ranging anywhere from 1 minute to two hours, preferably 1 min. to 1 hour, most preferably 1 min. to 30 min. * * * * *


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September is National Sewing Month
All links in my posts are orange. Any word with a double line beneath it is not my link. I apologize for this inconvenience. This change is effective beginning 09-10-2014.
Disclaimer: I am not compensated by any person/company. All opinions are my own unless in quotation marks.
Featured Sewing Blog
Heather Valentine's blog, "The Sewing Loft" is packed full of fun & education.
- Sewing IQ quiz which consists of 12 questions. It's fun, educational & some of the questions are tricky! (read carefully before answering)Hint: Q8 is the trickiest!
- Tips for Printing Patterns at home. Ever need some tips for ALL those pieces of paper? Hallelujah! These tips are great!
- …& much more!
Did you know?
You are most likely aware Joann Fabric & Crafts stores have classrooms where they teach crafts & sewing. However, the classrooms are not always in use. When they aren't the store offers "Open Time" for your meetings. The cost? FREE!
This is great! My house just isn't big enough for meetings and I would love to have a sewing circle.
Threads® Magazine Article Highlights
On Threads® Magazine's website offers many articles to help seamstresses gain expertise. There are lots of photos and the information is clearly written. A sewer doesn't need to have experience to understand the directions.
The New column "Threads Daily" currently offers the following articles:
- 19 Essential Fabric Tips & Tricks you should know.
- Project Runway Season 13; Episode 8 highlights.
- Q & A on September 24, 2014 with sewing expert Louise Cutter. Also, Louise Cutter's "Quick Sew" DVD giveaway. Available at the Threads Magazine store price regularly
$24.95now $19.96.
- How to Cut and Sew a Decorative Bias Facing.
- Watch It's Sew Easy Episode 512 online.
If you are an on-line member you have access to the "Insider" column.
"About Membership
Online membership provides you total access to premium Threads videos, articles, tips and much more. Plus, you get FREE tablet editions of Threadsmagazine with your paid membership.
Enjoy digital access to:
- Videos from top sewing experts
- Threads magazine's most recent issues
- A collection of essential resources from Threads
- Exclusive articles, the Insider pattern collection, and our 360° garment viewer
- Plus so much more! Scroll down to see all the benefits
That's over $350 worth of premium Insider-only content!"
Reader Tip
Use recycled bags for sewing tricky fabrics.
Giveaways & Events
#1 The daily entry on AllFreeSewing.com National Sewing Month 2014 Grand Prize Giveaway! Original post on Bagg Lady's Buzz
#2 NEW The daily entry on AllFreeSewing.com giveaway book; Start Stitching between September 15 – 29, 2014. Book review.
#3 NEW The daily entry on AllFreeSewing.com giveaway; 12 Yards of Assorted FreeSpirit Fashion Fabrics (Coats & Clark) between September 15 & October 15, 2014. Plus a free eBook "How to Make Your Own Clothes; FreeSpirit Fashion Fabrics.
Get Ready for the Million Pillowcase Sew-A-Thon 09/19-20 Original Post here. Event finished but Pillowcases are still needed!
#5 Don't forget the KAL/CAL began 09-09-2014. It's not too late to start! Original Post here. Clues 1 & 2 are already published.
#6 If you haven't registered for the Wild & Crazy Cuddle Giveaway remember registration ends 09-30-2014 Original Post here.
#7 If you haven't left a comment to register for the Storage Solutions giveaway by Threads magazine & Go-Organize Original Post here.
++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++Please accept my apology. I missed a week of posts due to unforeseen events in my life. Tomorrow New Charity Highlight


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former librarian turned editor, reader, writer, avid consumer of ya fiction, blogger (stackedbooks.org), introvert, obsessing over black licorice. word.
The fine folks at Book Riot gave me control of this week's Buy, Borrow, Bypass feature, and I got to lay down the verdict on these four one-word title YA books. Check it out (maybe I got a little brutal?).
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Just-in time: Rose closes strong, gets 1/2 point
Justin Rose speaks with Todd Lewis after Saturday play at the 2014 Ryder Cup.
McGinley leads with strength to 'establish tone'
European Captain Paul McGinley speaks with Todd Lewis after play Saturday at the 2014 Ryder Cup.
G-Mac ready to lead Europe in first singles out
Graeme McDowell speaks with Todd Lewis Sunday morning at the 2014 Ryder Cup.
Rose-y disposition: Justin talks Ryder Cup win
Justin Rose speaks with Todd Lewis after the 2014 Ryder Cup at Gleneagles.
Michael Jordan talks about his passion for the Ryder Cup
Todd Lewis talks with Michael Jordan about the Ryder Cup just moments before players tee off for Saturday four-ball matches.Thank you very much. Michael Jordan and I were talking a fac, about the fact that the showers here are kinda small. He has to duck down here in Scotland. And you've got the 23, and by the way, did you request the 23 band? No. Or it was given to you? Nah, it was given to me. It was a, it was a surprisingly great present that I received actually. You walked inside the ropes yesterday and saw. The intense pressure of the Ryder Cup , and I know you, of course you've been in some pressure situations. What did you take away from day one for Team
Morning Update From Gleneagles
Steve Burkowski and Todd Lewis report on the latest happenings from both teams at the 2014 Ryder Cup.centenary course. Rory McIlroy. Has some interesting comments this morning. Now captain Paul McGinley has been deflecting the fact that Europe is a slight favorite this week in the Ryder Cup but Rory McIlroy this morning said, yes we're slight favorites this year for a reason. We shouldn't shy away from that. We
Latest Team News With Burkowski and Lewis
Steve Burkowski and Todd Lewis check in with the latest team news Wednesday at the 2014 Ryder Cup.tee playing those ten holes. A couple of reasons they did so. Paul McGinley said, one, they wanna conserve some energy by playing just ten holes. Secondly, there's a Ryder Cup gala happening tonight and it's happening in Glasgow, which is about an hour's away via car, so they got time to come
Westy 'feeling old' 17 years after first Ryder Cup
Lee Westwood speaks with Todd Lewis Thursday at the 2014 Ryder Cup.Thank you very much. I'm here with Lee Westwood as Graham McDowell has a little fun with us as well. The veteran Lee Westwood . Your first. Yo, come on. Your first Ryder Cup , late 90s; how about that? Making me feel old. But let's talk about that a little bit. Bit younger than you though. Well that's true. Considering where you are. You're in your 40s now. And I know you've got a lot of great golf ahead of you. But do you cherish the moment here this week, maybe, a little more than you did earlier in your career? Yeah, I mean, you, you cherish every time you play in the Ryder Cup . It's such a special week and it's, it's special to be part of, you know, European team , and and be representing your continent. Lee, you, by the way, you've been working so hard in the gym, I know you've changed your diet. You've lost 23 pounds. You've actually added more muscle as well. What are the positives for your golf swing with this body? And maybe some negatives that you've had to work with? Yeah, just recently I've found that my body hasto get to the opening ceremonies. I appreciate your time. My pleasure. Lee Westwood . Guys
Early Europe Update From Todd Lewis
Todd Lewis reports on Europe's final day of practice before the 2014 Ryder Cup.who's going to be paired with who within the group. For instance Thomas Bjorn is likely going to play with Martin Kaymer. McIlroy and Garcia will play together. Gallacher and Westwood will likely play together. Dubuisson and Graham McDowell playing together. Ian Poulter and Justin Rouse will be paired together and Henrik Stenson and Jamie Donaldson will be paired together. Of course. The order of the pairings will be revealed later today. Interesting comments from Phil Mickelson of
McIlroy: Good to get tune-up in wind, cold
Rory McIlroy speaks with Todd Lewis Thursday at the 2014 Ryder Cup.to, you know, obviously we've. We have got a couple obvious ones, Ian Poulter and Lee Westwood and Thomas Burn, those sort of more experienced guys, but I feel like I am in a position where I know I
McIlroy, Dubuisson, top McDowell, Kaymer in match
Todd Lewis wraps up everything Team Europe on Wednesday at the 2014 Ryder Cup.will have a new piece of equipment in his bag for the Ryder Cup . He will have a new driver. He's using a prototype driver from his manufacturer. It is a black driver. Very different obviously than the red driver that he's used over the last 22 months. Talked to Rory, he said that he can hit the ball further in the air. About eight yards off the tee compared to his old driver. And he can work the ball both directions a little easier as well. As for Paul McGinley's team, well, the captain has deflected the idea that Team Europe is the favorite here this week over the Americans. As for
Donaldson on first Ryder: 'Helluva week so far'
Jamie Donaldson speaks with Todd Lewis Thursday at the 2014 Ryder Cup.The very first Ryder Cup for Jamie Donaldson . Jamie, so far this week, has it been everything that you've anticipated? And more. Its been a hell of a week so
Lewis: Europe Confident, Very, Very Loose
Todd Lewis reports on the European Team's Thursday at the 2014 Ryder Cup.three players did continue after those eight holes. Those players, Lee Westwood, Graeme McDowell , and Henrik Stenson They played the ninth, the tenth. And the 18th. Had a chance to spend some time today with Graham McDowell and Rory McDowell. Er. Excuse me. Rory McIlroy. Yesterday of course Phil Mickelson made those interesting comments saying that his team not only plays well together but they don't litigate against each other which raised some eyebrows because of course Rory McIlroy is suing his former management team. That Graeme McDowell has a stake in. Now, first off, the relationship between McDowell and McIlroy, according to both, very, very strong. As a matter
G-Mac: 'Keep righting the ship' is Euro's attitude
Graeme McDowell speaks with Todd Lewis Wednesday at the 2014 Ryder Cup.Now you're here with Graeme McDowell and Graeme, captain Tom Watson has been saying that he wants his team to remember Medina. That this is a mission of


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Abby's Awesome Birthday Party! by Abby - 9 months ago
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The Book Ninjas by The Book Ninjas - 10 months ago
"You don't want to mess with the book ninjas. We are prepared to dominate the 2014 WPL Battle of the Books. And even if we don't win, at least we have the coolest shirts." view full details
Havin' a Hootin' Time Singing with the LTN Wise Owl Chorus! by LTN Wise Owl Chorus (Grades 3-5) - 10 months ago
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Christmas Present by Brownee - 10 months ago
"Well my sister was tired of the typical christmas presents. She told me to be creative this year. Bad idea. Haha. My sister & brother in law have been married for 3.5 years and everyone keeps a..." view full details
Bixbee.com Crew by Bixbee.com Crew - 11 months ago
"The Bixbee Crew at a Holiday Kids Bazaar proudly sporting their Bixbee Custom T's. Bixbee is a designer backpack and accessory brand built on a mission to support education. For every backpack purc..." view full details
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"Rayito de Esperanza" by Beacon of Hope - about 1 year ago
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Cheering for Team Super Clark by J.R. - about 1 year ago
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Ethan's Diabetes SMACKDOWN by Ryan Howell - about 1 year ago
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Kids Style!!!- Arrington Family Reunion - Wash.DC by Arrington Family Reunion & Prom '13 - about 1 year ago
"This photo was taken on Sat., Aug. 3, 2013 during our Arrington Family Reunion Day Event just outside of the Wash. DC area. The Arrington kids, had soo much fun. They all wanted to take this pictur..." view full details


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Pin It I love pasta – especially easy recipes! This is one of those easy recipes and you can adjust seasonings to your preference to create a semi-homemade… Read More »


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" 3Com Megahertz 10/100 LAN + Modem56 - Network / modem combo - plug-in module - PC Card - 56 Kbps - x2, V.90 - EN, Fast EN "
* Prices may differ from that shown
This best-of-breed solution practically sets itself up-including those mind-numbing drivers. It combines the world's leading Ethernet technology and 3Com Megahertz 56K modem into a single PC Card. It also delivers today's fastest 10 Mbps connections with automatic 100 Mbps network configuration when you're ready. And a free upgrade when available to V.90, the 56K ITU-T standard is offered. It's today's easiest combo card to configure and use and the future-proof choice for tomorrow.


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Mil/aero market ups and downs
The military and aerospace (mil/aero) market has recently suffered some fiscal setbacks. It may come as a surprise that the economy was not to blame; rather, it was design and production delays.
This interesting, and somewhat jarring, tidbit comes from Richard L. Aboulafia, vice president of analysis at Teal Group Corp., team of aerospace and defense industry analysts in Fairfax, Va. He shared several more thought-provoking mil/aero market insights during his informative, if not eye-opening presentation, "Aircraft and defense markets: outperforming the economy," at Mentor Graphics' Integrated Electrical Solutions Forum (IESF).
The overall mil/aero market decline has been minor, especially compared with declines being felt in other industries. Some sub-segments of the mil/aero industry have suffered considerably since 2008. Business aircraft were hit harder than any other aerospace market, falling 28 percent (measured by value of deliveries) between its market peak of 2008 and 2010, Aboulafia admits.
It's a bit perplexing: Sales of the most expensive aircraft grew, while less expensive business jets took a proverbial nosedive (forgive the pun). The top half of the market, selling jets priced at $26 million and above, grew during that period—with a 1.5% increase in deliveries in 2008 through 2010. The lower half of the market, offering jets priced in the range of $4 million to $25 million, fell by a catastrophic 57.1%, Aboulafia explains.
Why the dichotomy? Aboulafia and other industry pundits, including this geek, have some thoughts (which are explored in the next installment). Be sure to read on, and certainly weigh in on what you're seeing and experiencing in the mil/aero market.
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Posted October 21st, 2011, by J VanDomelen
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aerospace, EDA, electric, electrical, geek, hardware, IESF, Integrated Electrical Solutions Forum, mentor, Mentor Graphics, Mentor.com, mil-aero, milaero, military, Richard L. Aboulafia, Teal Group Corp, Warfighters
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About J. VanDomelen Mil/Aero Blog
J. VanDomelen holds a Bachelor of Science in Information Systems and myriad certifications from Microsoft, Cisco, and CompTia in varying facets of computer software, hardware, and network design and implementation. He has worked in the electronics industry for more than 12 years in varied fields, including advanced systems design of highly technical military and aerospace computer systems, semiconductor manufacturing, open source software development, hardware design, and rapid prototyping. J. VanDomelen Mil/Aero Blog
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Commented on October 23, 2011 at 2:46 pm
By Aerospace: A market divided « J. VanDomelen Mil/Aero Blog
[...] business aviation market was the hardest hit of all the aerospace market segments, revealed Richard Aboulafia, vice president of analysis at Teal Group in Fairfax, Va. In fact, at Mentor's mil/aero IESF, he [...]
Commented on May 27, 2014 at 11:40 am
By Bizjet boom « J. VanDomelen Mil/Aero Blog
[…] commercial aviation—while military aviation is largely stagnant and general aviation, including business jets (bizjets), starting to emerge from a period of […]
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Celebrities Who Turned Fashion Designers
By Smart Cookie | posted Mar 20th 2013 at 5:35PM
So a little birdie told us that the sexy Malaika Arora Khan has plans to launch her own designer label. And while we're pleasantly surprised, we can't help but recall all the other celebrities who took to fashion designing and launched their own collections. Here's a look at some celebrity fashionistas who decided to share their style sense with us.
Image courtesy: BCCL/ Reuters
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- fashion designer,
- jewellery designer,
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Dear Martha (Stewart),
Please forgive me / all of us foodies for using your ideas ALL the time. It just means you are great! I googled 4th of July treats. And...I am sorry ....Martha! Yours are just the best. Thanks for letting me use your photos this time...I didn't have the energy to make each treat myself...but wanted to show my customers and fellow foodies some good ideas. I promise to never use your photos again. Martha, YOU ROCK!!!
(Martha Stewart photo)
(Martha Stewart photo)
Our New Favorite Halloween Book for Kids - We love to read around here and nothing makes reading to the kids more fun than an upcoming holiday! It's fun to build on their excitement and make the ...
9 hours ago


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Chris John Riley can break into your phone. Well, that's if you are running older versions of Box, LastPass, SpiderOak, Good for
Published on: October 23rd, 2014
Robert Tu taps away at his smartphone, squinting down at it in the grey light filtering in through the windows. He then
Published on: October 22nd, 2014
Canadian small to mid-sized businesses are more keen about the growing Internet of Things (IoT) industry than even their counterparts are, according
Building a good relationship with your customers is just like building any other relationship in life. It's all about trust. But how
Technology continues to change the interplay between B2B sellers and B2B buyers. One important element is the amount of data created by


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Discovering wildlife
Exploring New York's wild and natural world
Posts filtered on Category
2 new camera trapped species!
Life in Eufaula, Alabama is just fine, and I'm really enjoying it! The birding is great, the weather has been great, my dog is loving exploring with me, and the food is fantastic! Of course you know I brought my camera traps with me (Cuddeback Attack Flash and an IR Bushnell Trophy Cam), as I […] [Read More]
Best camera trap video of all time
Yes folks, I'm loudly and PROUDLY making the statement that THIS video is the best you'll ever see. If you're a follower, you know I've been in the Florida Keys interning at the National Key Deer Refuge on Big Pine Key. In addition to Key deer, a smaller subspecies of white-tailed deer, we have a […] [Read More]
Camera trap pics from the Keys!
All summer I've been camera-trapping here on Big Pine. Here are some cool images from the last round! [Read More]
Cute, cute, cute! Marsh rabbits!
Big Pine Key, where I live and work, is home to several endangered species. One that I'm interested in, because they're often forgotten because they aren't large and exciting mega-fauna, is the Lower Keys marsh rabbit (Sylvilagus palustris hefneri). The LKMR is a subspecies of the marsh rabbit, which is not considered endangered, but because […] [Read More]
Intern life at Key Deer NWR
I've been on Big Pine Key for 1 month, and I think I'm settled into the "swing" of things and pretty well acclimated. The hardest things to adjust to: heat and humidity, and not having my dog with me. I had to leave Addie with my parents for a few months. This is a temporary […] [Read More]
The continued "tail" of the squirrel…
Last week I posted a camera trap image (seen at left) of a stray cat with a strange looking red squirrel in it's mouth. Red squirrels are mostly…well, red. Of course there are variations, and they're not ALL truly red. But this was really something, the body appeared (in this picture) to be either naked […] [Read More]
Lately lackadaisical
I've certainly been lackadaisical lately, and I'm sorry (especially to myself) for not keeping up with this blog. I'm 10 days from graduation, still unemployed, and trying to figure out my life…I've been very busy. Throughout the semester, of course I've been camera trapping. I've kept the cams close, because I can't spend time wandering […] [Read More]
Finicky fisher– no more!
When I moved east to Schoharie County almost 2 years ago, I had a mental bucket list of critters that I would like to encounter while living and going to school here. Although I lived in rural areas in Western, NY, there are several animals in lower density there, than are found here. Primarily, the […] [Read More]
I just can't win!
Cuddeback, you are the bane of my camera-trapping life. Sometimes the camera doesn't work, and for no apparent reason. Other times, it's hypersensitive, and takes pictures of nothing. Lately I've been lucky, and it's taking pictures, even though it's so cold out. My last post I shared how overexposed the images are though, because of […] [Read More]
Stale chunks o' bread
Firstly, thank you so much to the few people who contacted me last week and purchased iPad raffle tickets from me!! (I still have a few to sell, btw!) This winter has sucked in the Northeast for camera trapping, in my opinion. It's been frigid, which really takes a toll on the batteries, and we've […] [Read More]
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GalleryThe Beyond Back to The Beyond
Source: The Beyond on Freebase , licensed under CC-BY
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Dr. Janet C. Sundquist, MD
Internal Medicine, Primary Medicine
- 100 High St
Buffalo, NY 14203
- 1 Office Location
- Email a Friend
- (716) 859-2589
Dr. Janet C. Sundquist has been practicing medicine for 26 years. Dr. Sundquist graduated from the University of Buffalo, SUNY School of Medicine and Biomedical Sciences in 1988. She practices medicine in Buffalo, NY and specializes in Internal Medicine. Dr. Sundquist is affiliated with Buffalo General Medical Center. She speaks English and Spanish.
Gender: Female
Years in Practice: 26 Years
Languages Spoken: English, Spanish
Medical School: University of Buffalo, SUNY School of Medicine and Biomedical Sciences
Graduation Date: 1988
Hospital Affiliations: Buffalo General Medical Center
Specialties: Internal Medicine
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Ok, but not as effective as first 6 months I've been on Astelin for about a year and a half now and it isn't working as well as it did the first six months. Still need Flonase, and have also added Claritin too. Too bad.
UPDATE: Ok, now we're in the peak allergy season and a few sneezes have made their way through. Still, I'd say that for me Astelin seems to be equally as effective as the combination of Clarinex and Flonase together. So I've saved my body one med, that's got to be good.
I've been using Astelin for a couple of months now and have to say I am quite impressed. Sure, it's winter still and not exactly the peak pollen season, but here in Southern California the acacia trees are flowering all over and tree pollen levels are "high". Normally a few sneezes would be making their way through, but Astelin must be working well because I have had no allergy symptoms.
Another plus is that I stopped taking Flonase when I started Astelin (my doctor suggested seeing how the one nasal spray worked on its own.) Even though I know that Flonase is a safe corticosteroid it still feels nice not having to take it.
Astelin takes a while to get used to - especially if you are used to taking a single pill once a day. There is something of an art to spraying it correctly and avoiding the intense bitter taste running down the back of your throat. What you have to do is lean over and look down at your feet, then spray into your nostril aiming in the direction of the inside corner of your eye. And you just breathe in slightly as you spray. Certainly more tricky than just taking a casual whiff of Flonase, but once you have it down its not a big deal.
Some sedation was noticeable the first week or so, but nothing that the morning cup of coffee didn't over-ride. Now I don't notice any sedation at all. I will update come spring / summer!


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Posts from Milk
Recipe: Hot Rum Cow
Straight Up Cocktails and Spirits
The other night I was looking for something warming to sip and decided to try out a recipe from a cocktail book brought back by a friend on a recent trip to Belfast: The Merchant Hotel Bar Book. As I flipped through the "Hot Drinks" section, something immediately caught my eye: Hot Rum Cow.
With its whimsical name and tempting list of ingredients (piping hot milk, dark rum, vanilla, aromatic bitters, and sugar), this Cow sounded like a winner.
Food Science: What is Pasteurization?
Last week we talked about how milk is homogenized and what that means for its nutritional value. This week, we talk about a related issue: how milk is pasteurized and why!
Food Science: What is Homogenization?
Kathryn's post about the cream on top of non-homogenized milk made us curious about what's going on with the homogenized milk most common in grocery stores. Let's take a look!
Straus Family Creamery
Sonoma County, CA
If you've shopped at Rainbow Grocery or Bi-Rite Market, you've probably seen those glass bottles with the cream-top milk and creamer. Most likely, they came from Straus Family Creamery in Sonoma County.
Look! Shelf-Stable Organic Milk
Survey: When Do You Add Milk To Tea?
Good Milk: Snowville Creamery
Hot or Not? The New Milk Jug
So, have you seen the new milk jug yet? What? You didn't know there was a new milk jug? Indeed there is. But if you don't shop at larger retailers like Wal-Mart and Costco you may not have seen it yet. These retailers are the first to carry milk sold in jugs that are supposed to be more environmentally friendly, as well as earth-friendly. They can be stacked better, so they take up less space, and they are cheaper and more efficient to produce and ship.
The only problem? People can't seem to pour out of them without spilling. We're curious - have you been using the new milk jug, and if so, what do you think? More info on the new milk jug below.
The Slice: The (Raw) Milk Itself
Good Question: How to Make the Perfect Cafe au Lait?
All the coffe coverage has Cortney thinking about perfect cafe au lait...
Any tips on how to make the perfect cafe au lait? Whether it was in Paris, Bilbao or Madrid, the ones I had in Europe were so far superior to any I have been able to find in the US. I'd like to know how to make my own!
- Cortney


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Welcome to Dubdisk Records, the UK's grimiest independent dubstep label!
Based in south-west England, we support a range of artists specialising in dubstep and other forms of electronic music. We don't put out anything which isn't dark and loud so everytime you see the Dubdisk logo expect to get your ears kicked in!
Why not have a listen, follow us on Twitter or friend us on Facebook and Google+!
Remember to support your local indie dubstep & electronic musicians, don't forget to visit the shop.
Latest release - Opiates Grime on a dark tip!
Opiates Grime are back on the industrial tip with some filthy beats to break ya legs to! Listen on YouTube or purchase from iTunes.
Out today - Prisoner brings the dark riddims!
Huge tunes from the man himself - Prisoner is back on it with some insanely brutal beats! A mix of classic samples and
storming leads, Dubdisk bring you only the darkest! Copies are available via our downloads page
or from all good online retailers.
Prisoner live tech demo!
Our resident beat masher Prisoner shows off some of his sick skills in a fully explained
tech demo
exclusive to Dubdisk! With some helpful pointers and a reveal of all of the kit used, Prisoner shows you how he gets up to his live sickness!
Full description on the
YouTube video.


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Humidity 42%
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Humidity 42%
Winds 6.9mph
Humidity 44%
Winds 9.2mph
Feb 24, 2014 6:03 PM by David Randall
"Late Night" returns to NBC tonight with new host Seth Meyers at the helm.
The move comes after more than ten years on "Saturday Night Live".
"It had all of the elements that I love about SNL, exist in late night which is you have to generate a lot of material, you get to have a really fun writing staff, and you get to be fluid because of how often you have to do it. So it seemed like a good fit, post SNL," Meyers says.
6 hours ago


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Welcome to Pearl Fiber Arts.
We're located in the heart of
Portland's Pearl District
on NW 11th Avenue near Glisan
Annual Stash Sale!
Labor Day Weekend
Saturday, Sunday, and Monday
11 a.m. to 6 p.m.
If you like bargains, come shop the Stash Sale!
Everything priced by the bag.
You'll find yarn, fiber, project bags, and more.
Prices start at less than $1!
Some sweater quantities available.
All sales final. Cash preferred, but credit accepted.
Visiting Portland?
Why not knit up a souvenir?
Come see our wall of locally hand-dyed yarns
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Create a memory!
Join us every Thursday from 6-9 for
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Bring a project or start something new
and enjoy the company of others
while you knit, crochet, spin, or whatever suits your fancy.
Join us for the
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Tuesday, August 12th from 7 to 9 p.m.
Bring your wheel or spindle and spin up some yarn!
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Online trolls say crash was MY fault, says cyclist kicked to the ground on Embankment
A cyclist who was kicked to the ground by a BMX biker as he rode through central London said today he is facing a barrage of abuse from people who think he is to blame.
One man stabbed and another found injured on nearby bus after fight in west London
One man was stabbed and another injured after a fight in west London this morning, police said.
Alice Gross funeral: Mourners say final poignant farewell to murdered schoolgirl in Hanwell
Crowds of mourners gathered today to say a poignant farewell to murdered schoolgirl Alice Gross as her funeral cortège passed through the streets near her home.
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Published: 03 June 2013
In the introduction to Gray's Anatomy, a collection of his best essays over the past quarter-century, the anti-utopian writer John Gray gives a modest proposal for the purpose of politics. "Politics," he writes, "is the art of devising temporary remedies for recurring evils. It is a series of expedients, not a project of salvation."
For governments, the motto might be "First, do no harm", and the mode of thinking that of the mechanic: identify the problem, find a solution, fix it. There are limits to this approach in politics. All the great advances of modernity were the result of a marriage between high ideals and low cunning. Politics isn't management consultancy. But Gray's intellectual framework does, I think, help us to comprehend an emerging disaster, which is George Osborne's housing policy.
"Housing" lacks poetic resonance. But in Britain it is the great scandal of our times. Property prices were one of the four domestic booms — along with immigration, public spending and private debt — that fuelled the years of growth preceding the crash. Property also played a major part in the crash.
It is a primary source of inequality, because those who own assets have such an advantage over those who don't. It transfers money from the young and poor to the old and rich. And housing benefit costs £24 billion each year.
So the problem is vast. Luckily, the solution is obvious: build, build, build. Forcibly deport all nimbys and build for England and St George. A massive programme of residential construction, particularly in and around London, would increase supply, reduce prices over the medium-term and create jobs for the young and low-skilled. Nor would it destroy English land, 90 per cent of which is unspoiled.
Yet confronted with the twin nuisances of nimbyism and planning regulation, Osborne has chosen otherwise. Rather than devise and apply the remedy, he is exacerbating the problem.
The Funding for Lending Scheme, which subsidises the cost of mortgages, has been augmented by a Help to Buy scheme that forces taxpayers — me and you — to underwrite billions in mortgages to people who can't afford a house.
These are among the stupidest policies ever devised in Whitehall, and a barely disguised admission of failure. It will benefit current rather than future owners, create distorting subsidies that are hard to remove, raise rather than reduce property prices, sustain our addiction to debt, and further inflate an asset bubble.
Politicians inflate asset bubbles for the simple reason that owners of assets are more likely to vote. But there has never been an economic bubble in history that didn't eventually meet a pin. The trick of modern democracy is to make sure the pin arrives after you have left high office. This is the Chancellor's gamble: that he can enjoy the bubble and delay the pin. It is myopic, selfish and inexcusable.
London's poor suffer the consequences most of all. Britain's housing policy is a moral, social, economic and geographic catastrophe. Yet by deluding the middle class into thinking they are getting richer, it might also be political gold. Sometimes, democracy stinks.
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Claudie Pierlot opens fifth London store
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Demi Lovato has become the poster child for sober living in Hollywood, but there are rumors that she may not be practicing what she preaches.
Despite a three-month rehab stay in November 2010 for drug use, eating disorders and self-harm, a source close to Demi has claimed the X Factor judge is "not as sober as she's leading everyone to believe and is still partying hard." Not only that, the same source told Radar Online that the only thing Demi has learned is how to keep the paparazzi from catching her in the act. Whoa!
What did Demi's rep have to say about the allegations? Find out after the jump!