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This process involves contacting a waste gas containing an oxide of sulfur with an aqueous medium having a pH below 7.1 in an autoregenerative cyclic process using limestone in combination with carbon dioxide, an added amount of a soluble sulfate of a cation such as potassium, lithium, sodium, magnesium or ammonium or mixtures of these compounds to remove the oxides of sulfur. The soluble sulfates may be added directly to the aqueous medium or may be formed in situ from the known carbonate, bicarbonate, oxide, sulfite, bisulfite, or hydroxide of these cations or ammonia after reaction with the sulfur oxides in the waste gas. Sulfur is removed from the cycle in the form of insoluble calcium sulfite and calcium sulfate.
Claims available in
Description (OCR text may contain errors)
United States Patent Cronkright, Jr. et al.
METHOD OF REMOVING SULFUR-CONTAINING GASES FROM WASTE GAS Inventors: Walter A. Cronkright, Jr.,
Somerville, N.J.; Bernard G. Mandelik, Houston, Tex.
[63] Continuation-impart of Ser. No. 171,267, Aug. 12,
I97 I, abandoned.
[52] US. Cl. 423/242; 423/166; 423/5 l2 [5]] Int. Cl C0lb 17/00 [58] Fieldof Search 423/242244, 423/166, 512
[56] References Cited UNITED STATES PATENTS 2,086,379 7/1937 Clark 423/243 [451 May 13, 1975 Shah 0 423/242 Villiers-Fisher 423/242 ll/l97l 1/1972 57 ABSTRACT This process involves contacting a waste gas containing an oxide of sulfur with an aqueous medium having a pH below 7.1 in an autoregenerative cyclic process using limestone in combination with carbon dioxide, an added amount of a soluble sulfate of a cation such as potassium, lithium, sodium, magnesium or ammonium or mixtures of these compounds to remove the oxides of sulfur. The soluble sulfates may be added directly to the aqueous medium or may be formed in situ from the known carbonate, bicarbonate, oxide, sulfite, bisulfite, or hydroxide of these cations or ammonia after reaction with the sulfur oxides in the waste gas. Sulfur is removed from the cycle in the form of insoluble calcium sulfite and calcium sulfate.
10 Claims, 1 Drawing Figure 1 METHOD OF REMOVING SULFUR-CONTAINING GASES FROM WASTE GAS This application is a continuation-in-part of pending application Ser. No. 171,267, filed Aug. 12, 1971 and now abandoned.
Oxides of sulfur such as sulfur dioxide and sulfur trioxide are components of many commercial effluents such as the effluent gas from coal fired electric power plants, flue gases such as boiler and furnace exhausts, smelter gases, off-gases from chemical and petroleum processes, stack gas produced from burning sulfurcontaining hydrocarbon fuels, such as oil, sour natural gas and coal, gaseous effluents from the manufacture of sulfuric acid and other sources. Due to the noxious effect of these oxides of sulfur on human, animal and plant life and on metals and other materials, pollution of the a'mosphere by these oxides has been a problem of serious concern and one of long standing. Notwithstanding the many proposals for the removal of these noxious gaseous components, none have proven satisfactory since they are highly inefficient and costly, involving significant losses of energy and inefficient use of the reacting species and process equipment. Because of the latter disadvantage it has been necessary to overdesign equipment used in the processes currently being operated.
Limestone or dolomite injection into the boiler of a commercial power plant is presently one of the major commercialized sulfur removal processes in the United States. It has the advantages of the lowest capital investment and operating costs of any available developed process. However, dry limestone process tests to date have shown disappointingly low sulfur dioxide removal efficiencies which lead to the requirement for impractically large quantities of limestone to achieve desired levels of decontamination.
Of methods being considered for wide commercial application, the wet process, wherein the waste gases are scrubbed with an aqueous slurry is most attractive from the standpoint of inexpensive treating materials and has been shown to give improved efficiency. Aqueous solutions or slurries oflimc, limestone, ammonia or organic liquids have been suitably employed in the removal of oxides of sulfur; although for reasons of econ omy, limestone or lime are most desirably employed. Other materials, being more expensive, would require reprocessing which adds to the overall capital requirement.
Limestone or lime slurries, however, are difficult and expensive to utilize because of their poor solubility in aqueous media. One method of minimizing this problem is to scrub sulfur dioxide from waste gases in a long residence time tower such as a packed column. Unfortunately, calcium sulfite and calcium sulfate precipitated from the scrubbing reactions deposit readily on packing and tower internals thereby necessitating fre quent shutdown for cleaning operations. Many methods are known by which to minimize or remove these scale deposits, but the basic problem remains.
Another alternate in the use of limestone slurries is to utilize a scrubbing apparatus that has limited susceptability to scaling such as a Venturi-type scrubber or spray tower. Again, due to poor solubility of limestone in aqueous media, several short residence time scrubbers, in series, must be employed in order to remove sulfur dioxide to the degree required. Such systerns have a high pressure drop and expans a great deal of energy in moving gas through the scrubbing system. In addition, large liquid to gas ratios are generally required thus adding increased auxiliary equipment cost to high scrubber cost.
Therefore, a method of removing sulfur dioxide from waste gases in a short residence time scrubbing system that utilizes a limestone slurry having substantially improved scrubbing capacity would rcduce the overall size and cost of such systems and would thereby mark a significant advance in the art.
It is an object of this invention to overcome the pres ent difficulties encountered in the removal of noxious oxides of sulfur from the commercial effluents men tioned above while improving the efficiency and economy of the wet process.
Another object of the present invention is to mark edly increase the scrubbing capacity of the limestone washing medium.
Another object is to provide a process for the removal of sulfur values from low value sulfur-bearing waste gases.
Still another object is to effect about 959? removal of oxides of sulfur from waste gases.
Another object of the present invention is to provide a particular cyclic, autoregcnerative process for the removal of sulfur dioxide from commercial waste gases.
These and other objects and advantages of this inven tion will become apparent from the accompanying dcscription and disclosure.
In accordance with the teaching of this invention, a process is provided for the removal of oxides of sulfur from the commercial effluents or waste gases described above, the method including a liquid phase process comprising scrubbing waste gas containing oxides of sulfur in a contacting zone with an aquueous medium having a pH below 7.1 containing calcium carbonate, carbon dioxide, and at least about 3 weight percent preferably between about 5 and about 27 weight percent of a soluble sulfate of sodium, lithium. potassium, magnesium or ammonia. The method further comprises formation of calcium sulfite and calcium sulfate in solid form which may be easily separated from the aqueous medium for disposal, further use, or subsequent recovery of sulfur values and the recycle of part of these solids, along with calcium carbonate to the waste gas contacting zone.
The scrubbing efficiency of an aqueous limestone slurry may be improved when such a slurry is promoted by small amounts of soluble sulfate, however, the improvement becomes pronounced as the level of soluble sulfate concentration is increased. There is no limit on the maximum amount of soluble sulfate which may be contained in the aqueous medium except that concentrations in excess of the saturation limit, about 40 weight percent depending on the choice of sulfate, will be lost from the process as solids. In the case of a magnesium sulfate promoted wet limestone process, the preferred concentration of soluble sulfate is from about 5 weight percent to about 27 weight percent.
The specific manner in which scrubbing efficiency of a limestone slurry is improved by promotion with a soluble sulfate is not known, however, the sulfate ion may reduce calcium ion cncentration thus freeing basic ions from their insoluble compounds. As a consequence of the increased dissolved scrubbing capacity casued by addition of a soluble sulfate it becomes possible to use the supernatent separated from spent slurry to remove additional sulfur dioxide from the gas. The total removal can thus exceed 95% of the sulfur dioxide in the waste gas without incurring the pressure drop penalties of multiple short-contact-time scrubbers or the plugging problems encountered when the total slurry is used in a packed tower.
Referring now to the drawings, a flowsheet of a preferred embodiment of the invention is presented in H0. 1.
22,800 SCFM of waste gas at a temperature of 300F and pressure of 15.1 psia. and having the following composition by volume:
SO, I800 ppm. S trace 0 3 CO 13% N & Argon 7071 H 0 14% is introduced to the Venturi section of contacting zone 2 by means of waste gas line 3. Entering gas is contacted with 740 gpm. of aqueous medium from line 4 containing principally, by weight, 4.0 percent calcium sulfate, 5.0 percent calcium sulfite, 1.0 percent calcium carbonate, 12.7 percent magnesium sulfate, and entrained carbon dioxide.
Gas leaving the Venturi section then passes through a packed section of contacting zone 2 comprising a three feet deep bed of ceramic saddles where the gas is contacted countercurrently by [85 gpm. of an aqueous supernatent from line 5 containing principally 14 weight percent magnesium sulfate, and entrained carbon dioxide and is then passed to the atmosphere through line 6. Total gas-liquid contact time in the contacting zone is 0.5 seconds. Sulfur dioxide content of the waste gas is reduced to l80 ppm. (by volume) and the thus treated gas leaves the contacting zone at a temperature of 130F.
The aqueous medium and aqueous supernatent streams are then combined and passed to make-up tank 7 where 12 pounds per minute of limestone are added from line 8. 740 gpm. of the resulting aqueous medium at a pH of about 5.4 are then recycled by way of line 4 to the contacting zone.
The remaining portion of the previously combined streams is passed to a separation zone 9 for removal through line 10 of 14 pounds per minute of precipitated solids which are predominantly calcium sulfite and cal cium sulfate in addition to small amounts of calcium carbonate and other solids. l85 gpm. of the resulting aqueous supernatent is then returned by way of line 5 to the packed section of the contacting zone 2.
The soluble sulfate of the present invention can be introduced into the aqueous scrubbing media as a sulfate or mixture of sulfate salts to provide the concentrations given above. However, it is equally advantageous to generate the soluble sulfate in situ by adding to the aqueous solution or slurry a carbonate, bicarbonate, hydroxide, sulfite, bisulfite, or oxide, or mixtures thereof, of the corresponding cations (Na*, K*, Li, Mg, or NHU). Such compounds include sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium sulfite, sodium bisulfite, sodium oxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, potassium sulfite, potassium bisulfite, potassium oxide, lithium carbonate, lithium bicarbon ate, lithium hydroxide, lithium sulfite, lithium bisulfite, lithium oxide, magnesium carbonate, magnesium bicarbonate, magnesium hydroxide, magnesium sulfite, magnesium bisulfite, magnesium oxide, ammonium carbonate, ammonium bicarbonate, ammonium hydroxide, ammonium sulfite, ammonium bisulfite, ammonium oxide.
Under the usual conditions employed in the process, these sulfate generating comounds form the soluble sulfate of the corresponding cation. Generally and in accordance with the present teachings, the addition of the soluble sulfate, soluble sulfate generating compound or liquid ammonia is in an amount stoichiometrically equivalent to provide between a 0.3 and 5.0 molal solution with respect to soluble sulfate or up to the saturation limit of the soluble compound.
Solids content of the aqueous media is preferably maintained below 20 weight percent and preferably, at least 5 weight percent of these solids is calcium carbonate. Usually, when such solids accumulate to levels above 15% it is recommended, particularly in a cyclic operation, to pass the scrubbing liquid through a filter or to similarly treat the aqueous medium to remove at least a portion of the solids. It is to be understood, how ever, that the scrubbing liquid can be a clear solution which may be obtained from recovering the aqueous supernatent,
The waste gases treated by the process of this invention are those discussed in the introductory portion of this disclosure. These gases contain between about 0.03 and 20 weight percent sulfur in the form of oxides, acids and volatile salts and usually contain between about 50 and about weight percent nitrogen and be tween about 0.1 and about 20 weight percent oxygen. When the gas is obtained from combustion sources, some solids such as fly ash and soot are also present in the gas. Since these solids and oxides of sulfur are most objectionable from the standpoint of health hazard, these components must be removed to levels below 500 ppm before the gas can be safely vented to the atmosphere. Although the process of the present invention permits removal of small amounts of sulfur dioxide (between about 0.0l and about 5 weight percent) from waste gases, it is not limited thereto and can be used to remove much larger concentrations from such gases as discussed above.
Generally, the present process comprises a series of treating stages including scrubbing, addition of calcium carbonate to the aqueous medium, precipitation of calcium sulfate and sulfite, and recycle of the aqueous medium. The limestone or calcium carbonate can be added to the circulating scrubbing liquid at any stage or between stages of the process but is preferably added after the scrubbing stage. The soluble sulfate or substance providing the cation of the soluble sulfate is added initially at any stage of the process. Since this material is recycled and regenerated in the cyclic system by precipitation of calcium sulfate and sulfite, there is no need for subsequent additions except as found necessary to make up normal losses.
The scrubbing step of the present process into which is introduced the untreated waste gas and the aqueous scrubbing medium containing solids may be carried out in one or a plurality of contacting zones and is preferably effected in a contacting zone having relatively short gas-liquid contact time, for example, a Venturi-type scrubber or spray tower. Representative gas-liquid contact times are generally less than three seconds and can be lower than 0.1 second.
When solids are removed from the aqueous medium to yield an aqueous supernatent, such aqueous supernatent may be separately introduced to one or more of the contacting zones in order to remove sulfur dioxide from the waste gas. The aqueous supernatent may be utilized with short or long gas-liquid contact times, for example, in packed or tray towers, spray towers, and Venturi-type scrubbers since solids accumulation on internal components of scrubbing equipment would not preclude their use.
Preferably, the aqueous supernatent is passed in countercurrent contact with waste gas in series with one or more gasliquid contact zones employing aqueous medium containing solids. One embodiment of this arrangement is depicted in the drawing as a combined contact zone provided with means for introduciton of aqueous medium containing solids to a Venturi section and separate means for introduction of aqueous supernatent to a packed section. In this manner, highly efficient sulfur dioxide removal may be attained.
Contacting of the gas and liquid phases proceeds at temperatures close to that of saturation of the gases, such temperatures are normally within the range of between about 100F and about 180F; under a pressure from 5 psia. to 50 psia., preferably from l2 psia. to 18 psia.
It is desirable that the liquid in the scrubbing zone have a pH between 4 and 7; however local acidic sites due to the formation of sulfurous acid may occur resulting in a lower pH. While pH controls solubility of components in the aqueous scrubbing media and is critical to the extent that extremes should be avoided, the pH range will normally be maintained within the stated range by operation of the process.
The limestone utilized in the process and added, for example, to the make-up tank, may or may not be previously calcined and other inexpensive sources of cal cium carbonate, such as dolomite may be substituted in whole or in part for limestone at this stage of the process. Carbon dioxide may also be added to the liquid mixture during this stage of treatment so as to adjust the pH below 7.1 if necessary. In normal operation of the process, however, carbon dioxide will be entrained in the aqueous medium from contact with the waste gas stream and/or evolution of carbon dioxide from reaction of calcium carbonate in the aqueous medium thus obviating such addition.
The zone of limestone addition is maintained at a temperature substantially within the range employed in the contacting zone, and at a similar pressure, preferably at the same temperature and a pressure between l l psia. and 25 psia.
The amount of calcium carbonate in the form of limestone or dolomite which is added to the aqueous medium is based on the amount of sulfur dioxide in the waste gas feed; however, a mole ratio between about 0.721 and about 2:l is recommended for efficient operation in the process of this invention. Higher ratios formerly employed in the art without the presence ofa soluble sulfate, can also be used if desired; although it is to be understood that such quantities of calcium carbonate are not required and, therefore, are merely wasted in the present process. For most efficient operation of the process, the molar relationship: soluble sulfate calcium carbonate sulfur dioxide, should be maintained in the contacting zone.
The solids in the slurry which are formed in the process by precipitation of the calcium sulfate and sulfite and any incidental fly ash, etc., removed from the gas are subjected to a separation treatment such as decantation, filtration or centrifuging or any other convenient method for separating solids from liquid. The resulting aqueous supernatent containing predominately water, soluble sulfate, entrained carbon dioxide, small amounts of bicarbonate, sultite, and bisulfite ion, and small amounts of dissolved calcium carbonate is recycled and introduced to the contacting zone preferably separate from the introduction of the solids containing aqueous medium as previously described.
When decantation is selected as the method of separation, the settling time for solids to separate is usually not more than 2 hours. The solids so separated can be discarded or subjected to further well-known treatments for the recovery of sulfur containing materials as elemental sulfur or $0 or as sulfuric acid. These further and particular stages of recovery are not included in the present invention and are left to the preference of those employing the instant process.
The recovery of solids in the present process can be effected continuously or the solid sulfate and sulfite of calcium can be allowed to build up to a certain level in the circulating scrubbing liquid before removal of solids is effected. It is recommended, however, that the solids in the slurry not be permitted to exceed 20 percent by weight for efficient operation. By the process of this invention, substantially all of the sulfur oxides of the waste gas can be removed for discard or recovery.
Examples and illustrative embodiments of the process of the present invention will now be described.
EXAMPLE 1 Runs 1 through 37 are presented for purposes of comparison to show the capacity of scrubbing media for removal of sulfur dioxide from waste gases with and without the inclusion of a soluble sulfate in such media.
In each of the following runs, a simulated waste gas, containing about 3.0 volume percent oxygen; about volume percent nitrogen and about 17 volume percent carbon dioxide in addition to varying amounts of sulfur dioxide as reported in Table l, is bubbled into the bottom of an elongated glass tube at a rate of about 1 liter per minute and through the liquid body of scrubbing medium contained in the tube at a temperature of 25C under atmospheric pressure. Since the simulated waste gas contained no solids, the viscosity of the scrubbing liquid is easily controlled. The gas is contacted with the scrubbing liquid for about 0.3 second which is comparable to the desired contact time in commercial gas scrubbers, e.g., a scrubber of the Venturi type. The flow rate was selected such that 1 weight percent of the aqueous CaCO slurry showed about 50% scrubbing capacity, i.e., utilization of the CaCO when sulfur dioxide breakthrough was detected. Breakthrough is measured by passing the scrubbed gas through a conductivity cell which measures the sulfur dioxide in the scrubbed gas exiting from the treating zone. The data for each run includes a correction for the amount of SO which would be removed by pure water or water containing solids other than CaCO under the conditions of operation. The millimoles of SO removed by water alone is subtracted from the net S0 absorbed due to components in the aqueous liquid to provide the value of Net S0 absorbed in the Table I.
At start up, the equipment is flushed with a mixture containing nitrogen, oxygen, carbon dioxide and sulfur dioxide, and the tubular glass scrubber is evacuated and then charged with the scrubbing liquid to be tested which, in most of the examples, is a slurry containing uniformly admixed calcium carbonate and water and may or may not contain the sodium or calcium salts 8 cally no effect on the scrubbing capacity of the liquid. Runs 4. S, 14 and 16, inclusive, illustrate the effect of employing sodium sulfate below the concentration limit of the invention, e.g., 1% with or without added mentioned above. The examples which contain no salt CaSO and CaSO; in the slurry. It is found that, at these other than calcium carbonate are set forth for the purlow concentrations, the improvement in scrubbing capose ofa control run, on which comparison with scrubpaeity due to added sulfate is not substantial. Run 5 2 :8 hqutld lmmalllmgthfi 5 11 Sulfate bgf bilfilcd suggests that low sulfate concentration is detrimental e Inn in runs simu ate t e imcstone cr mg s urwhen using relatively high CaCO concentrations. ries which have been used in known processes. About In runs 7 and 12, employing Na SO as the soluble 100 ml. water are used to prepare the scrub ing liquid compound, 1% of the soluble salt is sufficient to show for each some improvement in the scrubbing capacit d h" y an t is T116 conductivity C011 15 With 1111.0f21 8011111011 imprgvcmgnt is btained ga dless of the addition f containing 0.003 molal H202 and 0.00002 molal other i l bl alts such as CaSO and CaSO- How- Z l All instruments Of the l are then n r 15 ever, runs 9 and 13 indicate that concentrations of ized. In the conductivity cell any 50 gas in the scrub NA SO below 1% (e.g., 0.3%) provide no improvefi vapor is Oxidized y thfi Peroxide tO form H2SO4- merit whatever and that the additional presence of This procedure provides cummulative measurement of olid calcium sulfate and sulfite seems to provide a the $0 so that break-through is arbitrarily set at a total 70 negative result. leakage 010.025 millimoles of S0 Analysis ofthe feed Runs 20, 21, 24, 28 and 30 provide a comparison gas for S0 is accomplished by absorbing a known vol i h higher Concentrations of 2 4 the r ing time of gas in 50 ml. of a more concentrated pe id solution, i.e., 1 molal concentration. It is observed that solution and titrating the formed sulfuric acid with soan improvement of 55 to 80% in the utilization of diurn hydroxide. we CaCO can be obtained with the higher concentration In all experiments the total volume of gas passed of 2 4 and this 1mPrPVeme11t 15 Obtamed f through the scrubber at breakthrough is measured and Presence absence of "1501111318 Sulfams or sulmes from this total volume and from the feed analysis, the Such as Calclum Sulfate or Sumter amount of S0 removed by the scrubbing operation is "11115 31 through 37 h expenmems wcrc i d ducted such that the scrubbing step could be run sepaca cu ate 30 In Table l, runs 1 through 3 inclusive, show the effect i the dlssnlvmg. and preclpltanfm. Smps' After 1 I s v equilibrating a slurry with a gas containing CO the of increasing the amount of CaLO in the slurry from a v clear solution was obtained by filtration and 100 ml. 0.6/( to 1 K and then to 10% by weight concentration. were used in the scrubber. It was not the limestone uti- The scrubbing liquids of these examples are representalization that was important in these runs but rather the tive ot those employed in commercial limestone scrubdissolved scrubbing capacity of 100 ml. of solution. bing processes which use the wet method. The results t I h th't l i 3 t f 0rd h t V a t The improvement ratios for this set of experiments was g 1 V fi 1 S a 1 f re calculated on changes in the dissolved scrubbing caa t e E u rcmdmlds pacity compared to a control containing no sulfate and 50 F f l 68 an l 9 dclcummu um] equilbrated with a gas containing 17% CO the desirable limit of the liquid viscosity prohibits fur- The high improvement ratios found in runs 32 34 9 5 their Cacoa uddmon' plmcullrly It noted-by and 35 demonstrate the increase in dissolved scrubbing 9 1 1 h; that the aTlnOunFOfhmf'tSwm capacity caused by sulfate either in the presence or a bf cffmency of thfi CACOB 1 the scrub sence of other solids. Run 36 shows the increase in disbmg hqu'd Of h9g9 examples Propomonately solved scrubbing capacity that could be achieved by creases raising the partial pressure of CO to 1 atmohspere at- RUHS 18 and 31 Show the @fffllt 0f amosphere the absence of soluble sulfate and run 37 SO ZH O and CaSO .2H O addition to CaCO in a shows the combined effects of increased C0 partial slurry. It is seen that these solids, alone, have practipressure and soluble sulfate.
TABLE 1 Run 1 2" 3 4 S 6 7 8 9 Gas Flow-liters/min. 1.0 1.1 1.1 1.1 1.1 1.0 1.0 L0 1.0 v01. 7t 50.; in Gas .46 .46 .46 .46 .46 .s .8 .s .8 SLURRY (aCO -grams (milli .6 1.0 10. 1.0 10. 2.0 2.0 0.6 0.6 H 0 6 (10 100 101 100) 228 28) (162) (167) a v grams CaSO;.2H:O--grams v 4.0 4.0 1.2 1.2 Na,SO grams 0.1 1.0 lmillimolsl [0.7) (7.0) Na SO; grams [milli- 1.0 0.3 molsl (7.9] [2.4)
Gas Scrubbedliters 19.00 26.47 126.53 29.1 52.4 25.88 59.21 15.74 17.54 Milllmols sO iliter of gas 0.188 0.188 0.188 0.188 0.188 0.326 0.326 0.326 0.326 502 Scrubbetlmillimols 3.57 4.99 23.8 5.46 9.85 8.45 19.3 5.14 572 S02 leaked 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 0.025 absorbed 3.55 4.97 23.78 5.44 9.83 8.43 19.23 5.12 5.70 Wa ter Correction .55 .55 .55 .55 .55 .55 .55 .55 .55 Solids*+Water Correction millimols i 1.51 1.51 1.59 1.59 Net S0 absorbed milIimoIs 3.0 4.42 23.23 4.39 9.28 6.92 17.77 3.53 4.11 Scrubbing Capacity of CaCO 50 44.2 23.2 48.9 9.28 34.6 51.3 59.0 29.9
TABLE 1-C0ntinued Run Improvement Ratio Run A 1 I 1 32: bob 2 ##pm I I 1 @0 0 Run Gas Flow-liters/min.
Vol/X SO in Gas Vo1.% CO in regenerator gas SLURRY mols] CaSO,.2H,O grams CaSO .2H O grams Na,SO grams (millimols) Nz1 SO grams [millimols) Gas Scrubbed1iters Millimols SO,/1iter 01' gas S0 scrubbed millimols SO, leaked SO absorbed Water Correction So1ids*+Water Correctionmillimols Net SO absorbedmi11imo1s*** Scrubbing Capacity of CaCO Improvement Ratio Run Gas Flow-liters/rnin. Vol.9? $0 in Gas Vol/k CO in regen. gas
SLURRY CaCO;,grams (millimols] CaSO,.2H O grams CaSO .2H,O grams Na SO grams (Millimols) Na- SO grams (mi1limol Gas Scrubbed-liters Millimols SO /1iter 01' gas S0 scrubbed-millimols SO, leaked SO, absorbed Water Correction So1ids*+Water Cor rection-millimols Net S0 absorbedmillimols Scrubbing Capacity of CaC Improvement Ratio solids other than CuCO *not measured; ""by Components other than water Control for Run l-S; Control for Run 6 and 7; Control for Run 8. 9, and I3,
" Control for Run 12, 14, 15. and 16; "Control for Run 18, 20, 21. and 22; 'Control for Run 24-, "The average of runs 26 and 27 is the control for Run 28; Control for Run 30; "Control for Run 31, 32, 34. 35. 36 and 37;
"' Blank run on the scrubbing capacity of an aqueous 14; solution of Na,SO, in the absence of other Componcnts.
yed clear solution- 3.32 3.59
In an illustrative embodiment of the present invention about l volumes of an aqueous slurry containing about weigh percent solids. 6 weight percent MgO, 4 weight percent CaSO, and CaSO is introduced into the upper portion of a glass tube. The simulated waste gas of Example 1 containing 0.47% 50 is introduced into the bottom of the tube and is passed upwardly through the slurry at a rate of l liter/minute at a temperature of 25C under atmospheric pressure until the MgO is converted to MgSO by the action of S0 and O in the gas; whereupon 1 weight percent of CaCO is added to the slurry. After 1 hour of operation waste gas in withdrawn from the top of the glass tube. The waste gas contains less than 10 ppm S0 and S0 Accordingly, more than 99.7% of the oxides of sulfur is ab sorbed in the slurry. The improvement ratio of calcium carbonate utilization in this slurry over the standard aqueous limestone, CaSO CaSO slurry, as described in Example l, run 19, is 2.0.
In another illustrative embodiment of the present invention, about 100 volumes of an aqueous slurry containing about 6 weight percent solids, weight percent NH 6 weight percent CaSO and CaSO is introduced into the upper portion ofa glass tube. The simu lated waste gas of Example 1 is introduced into the bottom of the tube and is passed upwardly through the slurry at a rate of l liter/minute at a temperature of 25C under atmospheric pressure until (NH SO is formed; whereupon 1 weight percent CaSO- is added to the slurry. After 2 hours of operation waste gas is withdrawn from the top of the glass tube. The waste gas contains less than 10 ppm 80 and S0 Accordingly, more than 99.7% of the oxides of sulfur is absorbed in the slurry. The improvement ratio of calcium carbonate utilization in this slurry over the standard agueous limestone. CaSO CaSO slurry, as described in Example 1, run 19, is 2.2.
In an additional illustrative embodiment of the present invention, about lOO volumes of an aqueous slurry containing about 7 weight percent solids, weight percent KOH. 7 weight percent CaSO, and CaSO is introduced into the upper portion of a glass tube. The simulated waste gas of Example 1 is introduced into the bottom of the tube and is passed upwardly through the slurry at a rate of l liter/minute at a temperature of C under atmospheric pressure until K 50 is formed from KOH; whereupon 1 weight percent CaCO in the form of limestone is added to the slurry. After 1 hour of operation waste gas is withdrawn from the top of the glass tube. The waste gas contains less than 10 ppm S0 and S0 Accordingly, more than 99.7% of the oxides of sulfur is absorbed in the slurry. The improvement ratio of calcium carbonate utilization in this slurry over the standard aqueous limestone, CaSO CaSO slurry, as described in Example 1, run 19, is 2.0.
In an additional illustrative embodiment of the present invention. about 100 volumes of an aqueous slurry containing about 6 weight percent solids. 25 weight percent of (NH CO 6 weight percent of a CaSO and CaSO is introduced into the upper portion of a glass tube. The simulated waste gas of Example 1 is introduced into the bottom of the tube and is passed upwardly through the slurry at a rate of 2 liters/minute at a temperature of 35C under a pressure of 5 psig. until the (NH CO is converted to (NH SO whereupon 1 weight percent CaCO is added to the slurry. After 0.5 hour of operation waste gas is withdrawn from the top of the glass tube. The waste gas contains less than 10 ppm S0 and S0 Accordingly, more than 99.7% of the oxides of sulfur is absorbed in the slurry. The improvement ratio of calcium carbonate utilization in this slurry over the standard aqueous limestone. CaSO,, CaSO slurry, as described in Example I, run 19 is 2.2.
The scrubbing liquids of each of the foregoing embodiments can be treated for regeneration of soluble sulfate and recovery of sulfur values as calcium sulfate and calcium sulfite in the manner set forth above in the description of the drawing.
EXAMPLE 2 This example illustrates the comparative S0 removal efficiencies of limestone slurry systems promoted respectively with magnesium sulfate, sodium sulfate, and ammonium sulfate as compared with unpromoted limestone slurry systems when such systems are utilized in a Venturi-type scrubber.
Test runs summarized in Table ll were made in an unsteady-state condition by passing 1.000 SCFM of simulated waste gas having the constant volume composition of 15% carbon dioxide, 02 to 0.3 percent sulfur dioxide, and balance air through an 8-inch Venturitype scrubber in co-current contact with an initially fixed composition limestone aqueous slurry system. The solids component of the slurry systems was calcium carbonate, calcium sulfate, and calcium sulfite. Since the solids composition was fixed at the beginning of each run without subsequent additions or removals, ratios of the aforementioned solids as well as solution characteristics of the slurry changed during the duration of each run. Each of the runs utilizing promoted slurries was terminated when the percent removal of sulfur dioxide decreased sharply. Runs 1 and 2 utilizing unpromoted limestone slurries. were terminated arbitrarily since percent sulfur dioxide removal remained at a relatively constant low level.
An agitated slurry tank was used to receive scrubber effluent and to serve as a pump tank for recirculation of the slurry to the scrubber. Slurry temperatures were maintained in the range of from about l25F to about l35F.
Prior to the test runs summarized in Table II, simulated waste gas was scrubbed in the equipment described with an aqueous sodium carbonate solution which has a high potential for absorbing sulfur dioxide and essentially zero sulfur dioxide back pressure. Accordingly, it was found that the mass transfer limit of the scrubber under these operating conditions was about Thus, the percent sulfur dioxide removal data summarized in Table ll can be considered against the background of this limitation.
The data presented in Table ll illustrates that the per cent sulfur dioxide removal from simulated waste gas is significantly increased by scrubbing such gas with promoted limestone slurries that are representative of the present invention as compared with unpromoted limestone slurries.
TABLE ll Promoter none MgSO Na-,,SO (NH SO Run 1 3 4 6 7 9 l0 Slurry Rate, gpm. 20 30 33 33 33 33 33 33 33 33 33 Promoter Concentration, ll.2 24.8 15.2 l3.4 l3.0 12.5 13.3 l3.3 27.0
13 14 TABLE 11 Continued Promoter none M gSO, M1 80, (N H, ),SO,
Run 2 4 5 7 8 9 10 wt. percent pH Venturi, initial 5.3 6.2 5.9 5.1 5.4 6.3 6.1 6.3 6.6 5.8 6.5 final 5.0 5.4 4.9 4.4 4.6 5.4 5.3 6.2 4.9 4.8 4.8 Run length. hours 6.5 5.0 13.7 9.5 6.0 7.2 7.8 4.0 6.5 7.0 8.7 Initial Wt. percent solids 5.0" 5.4 10.2 5.0 9.6 7.8 10.0 14.8 5.5 13.5" 105" Initial percent CaCO 94.9 68.6 48.3 94.9 68.5 56.] 37.4 30.4 94.4 230 30.8
in so: 5 S0 Removal. max! 27.3 26.8 67.7 55.9 59.0 51.9 49.7 53.9 66.7 63.4 71.8 Wt. percent solids at max. 5.0" 4.3 10.3 4.8 7.2 7.6 10.9" 14.4 5.4 12.5 98
SO, removal Wt. percent CaC'O in solids 89.3 59.6 22.2 61.8 64.9 31.6 19.6 28.7" 37.7 23.0 27.7
at max. SO, removal "'Bascd on hourly sampling period "lntcrpolatcd Many modifications and variations of this process will become apparent from the above disclosure without departing from the scope of this invention.
Having thus described our invention, we claim: 1. A process for removing sulfur dioxide from industrial waste gas which comprises:
scrubbing waste gas in a contacting zone with an aqueous medium having a pH below 7.1 containing clacium carbonate, carbon dioxide and at least about 3 weight percent of a soluble sulfate selected from the group consisting of sodium, lithium, potassium, magnesium, and ammonium sulfates;
precipitating solids selected from the group consisting of calcium sulfite and calcium sulfate from the aqueous medium;
removing a portion of said solids; and
introducing a remaining portion of the solids with said aqueous medium to the contacting zone.
2. The process of claim 1 wherein gas-liquid contact time in said contacting zone is less than 3 seconds.
3. The process of claim 2 wherein said contacting zone is a venturi scrubber.
4. The process of claim 2 wherein said soluble sulfate in the aqueous medium is present in the range from about 5 weight percent to about 27 weight percent.
5. The process of claim 1 wherein said soluble sulfate is generated in the aqueous medium by the addition of ammonia or the oxide, hydroxide, carbonate, bicarbonate, sulfite or bisulfite of sodium, lithium, potassium, magnesium or ammonia or mixtures thereof.
6. The process of claim 4 wherein temperature of the contacting zone is from about 100F to about 180F and the pressure is from about 12 psia. to about 18 psia.
7. The process of claim 1 wherein at least part of the aqueous medium is recovered as an aqueous supernatent containing at least about 3 weight percent of a soluble sulfate selected from the group consisting of sodium, lithium, potassium, magnesium, and ammonium sulfates and said aqueous supernatent is separately introduced to the contacting zone.
8. The process of claim 4 wherein at least 5 weight percent of the solids introduced to the contacting zone with said aqueous medium are calcium carbonate and said calcium carbonate is added to the aqueous medium as limestone or dolomite.
9. The process of claim 2 wherein the waste gas contains oxygen, carbon dioxide and from about 0.01 weight percent to about 5 weight percent sulfur dioxide.
10. A process for removing sulfur dioxide from industrial waste gas which comprises:
scrubbing waste gas containing from about 0.01
weight percent to about 5 weight percent sulfur dioxide in a contacting zone wherein gas-liquid contact time is less than 5 seconds with an aqueous medium having a pH below 7.1 containing calcium carbonate, carbon dioxide, and from about 5 weight percent to about 27 weight percent of magnesium sulfate precipitating as solids, calcium sulfite and calcium sulfate from the aqueous medium;
removing a portion of said solids;
introducing a remaining portion of the solids with said aqueous medium to the contacting zone, said solids containing at least 5 weight percent calcium carbonate based on total solids;
recovering at least part of the aqueous medium as an aqueous supernatent containing at least about 5 weight percent of magnesium sulfate; and introducing said aqueous supernatent separately to the contacting zone.
Patent Citations
Referenced by
Legal Events
Original Image


text:
LOS ANGELES (AP) — Patrick Dempsey says he wants to rescue a coffee house chain and more than 500 jobs.
The "Grey's Anatomy" star said Wednesday he's leading a group attempting to buy Tully's Coffee. The Seattle-based company filed for Chapter 11 bankruptcy protection in October.
Dempsey said he's excited about the chance to help hundreds of workers and give back to Seattle.
The actor has a strong TV tie to the city: He plays Dr. Derek Shepherd on "Grey's Anatomy," the ABC drama set at fictional Seattle Grace Hospital.
Tully's has 47 company-run stores in Washington and California, as well as five franchised stores and 58 licensed locations in the U.S.
Any sale would have to be approved by a judge. A bankruptcy court hearing is set for Jan. 11 in Seattle.
WH Totally Supports What Planned Parenthood Is Doing, Notes Its 'High Ethical Standard' | Leah Barkoukis
Video: Visitors Leaving National Archives Mostly Clueless About Their First Amendment Rights | Matt Vespa
In Honor of His 103rd Birthday, Here Are The 20 Best Quotes From The Late, Great Milton Friedman | John Hawkins
Update: Univ. of New Hampshire president stands up for free speech after "language guide" flap | Mary Katharine Ham

subset: commoncrawl


text:
Windows 8 Mail leaves users pining for the desktop—or even their phones
Metro Mail has the skeleton of a good client, but hasn't been fleshed out.
Metro Mail has the skeleton of a good client, but hasn't been fleshed out.
Touchscreens featured prominently in PCs at this year's Computex.
Moving off of Windows 7 may be a tough sell for Microsoft.
The Metro-style apps put the Xbox branding front and center.
No auto file syncing, but direct integration with Metro and Web Office apps.
A move to appease OEMs, not antivirus developers.
Simple apps highlight Microsoft's plans for the Metro interface.
It's no iCloud, and maybe that's a good thing.
Private, but not very advertiser-friendly.
In a sparse app store, Microsoft's featured picks are about as good as it gets.
Buy a Windows 7 PC starting tomorrow, get a cheap upgrade to Windows 8.
Hot corners are better, but new quirks have been introduced.
Store puts all Metro apps in one place, but needs better discoverability.
Microsoft's listed requirements fall short for daily use.
Ladies and gentlemen, start your downloads!
Your very own personal assistant, a better browser... and something called the Start menu.
Nearly a year in, Hacker's List maintains good intentions. Its users on the other hand...
From error handling to app thinning, Apple continues to nudge devs away from ObjC.
The occasional frustration still beats the very low bar set by car manufacturers.
iPhones have eaten the iPod, but this new release is still useful for specific purposes.


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We are glad to bring you to our free ringtones website, where you can easily find free ringtones for your smart phone. Today we have a ringtone of "Changed the Way You Kissed Me" by Example as well as 1593 other ringtones by Example. "Changed the Way You Kissed Me" is a top-rated song from the "Changed The Way You Kiss Me" album that was made by Example at their recording studio together with other 5 tracks. You can listen to all 58 Example – "Changed the Way You Kissed Me" ringtone variations available here and download it for free right here. You can also find other 7 albums produced by Example for all time. "Changed the Way You Kissed Me" is referred to British, and you may listen to a huge amount of British ringtones absolutely for free. And finally, we have collected lyrics for this track and you can view it here as well. So feel free to browse, listen, download ringtones at Audiko.net. Make your phone sound cool!
Example Changed the Way You Kissed Me Ringtone
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October 29, 2010
Album Review: Good Charlotte - Cardiology (Polydor)
Monstrously offensive record which doesn't really deserve your time/money/earsMore on Good Charlotte
1 / 10 Whoa! A quick glance at the tracklisting for 'Cardiology' suggests Good Charlotte might have started covering The Smashing Pumpkins ('1979') and The La's ('There She Goes'). Which is, if not downright creepy, then just a little bit beguiling. But no, both songs are stone-cold Madden originals. Booo! If you like your rock'n'roll played by four fat talentless fucks and Morrissey's old drummer Dean Butterworth (seriously, wtf?!), then… oh just sod off, yeah? Disgustingly derivative and Pro Tooled to the max, 'Cardiology' is monstrously offensive – the latest shit-streak by music's laziest sons. But seriously, what did you expect? Amazing indie covers?
Matt Wilkinson
Matt Wilkinson
To read all our reviews first - days before they appear online - check out NME magazine, on sale every Wednesday
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Siemens SISHIP LV drives and SINAMICS components to power customer's environmentally friendly, next-generation fishing vessel, saving up to 30% in annual fuel and maintenance costs.
Based in Seattle, Blue North Fisheries (BNF) operates five fishing boats called "freezer long liners" in the Bering Sea and Gulf of Alaska and one smaller seiner in Alaska, Washington and Oregon. BNF's largest vessel is 180-feet long with a crew of 23, while its smaller seiner is 58-feet long with a crew of six. Established in 1983, BNF has grown to approximately 150 employees. It harvests and sells more than 20,000 metric tons of fish and fish products each year.
Challenge: To design a fishing vessel that delivers the most premium fish products for each measure of fuel burned in the most environmentally friendly, efficient and reliable way
BNF's fishing fleet is out to sea most of the year, harvesting Pacific cod from ocean depths of up to 3,000 feet or more. Long line fishing uses a main line that can be many miles in length with many branch lines, each with a hand-baited hook.
Weather in the Bering Sea and Gulf of Alaska is brutal more often than not. Waves up to 20 feet or more are constantly washing corrosive salt water over the decks of BNF's older boats, some of which are WWII-vintage. Maintenance on the vessels can't be deferred, but neither can they be at port too long, since they're the source of the company's product—and revenue. Still, with the harsh conditions they face, the boats are in constant need of maintenance and repair. And with their advanced age, those costs are only rising.
At the same time, the vessels' diesel engines, which are also old, gulp fuel from tanks that cost hundreds of thousands of dollars to fill. With maintenance and fuel costs rising, BNF's management decided the time had come to modernize their fleet. Even more, they decided to build one of the most environmentally friendly and technologically advanced fishing vessels in the world.
Solution: Anext-generation long lining fishing vessel with diesel-electric propulsion featuring a Siemens BLUEDRIVE SISHIP LV drive system
For their first new vessel, which will be christened the "Blue North," BNF chose the 58.35 meter (191 feet) ST-155, a new long liner designed by Skipsteknisk AS,a Norwegian firm. Its center hull features a breakthrough fishing concept called a "internal hauling pool." Inside this weather-protected enclosure, BNF's crew will haul in the long line, reducing fish losses and enjoy much more safety, even in the worst weather.
According to BNF President and CEO Kenny Down, the new Blue North will not focus on catching more fish; instead, its onboard processing facility will use more of the fish that are caught.
That's because it will employ more effective fishing methods along with faster, more efficient on-board processing of cod products. This provides fresher, better quality cod products for the nation's leading food stores and their discerning customers, who are increasingly seeking environmentally sound and sustainable sources for their food.
"Present fishing practices are extremely wasteful and inefficient," Down says. "With our new vessel, we believe we can implement significant processing changes that will make considerable sustainability and efficiency differences."
To improve engine efficiency while reducing fuel costs and emissions, BNF elected to power their vessel with an ultra-compact, twin-bladed, dual-azimuth, diesel-electric propulsion (DEP)system. It's the first fishing vessel in North America to incorporate Siemens BLUEDRIVE DEP technology.
Instead of using diesel engines to drive a propeller mechanically, DEP uses diesel generators to produce power that drives the vessel's electric motors as well as its fish processing plant, freezers, lighting, heating and marine electronics. Thanks in part to the Siemens BLUEDRIVE DEP technology, and Caterpillar engines, the Blue North will be one of the first fishing vessels to meet new Tier III emissions standards set by the U.S. federal government. The Blue North's propulsion design uses the well-proven technology of Siemens Marine & Shipbuilding to turn a Z–drive propeller directly, without the cost, space and maintenance required by excessive reduction gearing and long drive-shaft lines conventional long lining vessels use. The Siemens Power Management System combined with Siemens BLUEDRIVE VFD drive technology optimizes the vessel's power efficiency, safety and reliability.
BNF's decision favored the Siemens system over the competitor's solution due to the Siemens technology, experience and reliability. It also resulted from a trusted advisor relationship that Siemens Marine Global Account Manager Luke Briant had cultivated with BNF over nearly three years. During this time, he helped the customer develop various propulsion designs with several naval architects and provided numerous calculations for BNF's business models about reducing fuel and maintenance costs.
"Siemens BLUEDRIVE technology has been used in Norway's fishing industry for the last 10 years," Briant explained. "BNF's owners and CEO traveled to Norway to meet with Skipsteknisk AS and the Siemens Marine Center of Competency for LV propulsion in Norway. While there, BNF surveyed other long liners with Siemens BLUEDRIVE technology and saw for themselves that Siemens could deliver on the reliability and efficiency calculations we had worked through."
Results: Up to 30 percent fuel savings and overall reduction in OPEX and faster ROI—and a revolutionary model for the entire fishing industry
Briant estimates that the Blue North equipped with Siemens BLUEDRIVE technology will save up to 30 percent in fuel consumption. In addition, he says the total greenhouse gas emissions are much lower compared to vessels with direct-drive diesel propulsion or with alternative DEP systems. The Siemens BLUEDRIVE technology will also help BNF reduce its diesel engine maintenance costs compared to other DEP systems now on the market.
For BNF, the savings in fuel and maintenance costs will help improve profitability. Also, boosting profits will be the new vessel's ability to process more of each fish that's caught as well as selling once-discarded parts.
But in addition to increased profitability, Down points out, that BNF's new vessel will enable it to provide a better quality product to stores and their customers. "Through grocery retailers," he said, "we'll sell our fish to environmentally conscious consumers who know they're buying a quality product that's from a low-impact, sustainable, monitored and regulated fishery."
"Ultimately, by having a vessel with such a small carbon footprint, BNF will deliver by weight the most high quality cod products with the least fuel consumed of any long lining vessel operating in North America today," Briant said.
"Once the Blue North is launched — with its Siemens BLUEDRIVE propulsion technology, Z drive propellers, high-end processing and fishing equipment, habitability standards and overall cutting edge design from Skipsteknisk AS — it will be the ultimate standard in long lining vessels in North America and possibly worldwide."
The Spanish company SENER, Ingeniería y Sistemas S.A has closed a contract with U.K.-based BAE Systems PLC for the integration between FORAN CAD/CAM System and
Many plastics and metallic alloys present machining challenges as some deform and are difficult to maintain exacting tolerances, while others require strict and
Yacht service, refit, repair and maintenance yard Marina Barcelona 92 (MB'92) has awarded a contract to Pearlson Shiplift Corporation (PSC) for the design and supply
A small section of the Upper Houston Ship Channel was closed Tuesday morning after a report of 1,000 gallons of diesel entered Greens Bayou from a cement facility, the U.
Strainstall designs and delivers a load measurement solution for the world's largest floating wharf at Port of Dampier.
Strainstall, part of James Fisher and Sons plc,
Costa's two new cruise ships will be the largest ever built based on guest capacity; Costa will join sister brand AIDA Cruises in building the first-ever cruise
Rolls-Royce announced delivery of the twin fixed pitch propellers to Bath Iron Works for installation on the U.S. Navy's most modern surface combatant, the future USS Zumwalt,
Damen Maaskant Shipyards Stellendam have a decade-long relationship with the family-run Groen Offshore, Guard & Support, having built seismic research vessels and
All American Marine, Inc. (AAM) has entered into a contract with the University of New Hampshire (UNH) for the design and construction of a new aluminum catamaran research vessel.
Idreco (International Dredger Constructions) of the Netherlands informs it has designed, built and installed its second dredger, an ISD 600 with a digging depth of 30 meters,
A third Nova Scotian company has secured a multimillion dollar contract with the Cape Sharp Tidal project, which has potential to be the first grid-connected tidal array in the world.


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If you've seen any of Korean director Hong Sang-soon's previous films ("Woman on the Beach," for example, which played at the Grand Illusion in 2008), you'll immediately recognize "In Another Country" as Hong's handiwork. His trademark themes, visual style and multipart story structure have become so familiar that some critics have charged him with stagnant repetition.
"In Another Country" doesn't deserve that kind of flippant dismissal. While it's not as rewarding as "Woman," it curiously unfolds as a triptych involving three different French women named Anne, each visiting a Korean seaside village and intermingling with the same or similar characters.
To fill those roles, Hong scored a casting coup: He called upon French film legend Isabelle Huppert to play all three Annes. When the film's structural novelty begins to wear off, we've still got Huppert's subtle performances to marvel at.
So you've got three Annes (a single filmmaker; the cheating wife of a businessman; a recent divorcee still stinging from her ex's infidelities) in three discreet yet subtly interconnected story lines. They involve supporting characters appearing in each story line as variants of themselves — with one exception: Each Anne encounters an awkwardly smitten lifeguard (Yoo Jun-sang) who's woven into all three story lines.
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I can't say for sure if it all hangs together (or even if this synopsis is totally accurate) because by the time its third story kicked in, "In Another Country" lost me. Hong's small, insular, character-based films have frequently been compared to the work of French director Eric Rohmer, and to some extent that honor applies here. But while it's always fascinating to watch Huppert (who turns 60 in March) as she rises to an acting challenge, I kept wishing this actually was a Rohmer film, which probably would've been half as clever but far more engaging.


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2007 End Of The Year Listiness
31 Dec, 2007 by John Hawkins
Print this article Font size -16+
RWN returns to a regular schedule on Wed. Today, we have end of the year lists from all over the web…
The Top 20 Stories Of 2007
RWN's Favorite 15 Quotes Of The Day For 2007
The 2nd Annual Worst Quotes From The Daily Kos (2007 Edition)
The 10 Worst Quotes From The Huffington Post For 2007
Top 10 Scientific Breakthroughs of 2007
2007's winners and losers
The Top 20 Non-Eye Candy Stories Of 2007 On Conservative Grapevine.
Top 10 Britney Spears pics of 2007
Funniest news stories of 2007
The 101 Dumbest Moments in Business, 2007
Dishonest Reporter 2007 Awards
Top Ten News Stories of 2007 According To National Geographic
Top 10 Stories of 2007 According To WebMD
The Top 10 Hometown Hotties Of 2007
The Top 10 Worst Gadgets of 2007
The 10 Best and Worst Things to Happen to Men in 2007
The Top Ten Stupid Criminals of 2007
The 6th Annual Right Wing News Conservative Blog Awards
2007: Seven Things We Should Pretend Never Happened
Also see...
Father Hands Out Haymakers to Teenage Girl Punks for Attacking His Daughter [Video]Jun 29, 2015 | By Terresa Monroe-Hamilton
This dad punches the crap out of two girls attacking his daughter. Tell me you wouldn't do the same if a pack of thugs were beating on your child. I...Read More
John Hawkins
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Question: "Just how many hours do you sleep each night? Between all the work you do on your blogs (which


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Arizona Cardinals
Arians praises Cards' staff, players for work in OTAs
Within a couple of weeks of his mid-January hire, Bruce Arians had rounded out his 21-member coaching staff.
He fused together a team of experienced, long-tenured coaches with young, up-and-coming names to create a staff that outnumbered former Arizona Cardinals' head coach Ken Whisenhunt's regime by four. Then, Arians said that his staff -- one of the largest in the NFL -- would take pay cuts in order to up the coach-to-player ratio.
As OTAs resumed on Monday, Arians spoke highly of his staff and the work they've done this offseason.
"I've been really pleased," the coach said following Monday's activities. "The staff has done a phenomenal job, especially in fundamentals and teaching techniques."
Arians went on to speak to the all-around progress that he has seen his coaches put into effect as the changing-of-the-guard process continues.
"In each phase, at every position, in each group, we've got 95 percent of everything installed, both sides of the ball and the kicking game."
That considered, the coach couldn't help to reiterate: "I've just been really pleased. I can't say enough good things about this staff."
But he didn't limit his praise to his fellow coaches. The players, too, Arians insisted, were right on track.
"This group is way beyond where I thought they'd be right now," he said, speaking of the names on his roster.
In addition to being generally ahead of schedule with their OTA progress, Arians pointed out the sharpness of his players as they resumed activities after a week off.
"After a week off, I expected it to be a lot sloppier," he explained. "We had a couple of false starts and offsides, but all in all, I was really pleased with where we picked back up in all phases."
Thursday will be the final day of Cardinals organized team activities. Next week, non-veterans will participate in a mandatory three-day minicamp.
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- Hardware - Monday July 27The Sign of Our Times award, the 2nd Place Isn't So Bad award and more


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Written on: 27/10/2012 by grandmamorag (1 review written)
Why can't all deliveries be like this? From ordering through to delivery it would be impossible to improve on your service. With no access to my laptop at the time I had to phone in my order. The lady who took my order was efficient and quick. I received an e-mail that same day confirming my order and the following morning got a text to say that my order was being delivered that same day and an approximate time with an option to change it. I was even given the delivery driver's name and the company who were delivering.Impressive from start to finish.
As rated by our community of reviewers
" Waterproof saocks " Read More
" Does the job but cheaper on Amazon " Read More
" Wont Refund for out of stock item " Read More
Written by oh4fooksake
" Great Service at Sheffield " Read More
" Items not in stock " Read More


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Used Chevrolet Silverado 3500 in El Paso, TX
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2001 Chevrolet Silverado 3500 4 Dr LT 4WD Crew Cab LB Review
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overall great truck by chevy duramax diesel has plenty of horsepower and mostly torque love to take the truck on long trips because theres tons of room in the cab and is very dependable with the diesel engine and military tough Allison Transmission
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Avg. Dealer Rating: (1 review) "Mileage was over 10,000, not the 2600 stated on cargurus. Vehicle damaged and dirty."
2015 Chevrolet Silverado 3500HD LT Crew Cab 4WD Used Cars in Las Cruces, NM 88005
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Avg. Dealer Rating: (5 reviews) "If I could do half a star I would that's how bad their service is. Salesperson was supposed to get back with me never did, then was told manager would be calling me 3 weeks later still no call. Would not recommend horrible customer service"
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This property allows you to book online with a credit card. After submitting a reservation request, the owner or manager has 24 hours to accept, at which time your card will be charged and you will receive an email confirmation
Recent Northwest reviews
"Great cabin! Very clean and everything you could ever need! We had a great time! Family friendly, spacious and stocked!!! We will be repeat customers for sure!!"Guest: Shannon S. Date of Stay: August 2014 Review Submitted: March 14, 2015View listing
"Very nice stay with family and friends. Enjoyed the loons. Location's large lot offers a good deal of privacy."Guest: Gib Date of Stay: June 2015 Review Submitted: July 19, 2015View listing
"Had a great time with 25 friends at the Bear Point House. The house was beautiful and right on the lake as described. There was enough places for people to sleep (airbeds/couches) and enough room for our activities in the house, outside, and on the water. The place is secluded enough from neighbors so we did not have to worry much about noise. Doug was very easy to work with and I got my damaged deposit mailed 3 days after my stay."Guest: Seng Y. Date of Stay: May 2015 Review Submitted: June 16, 2015View listing
"This place is absolutely fantastic, great view of the lake, a perfect place to spend time relaxing at the lake."Guest: Bill Date of Stay: June 2015 Review Submitted: June 17, 2015View listing
Featured Destinations: Smoky Mountain Cabin Rentals, Wailea Beach Villas, Anna Maria Island Rentals, Wisconsin Dells Cabins


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Calling Out To Carol
Song Info
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About "Calling Out To Carol"
Lyrics for Stan Ridgway - "Calling Out To Carol"
Calling out to carol
She could really twist the screws
What'cha doin' monday
And are you back on the booze?
Now, I've been dooin' some thinkin'
About colorado springs
A dirty denim jacket
And a seven-dollar ring
Well, I've been keepin' busy
I've got lots of pots boiling on the stove
Who's that in the background
I'm sorry that I asked¨c¨ci guess I should have known
Callin' out to carol on the telephone call
Message on a wire comin' through a wall
Talk about old times but not too long ago
Carol was the girl that everybody got to know
When'd you change your number? hey, carol!
It's different than you had
Have you got protection?
I know some police are bad
But that's not why I called you up, now
You know I quit that scene
I told ya 'bout your pictures
I guess I'll buy that magazine
And I still remember
All those days we spent alone
You went one way while I went the other
Sometimes, I guess, that's the way things go
[Chorus: x2]
When they called me in the morning
And told me that she'd gone
I didn't want to hear it
So I just hung up the phone
Callin' out¨c¨ccallin' out to carol
Callin' out¨c¨ccallin' out to carol
Callin' out¨c¨ccallin' out to carol
Callin' out to carol
Callin' out to carol on a telephone call
Message on a wire comin' through a wall
Is this line in service¨c¨coperator says no
But carol was a girl that everybody got to know


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By Tim Brown | August 14, 2008
-- Time-Out Chicago has a brief interview online with CM Punk where he discusses his childhood and getting into wrestling. You can check it out at this link.
-- Mention of SmackDown diva Maryses run-in with an aggressive paparazzi at the WWE Summerfest convention last week has been made on several celebrity gossip websites. Hellarious.com writes Was it really worth all that fuss for some chick nobody has ever heard of? Maybe he got $10 for the shots if he was lucky, You can check out the article and pictures at this link.
-- PhillyBurbs.com is running a story on Raven suing WWE. You can check it out at this link.
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text:
Lineup (30)
Take this to the festival: Email lineup Print lineup
(457,272 listeners)
house, electro house, progressive house, electronic
Afrojack, aka Nick van de Wall is a Grammy Award-winning DJ from Spijkenisse, The Netherlands. He has gone from strength to strength since starting his own label Wall Recordings back in 2007 which soon accelerated a collection of quality releases from Don't Be to Proper Introduction and Thief.
(339,455 listeners)
house, progressive house, electronic, swedish
Alessandro Lindblad (born July 7, 1991 in Stockholm, Sweden), commonly known by his stage name Alesso, is a Swedish DJ and electronic dance music producer.
(95,176 listeners)
electronic, electro, british, disco
B U R N S was born in Glasgow on Halloween in 1985. His mother was an artist and painter. His father was a professional heavyweight boxer. Growing up, watching both parents work made a deep impression on BURNS and combined to give him an appreciation of both beauty and power, a combination that comes through in his own work, in his love of melody and of sonic impact.
Calvin Harris
(1,750,241 listeners)
electronic, dance, electro, disco
Adam Richard Wiles (born 17 January 1984), better known by his stage name Calvin Harris, is a Scottish singer, songwriter and record producer. He was born and grew up in Dumfries, Scotland. His interest in electronic music surfaced in his early teenage years, producing his first bedroom demo by the age of 15.
(536,937 listeners)
D'Angelo is the name of more than one artist 1) US soul singer, songwriter & producer 2) Brazilian jazz/samba group 1) D'Angelo (born Michael Eugene Archer on 11 February 1974 in Richmond, VA, United States) is a neo-soul singer, keyboardist, and guitarist. He has released three albums, "Brown Sugar" (1995), "Voodoo" (2000), and "Black Messiah" as D'Angelo and the Vanguard (2014).
Dirty Projectors
(444,338 listeners)
experimental, indie, freak folk, folk
Dirty Projectors are an experimental pop group led by singer/songwriter and multi-instrumentalist Dave Longstreth which formed in 2002 in Brooklyn, New York, United States. The current lineup of Dirty Projectors is Dave Longstreth (vocals, multiple instruments), Amber Coffman (vocals, guitar), Nat Baldwin (bass), Mike Johnson (drums), Olga Bell (vocals, keyboard) and Haley Dekle (vocals).
DJ Shadow
(1,159,799 listeners)
trip-hop, electronic, hip-hop, turntablism
Considered a prominent figure in the development of instrumental hip-hop, DJ Shadow (real name Josh Davis) has proven himself with groundbreaking, genre-defining solo output on such respected labels as Solesides and Mo' Wax.
(2,808,470 listeners)
There are two artists with this name. 1. Aubrey "Drake" Graham (born October 24, 1986 in Toronto, Ontario) is a Grammy award nominated Canadian actor, rapper and singer signed to Young Money/Universal Motown. Drake shot to global fame upon the release of his critically acclaimed 2009 mixtape So Far Gone and Best I Ever Had, a single from the mixtape which peaked at #2 on the Billboard Hot 100.
Gary Clark Jr.
(182,541 listeners)
blues, blues rock, soul, guitar
Gary Clark Jr. (born February 15, 1984) is an American guitarist and actor based in Austin, Texas. Described as being the future of Texas blues, Clark's resume has included sharing the stage with various legends of rock and roll. He has stated that he is "influenced by blues, jazz, soul country, as well as hip hop".
Janelle Monáe
(478,151 listeners)
soul, rnb, female vocalists, alternative
Janelle Monáe is a U.S. singer, songwriter, dancer, producer, and performer. Monáe was born Janelle Monáe Robinson on 1st December 1985 in Kansas City, Kansas. She moved to New York to study theatre at the American Musical and Dramatic Academy. Her original plan was to pursue a career on Broadway, but she soon changed her mind and returned to music.
(3,052,645 listeners)
hip-hop, rap, hip hop, east coast rap
Shawn Corey Carter (born December 4, 1969 in Brooklyn, New York, United States), is an American rapper and former president and CEO of Roc A Fella Records. He is more commonly known by a variety of stage names including Jay-Z, S. Carter, Jigga, Hova, J-Hova, Hov, and Young Hov.
Jill Scott
(540,207 listeners)
soul, neo-soul, female vocalists, rnb
Born Jill Heather Scott in the North Philly neighborhood of the City of Philadelphia, PA on April 4, 1972. She began her career as a performance poet. She was discovered by Amir "Questlove" Thompson of The Roots. Questlove invited her to join the band in the studios. Which resulted in the live version of "You Got Me" in 1999.
Meek Mill
(406,373 listeners)
hip-hop, rap, philly, meek mill
Robert Williams (born May 6, 1987), better known by his stage name Meek Mill, is an American rapper from Philadelphia, Pennsylvania. He was briefly signed to T.I.
Michael Woods
(98,609 listeners)
trance, electronic, progressive trance, progressive house
Michael Woods is one of the UK's most popular producers having remixed everyone from Ian Van Dahl & Sonique to Iio & Energy 52.
Miike Snow
(981,267 listeners)
electronic, electropop, pop, synth
Miike Snow is an electropop band from Stockholm, Sweden formed in 2007, consisting of American songwriter Andrew Wyatt and Swedish producers Christian Karlsson and Pontus Winnberg. Their eponymous debut album was released in 2009 to much critical acclaim, with the lead single 'Animal' appearing on shows such as Gossip Girl.
Nicki Romero
(72 listeners)
(174,174 listeners)
hip-hop, rap, swag, underground hip-hop
Odd Future Wolf Gang Kill Them All (OFWGKTA) is a hip-hop collective from Los Angeles, California, USA formed by Tyler, The Creator in 2007. Commonly referred to as OF, Odd Future, Wolf Gang, Golf Wang, and various other pseudonyms, the collective is known for their dark, violent, and offensive lyrical content, as well as their energetic live shows and general "don't give a fuck" attitude.
Otto Knows
(199,959 listeners)
house, dance, progressive house, swedish
Otto Jettmann better known as Otto Knows is a Swedish DJ and music producer who has had a number of hits in Sweden, Belgium and the Netherlands and has collaborated with a number of artists including Tim Berg (Avicii), Sebastian Ingrosso, Alesso and has made remixes from ATB, Imogen Heap and others.
Passion Pit
(1,525,963 listeners)
electronic, indie, indie pop, pop
Passion Pit is an electronic band from Cambridge, Massachusetts, United States, formed in 2007. The band consists of Michael Angelakos (lead vocals, keyboards), Ian Hultquist (keyboards, guitar), Xander Singh (synthesizer, samples), Jeff Apruzzese (bass, synth bass), and Nate Donmoyer (drums).
Pearl Jam
(2,536,962 listeners)
grunge, rock, alternative rock, alternative
Pearl Jam is an American rock band that formed in Seattle, Washington, in 1990. Since its inception, the band's line-up has included Stone Gossard (guitar), Jeff Ament (bass), Mike McCready (guitar), and Eddie Vedder (vocals). The band's fifth and current drummer is Matt Cameron, of Soundgarden, who has been with the band since 1998.
Prince Royce
(150,632 listeners)
bachata, latin music, mierda, brutal death metal
Geoffrey Royce Rojas was born and raised in the Bronx, New York. His parents are both from the land of bachata, The Dominican Republic. His parents got divorced, so it was just him, his mom, and siblings.
Rita Ora
(418,664 listeners)
pop, dance, female vocalists, rnb
Rita Sahatçiu Ora, better known as Rita Ora, is an Albanian-British singer-songwriter from London, UK. Born in Pristina, Kosovo in 1990, Ora's family moved to London where she was raised. According to the Hot Right Now Songfacts, during her early teens Ora attended the Sylvia Young Theatre School, whose other notable alumni include Emma Bunton and Amy Winehouse.
(943,145 listeners)
hip-hop, rap, old school, hip hop
Run-D.M.C. was a hip hop group founded by the late Jason "Jam Master Jay" Mizell that included Joseph "Run" Simmons and Darryl "DMC" McDaniels. The group had an enormous impact on the development of hip hop through the 1980s and is credited with breaking hip hop into mainstream music. The three members of Run-D.M.C. grew up in Hollis, Queens, New York, USA.
(979,195 listeners)
electronic, indie, alternative, dub
Santigold (born Santi White on September 25, 1976) is a musician, songwriter and producer from Philadelphia, Pennsylvania, USA who formerly went under the stage name Santogold. She is perhaps best known for the song L.E.S. Artistes which became a hit in the UK and on American alternative radio.
(65,550 listeners)
* Official MySpace There is more than one artist with this name: 1) Savoy is an electronic trio based in Boulder, Colorado, USA. Made up by Ben Eberdt, Gray Smith and Mike Kelly, the band has played all over the United States. Their MySpace is http://www.myspace.com/savoyband , their official site at http://www.savoyband.com
(1,282,260 listeners)
dubstep, electronic, breakcore, electro
Skrillex is the pseudonym used by Los Angeles, California, USA musician Sonny Moore to differentiate his electronic solo work from his work with From First to Last and his other solo projects.
The Hives
(1,399,385 listeners)
rock, garage rock, indie, swedish
The Hives are a garage rock band from Fagersta, Sweden that emerged in the US and the UK in the early 2000s, but existed for nearly a decade before that, playing punk rock. The Hives are: "Howlin" Pelle Almqvist (vocals)
The Knocks
(161,396 listeners)
electronic, synthpop, street punk, indie dance
The Knocks are an electronic music duo consisting of Ben "B-Roc" Ruttner and James "JPatt" Patterson.
(1,266,814 listeners)
Olubowale Victor Akintimehin Folarin (born September 21, 1984 in Washington, D.C.), better known by his stage name Wale, is an American rapper and producer.
(209,160 listeners)
1. American punk band from Los Angeles, California formed in 1977. 2. Australian rock band formed in 1977. Tag as X (Australia) 3. A Japanese metal band which changed their name to X Japan in 1992 4. Czech punk band formed in 2003.


text:
Read an Excerpt
The Legacy Of Croft Castle
By Jean Barrett
Harlequin Enterprises, Ltd.Copyright © 2004 Harlequin Enterprises, Ltd.
All right reserved.
Chapter OneHad their home become a place of evil?
It was certainly not a pleasant question to ask yourself. But Lady Danely found herself doing just that as she huddled in the chair, her gaze on the pair of stone gargoyles that supported the hood of the sitting room's fireplace. She had never liked them. They had always struck her as chilling in their grotesqueness. At this moment the gargoyles seemed particularly malevolent.
She supposed her sudden shudder of foreboding was under-standable, considering all that had been happening in the ancient castle. The trouble was, it was getting worse. Much worse. And now -
Lady Danely cast her anxious gaze in the direction of the closed door to the bedroom. What was taking them so long? She couldn't bear much more of this waiting.
Orders or no orders, she was on her feet and prepared to invade the bedroom when the door opened and the youthful figure of Dr. Finch emerged, medical bag in hand.
"He's getting dressed."
"Is he -"
"He's all right, Judith."
"Thank God."
"This time," Dr. Finch added severely, his warning implying that the next time Guy had an attack it could be something far more serious. "That angina of his is a problem. He's under far too much stress with it."
He knows about our troubles here, Lady Danely thought. It wasn't surprising. Dr. Finch's sister would have told him all about them. He had been visiting his sister when Guy suffered his attack. Judith had blessed both his presence on the island and his prompt arrival at the castle.
What Dr. Finch didn't know, unless Guy had confided it during his examination, and Lady Danely doubted her proud husband would have done so, was the awful scene that had triggered his attack.
Judith could still hear them - the thumps and thuds in one of the guest rooms overhead, the crash of overturned furniture, the shatter of glass. All of it had been followed by the terrified shriek of Mrs. Forbes-Walsh fleeing from her room. Guy had rushed toward the stairs and paid the penalty for his alarm with a seizure.
The horror had been the latest in the series of ghostly happenings that seemed determined to destroy them. She and Guy couldn't go on like this, Judith thought. Not now when this force, whatever it was, threatened her husband's life.
"I told Guy," Dr. Finch said, "that he's to ring up my surgery and make an appointment at the earliest opportunity. I want to do a complete workup on him. If there are any other incidents before then, you have old Dr. Merrick here on the island. Retired or not, the man is still capable in an emergency."
Judith thanked him and he departed. Her husband, Lord Danely, appeared from the bedroom, tucking the folds of his shirt into his trousers.
"You ought to be resting."
"Sorry to give you a scare like that, old girl, but the spasms have completely passed. I'm fine now."
He wasn't fine, and Judith knew that. Although they were both in their early fifties, she was still a slim, handsome woman with an unlined face beneath a cap of silver hair. But no matter what Guy pretended, the last few weeks had aged him. She could see it in the slump of his shoulders. Could swear that the ginger hair on his head, already on the scant side, had thinned even more and that the grooves on either side of his carefully trimmed mustache had deepened.
"Was that the phone I heard while Finch was checking me over?"
Judith had hoped he wouldn't have been aware of its ring from the other side of the closed bedroom door. She hated having to share more bad news with him. On the other hand, if there was any hope of relieving the stress that was endangering his health, he needed to understand that something must be done.
"It was another cancellation, I'm afraid. Of course she had some excuse about an illness in the family. None of them want to admit the actual reason for canceling their reservations. They're all scared."
I'm beginning to think that I am, too. But Judith didn't relate her thought to Guy. He would be deeply troubled by such an admission. Instead, she went to him, placing an earnest hand on his arm.
"Darling, this is getting serious. It's May already. We should be fully booked. Instead of which, with Mrs. Forbes-Walsh refusing to spend another night in the castle, we're empty."
"It's all a lot of mischief. Whoever is responsible for it will get bored soon and quit."
Whatever his certainty, Judith didn't miss the bleak note in his voice. It was just short of desperation. There was so much at stake for them.
"Guy, I think we have to face at least the possibility that Croft Castle is haunted, and that we need professional help. There must be some specialist who -"
"A ghost hunter?" He snorted in disgust. "All a lot of rubbish."
Judith had lived in this country for over twenty years, and she had yet to understand its people. They were supposed to be proud of the ghosts that haunted their stately homes. Yet here was her own husband - thoroughly British - refusing to consider, in the face of growing evidence, that they might be suffering from an evil intent on destroying them. While she, his practical, American-born wife, was ironically prepared to believe just that.
It was Guy's family pride, of course. He feared that the rumors might turn into widespread publicity if they were to call in any investigator, that Croft Castle would become a target for jests.
"No, love," he said, "if it comes to the worst, we'll let the police handle it."
Judith gazed at him in helpless despair. There had to be some way to convince him of the urgency of their situation. That he was risking not just their future, but his very life if they didn't -
Her head turned as the door to their private apartment burst open. The tall, rawboned figure of Croft Castle's cook rushed into the sitting room. Her hands and arms were covered with flour to her elbows, a smudge of it on one ruddy cheek. The stuff drifted down on the Persian rug.
Oh, dear, thought Judith, I suppose she's left a trail all the way from the kitchen. "What is it, Imogen?"
"Turn on the telly!" the cook commanded with the brusque-ness she never failed to use, whether it be with maid or employer. Except this time, Judith detected a genuine excitement in her tone. "The Derek Manners program up in London! Not that he has any."
"Imogen, why -"
"Miss it if you don't look lively! And this is one you don't want to miss! Said as much to myself when I caught it on the set in the kitchen. Right. I'll just get on with it then, shall I?"
Not expecting an answer, the cook retreated, pulling the door shut behind her. It wasn't like Imogen to be mysterious, thought Judith, reaching for the remote. After all that had been happening, she was almost afraid to turn on the set. But she did.
The screen came to life on the close-up of a young woman's face. Judith stared at the image in shocked recognition.
Excerpted from The Legacy Of Croft Castle by Jean Barrett Copyright © 2004 by Harlequin Enterprises, Ltd.. Excerpted by permission.
All rights reserved. No part of this excerpt may be reproduced or reprinted without permission in writing from the publisher.
Excerpts are provided by Dial-A-Book Inc. solely for the personal use of visitors to this web site.