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A seismic streamer section includes a flexible tube with bulkheads at intervals therealong, end means to make electrical and mechanical connections with adjacent sections, tension lines extending from one end means to the other through the bulkheads, hydrophones in the tube between the bulkheads, an electric bundle including through conductors extending from one end means to the other through the bulkheads to various ones of the hydrophone. Each hydrophone comprises a drum shaped case with dished ends and convex sides providing standoff from the bundle and lines for piezoelectric wafers supported inside the ends. A cylindrical metal ring forms the side of the case. Stainless steel cups disposed with their bottoms adjacent and having their rims welded to the rims of the ring form the ends of the case. The piezoelectric wafers are conductively secured one each to the inner surfaces of flexible diaphragms forming the bottoms of the cups. Flat metal discs are conductively secured one each to the mid-portions of the adjacent faces of the wafers. Flexible metal wires are integrally connected one each at one end to the outer peripheries of the discs. The other ends of the wires are inserted into and soldered to a metal tube extending radially through the ring. The tube is ceramically insulated from the ring and sealed thereto fluid tight. The tube may be bonded in place to the ring. The metal discs are separated by a distance equal to the sum of the permissible maximum inward displacements of the wafers. An elastomeric bumper may surround the ring.
1. The method of manufacturing a hydrophone including the steps of
(a) electroconductively fastening the leaf forming the body of a lollypop shaped electric conductor to one side of a piezoelectric wafer,
(b) electroconductively fastening the other side of said wafer to one side of a diaphragm,
(c) repeating steps (a) and (b) with the leaf of another electric conductor, another wafer and another diaphragm,
(d) and the further step performed before, during, or after steps (a), (b), and (c) of insulatingly mounting an electrically conductive tube in an aperture in a conductive ring to form a feedthrough terminal,
(e) and after steps (a), (b), (c) and (d) threading the distal ends of handle portions of said lollypop shaped electric connectors attached to each wafer through said feedthrough terminal,
(f) inserting said diaphragms coaxially in said ring by holding on to flanges extending axially from the rims of the diaphragms,
(g) moving said diaphragms into said ring until lips on the flanges engage the ends of the ring,
(h) welding said flanges to the ends of said ring,
(i) filling with electroconductive solder said tube of said feedthrough terminal to join said tube and said electric conductors therein electroconductively.
2. Method of claim 1 wherein said electric conductors are left protruding outwardly from said tube, followed by
cutting off the portions of said electroconductive means protruding beyond said outer end of said feedthrough terminal.
3. Method of claim 1 or 2, including the step performed at any time of
securing a metal post to said ring.
4. Method of claim 3, followed by the step of
stabbing said feedthrough terminal and post through apertures in an elastomeric, annular bumper and stretching said bumper around said ring and over said lips with said post and tube protruding through said aperture.
5. Method of claim 1 wherein said electric conductors are flat and said leaves are placed in close proximity and parallel to each other as their distal ends are inserted in said tube.
6. Method of claim 1 wherein step (d) is performed by molding ceramic material between the exterior of said tube and the sides of said aperture in said ring while said tube is in place in said ring.
U.S. patent application Ser. No. 320,417, filed Nov. 12, 1981, entitled "Seismic Apparatus" is a continuation-in-part of the present application.
This invention relates to hydrophones and more particularly to such hydrophones used in seismic streamers for seismic exploration under water.
Seismic streamers are usually made up from a plurality of sections each several hundred feet long, coupled together electrically and mechanically. Each section comprises a tube of flexible plastics material, such as polyurethane, several inches in diameter and about an eighth of an inch thick, within which a number of hydrophones are disposed at intervals of a foot or two along the length of the section. In between the hydrophones are other electrical components such as transformers. Bulkheads distributed along the length of the section, e.g. between each adjacent pair of hydrophones, keep the tube round so as not to press in on the hydrophones. Steel lines extend the length of the section to take tension imposed on the section, the lines extending inside the tube through passages in the bulkheads and alongside of the hydrophones. Electrical conductors extend from each hydrophone to one end of the section, and additional electrical conductors extend from the one end of the section to the other. The electrical conductors extend through passages in the bulkheads and alongside of the hydrophones. The streamer section is filled with oil to provide a desired overall specific gravity near to 1.0, and to keep salt water out of the tube and away from the electrical conductors and electrical components, and to transmit to the hydrophones pressure waves of acoustic and near acoustic frequency (hereinafter referred to simply as acoustic waves or frequency). The pressure waves in the water in which the tube is immersed pass through the flexible tube and through the oil in the tube to the hydrophones. When the section is not in use it is wound on a reel that is several yards in diameter.
It will be apparent that a hydrophone employed in a streamer section must have enough strength and toughness to withstand a certain amount of abuse during reeling and unreeling. In addition, the hydrophone must have enough rigidity to minimize mechanical strains, keeping them small in comparison to acoustic deformations of the pressure sensitive diaphragms of the hydrophone. Furthermore, the diaphragms must be shielded from the tension lines and electrical conductors which pass alongside of the hydrophones, since these linear elements may exert considerable lateral force when pulled taught during use. It is also desirable to protect the electrical parts of the hydrophone, i.e. the piezoelectric elements mounted on the diaphragons, from mechanical destruction due to contact with the tension lines and electrical conductors. Finally, the hydrophone's gas (air) chamber, must be sealed liquid tight to prevent entrance of oil or other liquid into the chamber, for such liquid would fill up the chamber and render the hydrophone insensitive to acoustic waves. On the other hand, means must be provided to limit the inward travel of the diaphragms under excessive pressure, e.g. due to the streamer being subjected to excessive hydrostatic pressure.
In response to the foregoing requirements it has heretofore been disclosed that a hydrophone may be constructed as described in U.S. Pat. No. 3,970,878--Berglund--the disclosure of which is incorporated herein by reference. According to that patent a hydrophone comprises a pill box shaped chamber housing peizoelectric wafers on the inside of the top and bottom of the case. In one embodiment the case includes a glass ring to which are bonded diaphragms made of beryllium-copper, phosphorbronze, stainless steel or glass. According to a commercially adopted embodiment of the construction shown in the Berglund patent, the pill box shaped chamber is formed by two brass cups placed rim to rim and soldered together. Piezoelectric wafers are conductively secured to the insides of the flexible diaphragms forming the bottoms of the cups. Flanges extending radially from the rims of the cups are received within elastomeric channels provided inside a protective housing. Within the chamber formed by the cups is a plastics material spacer which limits inward displacement of the diaphragms and the wafers secured thereto. The brass cups themselves serve as one pole of the hydrophone, being connected internally to the outer side of each wafer. The inner sides of the wafers are tied together and a conductor connected thereto is brought out through a glass bushing in a hole in one of the cups. The chamber formed by the cup is thus composed entirely of corrosion resistant metal and ceramic material so that it is impervious to destruction by oil or any salt water which may leak into the tube of the streamer section or by any corrosive gas associated therewith, whereby the chamber remains fluid tight.
Although the foregoing construction has been highly successful commercially, the thought has occurred that its construction would be improved if the plastics material spacer could be eliminated. The present invention accomplishes that result and in addition eliminates the outer protective housing and considerably reduces the size and cost of the hydrophone. At the same time all of the advantages of the prior construction are retained.
According to the invention, a hydrophone for a seismic streamer section includes two conductively coated piezoelectric wafers, each conductively secured at one face to the inner side of one of two flexible metal diaphragms. The diaphragms are supported at their perpheries by axially outwardly extending flanges formed integral therewith having lips which are welded to the upper and lower rims of a cylindrical or preferably externally double convex metal ring to form a fluid (liquid and gas) tight case. The flanges position the wafers in close proximity to limit their inward flexure under excessive external pressure.
The ring has sufficient axial extent:
(a) to create sufficient external standoff distance to keep the diaphragms out of contact with adjacent electrical conductors and tension lines in the streamer section,
(b) to provide sufficient rigidity to the ring to reduce diaphragm displacement due to ring strain, e.g. due to lateral pressure from adjacent electric conductors and tension lines in the streamer section, to an insignificant amount compared to expected diaphragm displacement due to changes in hydrostatic pressure thereon,
(c) to support a metal pin grounded to the ring to provide one external electrical connection post for the hydrophone, and
(d) to pass and support an exteriorly ceramically insulated metal tube providing another external electrical connection post for the hydrophone.
The integral diaphragms and flanges form metal cups. Preferably the cups and the metal ring are made of stainless steel or other corrosion resistant metal having sufficient electrical resistivity to facilitate electric welding. Otherwise the cups and ring could be soldered together.
Flat electrically conductive metal discs conductively secured one each to mid-portions of the adjacent faces of the piezoelectrical wafers have integral flexible electrically conductive metal wires extending one each from their peripheries. The outer ends of the wires are soldered into a ceramic insulated electrically conductive metal tube extending through the side of the case. The portion of the metal tube extending outside the case provides one electric terminal of the hydrophone. A solid electrically conductive metal pin secured to the exterior of the ring provides the other electric terminal of the hydrophone, the stainless steel case having enough electrical conductivity to electrically connect the crystals to the solid metal pin.
For a detailed description of a preferred embodiment of the invention reference will now be made to the accompanying drawings wherein:
FIG. 1 is a sectional view of a hydrophone embodying the invention;
FIGS. 2 and 3 are respectively a perspective and elevation of a piezo-electric wafer used in the hydrophone shown in FIG. 1;
FIGS. 4 and 5 are respectively a perspective and sectional view of a cup forming the upper end of the hydrophone case;
FIGS. 6 and 7 are respectively a perspective view of a ring forming the side of the hydrophone case and a sectional view of a cup forming the lower end of the hydrophone case;
FIGS. 8 and 9 are respectively a perspective and side view of an interior electrical connector employed in the hydrophone;
FIG. 9A is a plan view of one of the piezoelectric wafers and assocated electrical connector;
FIG. 10 is a perspective view of a bumper employed in the hydrophone;
FIG. 11 is a perspective view of a bulkhead connector employed in the hydrophone;
FIG. 12 is a section similar to FIG. 1 showing the hydrophone with bumper in place therearound, the section plane being displaced azimuthally a few degrees to show the case-grounded connector terminal;
FIG. 13 is an axial section through a seismic cable section employing a hydrophone in accordance with the invention; and
FIG. 14 is a section through a modified form of ring which may be employed for the side of the hydrophone case and a modified form of mounting of the feed through terminal in the ring.
FIG. 15 is a plan view of a piezoelectric wafer secured between a case diaphragm and a conductor leaf in accordance with one stage of the method of the invention;
FIG. 16 is a pictorial view showing the subassembly of FIG. 15 being assembled with a ring of the hydrophone case in a later stage in the method of the invention; and
FIG. 17 is a plan view showing a still later stage in said method in which the diaphragm support flange has been welded to the case ring.
The drawings are to scale and the conventions of the U.S. Patent and Trademark Office for patent cases have been employed to indicate materials.
Referring now primarily to FIG. 1 and also to FIGS. 2-13 as the context indicates, there is shown a hydrophone including a stainless steel ring 21 forming the side wall of a drum shaped case. As shown in FIGS. 1,6,12 and 13, ring 21 may have cylindrical inner and outer peripheries. However for increased strength and rigidity for any given weight it is preferred that the outer periphery be double convex, i.e. of larger diamenter around the middle of the ring and of smaller diameter at the ends of the ring; such a modified ring is shown at 21A in FIG. 14, the double convex or barrel shaped exterior surface being indicated at 22.
Two stainless steel cups 23, 25, which should be identical, form the ends of the drum shaped case. Each cup includes a flat circular flexible diaphragm 27, 29, an axially extending flaring flange 31, 33, and a flat lip 35, 37. Lips 35, 37 are electrically welded to ring 21 around the entire perimeter of the ring to form a liquid tight and preferably gas tight seal, i.e. a hermetic or fluid tight seal. As previously explained, a liquid tight seal is required to prevent liquid from seeping into the case, for if the case were filled with liquid the diaphragms would be unable to flex under changes of external pressure. It is also desirable that the seal be gas tight to keep corrosive sea atmosphere or gases from displacing the relatively harmless land air with which the case is filled when the hydrophone is manufactured.
Although stainless steel is a preferred material for the cups and ring, providing enough electrical resistivity to enable the parts to be welded together electrically, other materials may be used for the cups and ring. If the cups are to be soldered to the ring, beryllium-copper or other brass is a good material.
The diaphragms must be thin enough to flex under the changing water pressure produced by acoustic waves. In the case of brass, a thickness of 0.012 inch is satisfactory, and this should be appropriate for stainless steel diaphragms as well. The cups may be cold stamped from sheet metal, which may result in the diaphragm and lip having the same thickness and the axial flange or side of each cup being somewhat thinner. A fillet of 1/32 inch radius is provided at the juncture of the flange and diaphragm. With a cup having an exterior height of 0.210 inch, the radial flare of the side of each cup may be 0.011 inch from a diaphragm external diameter of 0.740 inch. The lip may have a width of 0.120 inch corresponding to the thickness of the ring. The outer diameter of the ring may be 0.870 inch.
Conductively secured to the inner face of each diaphragm is one of two piezoelectric crystal wafers 41, 43, which should be identical. Each wafer includes a circular disc shaped element 45 of piezoelectric material, e.g., a symmetric or asymmetric lattice piezoelectric crystal or polarized ceramic. Circular disc shaped central areas 47, 49, on the opposite faces of each wafer are covered with an electrically conductive metal, e.g. a deposit of silver. Specifications for a typical wafer are as follows:
______________________________________Wafer Material Polarized (G-1512 Gulton Ceramic Industries, Inc., Fullerton, California)Wafer Thickness 0.010 inchWafer OuterDiameter 0.550 inchUncoated perimeter 0.020 inchCapacitance 0.018 MFD (0.009MFD for two in parallel)Coupling Measurement Fa/Fr 1.1600 min.Wafer Thickness atUncoated Edge 0.020 inchDiameter of MetalCoated Area 0.510 inch______________________________________
Each wafer has one of its metal coated surfaces bonded to the inner face of one of diaphragms 27, 29 by conductive cement, e.g. a conductive epoxy. If the wafers are made of a crystal having an asymetric lattice or, as is preferred, the wafers are made of polarized ceramic material, the wafers should be disposed with like poles bonded to the diaphragms, the other poles (which are also like unto each other) being adjacent. To the outer metal coated surface of each wafer is conductively bonded the circular conductive metal disc portion 51 of one of two interior electrical connectors 53, 55. Such conductive bonding may be effected with a conductive epoxy cement. Each disc 51 has integrally formed therewith a metal wire electric conductor of the same thickness as the disc, as shown at 57, 59.
A feed through electrical terminal or connector 61 extends through ring 21. A feed through electrical terminal provides means for electrically connecting devices that are on opposite sides of a wall that must be liquid or fluid tight. It comprises an elongated conductor and an electrically insulating bushing therearound. It may further include a tube around the bushing, and means for securing the tube to the wall. See, for example, the Catalog of Hermetic Seal Corp., "Single Seal Terminals" HSC Series 1000 and 1200, and electrodes, pages 1, 4, and 30, eg TT40, T, K 1236*, and K 1236-F.
As shown in FIG. 1, terminal 61 includes an electrically conductive metal tube 63 with a preferably electrically conductive metal sleeve 65 thereabout secured thereto and insulated therefrom by a glass (or other ceramic) bushing 67. Sleeve 65 has a radial flange 69 of preferably electrically conductive metal forming integral therewith. The periphery of flange 69 is preferably electrically welded, or else in other manner welded or soldered to ring 21 to form a liquid tight, preferably air tight, i.e., hermetic, seal.
Preferably, however, as shown in FIG. 14, sleeve 65 is omitted and bushing 67 is bonded directly to ring 21. The construction of connectors 53, 55, comprising discs 51 with integral tabs or wires 57, 59, makes it possible to assemble the wires 57, 59 into the tube 63 when it is already mounted in ring 21. The inner end of tube 63 may be flush with the inner periphery of ring to further facilitate such mode of assembly, as shown in FIG. 14.
In both the FIGS. 1 and 14 constructions, after Conductors 57, 59 are received in the inner end of tube 63 and the tube is filled with solder 70 to connect the conductors electrically to the tube and to close the tube, sealing it liquid tight and preferably air tight, i.e. hermetically.
In the foregoing manner solder filled tube 63 becomes one electric pole of a hydrophone electric circuit comprising the two wafers 53, 55 connected in parallel. The case itself forms the other pole of the hydrophone circuit, each wafer having one face electrically conductively connected to one of the diaphragms forming the ends of the drum shaped case of the hydrophone. A solid electrically conductive flanged metal pin 71 (FIG. 1) is screwed into the ring 21 up to its flange to provide a binding post for making external connection to the case.
Around the exterior of ring 21 and overlapping its ends may be placed an elastomer bumper ring 81. Ring 81 has upper and lower inturned flanges or lips 83, 85 which overly lips 35, 37 of cups 23, 25. A pair of holes 87, 89 (FIG. 10) provide for passage of tube 63 and rod 71 through the bumper. The bumper is preferably made of an oil and water resistant material such as polyurethane or polyvinyl chloride having a durometer hardness of between 40 and 80 on the Shore A scale. If desired, bumper ring 81 may be omitted, its purpose being merely to insulate the hydrophone wafers from noise created, e.g. by rubbing of electric conductors thereagainst. In this connection it may be noted that by making the ring of the case externally double convex as shown in FIG. 14, contact of the base case with linear elements such as cables and wires is reduced to nearly point contact.
Referrig now to FIG. 13 there is shown a seismic streamer cable section employing the invention. The section includes a flexible polyurethane tube 101 filled with oil and closed at its ends 103, 105. Suitable electrical and mechanical connectors, shown schematically at 107, 109, are provided at the ends of the streamer section for making connection with other streamer sections. The tube is several inches in diameter and about a hundred yards long. At intervals of about a foot or two along the length of the streamer are bulkheads 111. Three mechanical tension taking lines 113 (only two shown), disposed 120 degrees apart about the streamer axis, extend through holes in the bulkheads and through the length of the tube and to the connectors 107, 109 at the ends of the section. A bundle of electric conductors 115 includes wires extending the length of the section between connectors 107 and 109 and further wires extending from one of the connectors to each of a plurality of hydrophones 121 disposed along the length of the section, one hydrophone, usually, between each bulkhead. Other electrical components such as a transformer 123 may also be connected to wire bundle 115.
It will be seen that due to the standoff distance X (FIG. 1) between each hydrophone diaphragm and the ends of ring 21, the diaphragm is protected against contact with wire bundle 115, even when the latter is pulled taut. Also, the diaphragms are protected by such standoff distance from contact with mechanical tension lines 113 and the inside of tube 101. Further standoff is provided by bumper 81 if same is employed. In addition, bumper 81 would reduce transmission of mechanical noise due to ring 21 rubbing against were bundle 115, lines 113, or tube 101, or transformers 123.
FIG. 13 also illustrates the manner of connection of hydrophone 121 to wire bundle 115, two wires 131, 133 from the bundle being soldered to terminals 63, 71.
It will be apparent that the hydrophone is unresponsive to acceleration, i.e. seismic tremors, since the piezoelectric wafers are connected with their adjacent faces in parallel. Acceleration would bow both diaphragms and their associated wafers in the same direction producing neutralizing potentials. On the other hand, acoustic waves in the water will cause both diaphragms to move in or out, bowing the wafers in opposite directions, causing like charges to appear on the inner faces of both wafers and a charge opposite thereto to appear on the outer faces of both wafers.
Should the cable section be subjected to excessive hydrostatic pressure, diaphragms 27 and 29 will move toward each other until metal discs 51, 52 contact each other, stopping further inward motion and protecting the crystals against excessive deformation. The initial or unstressed spacing y between the adjacent faces of discs 51, 52 when the discs are not displaced at all is equal to twice the permissible displacement of the center of each wafer relative to its periphery.
It will be noted that conductors 57, 59 have enough flexibility and length to allow free movement of the diaphragms without interference from the conductors.
It will be appreciated from the foregoing description that a part of the invention lies in the method of assembly of the hydrophone. In this regard the following steps are to be noted.
1. First Terminal and Ring
A tubular terminal is positioned in a passage through the side of the ring of the case and secured to the ring, either by bonding in place, as shown in FIG. 14 or by welding to the ring an outer sleeve in which the tube is already insulatingly mounted, as shown in FIG. 1.
2. Conductor and Wafer
To an outer metal coated surface of each of the two piezoelectric wafers is conductively bonded the circular metal disc portion of a lollypop shaped electrical conductor, e.g., with conductive epoxy cement, as shown in FIG. 9A.
3. Wafer and Diaphragm
Each of the two wafers is conductively secured at its other outer metal coated surface to the inner face of one of the two diaphragms, as shown in FIG. 15.
4. Diaphragm and Case
Each diaphragm is assembled to the ring by first feeding the distal end of the flat lollypop shaped conductor through the tubular terminal as shown in FIG. 16, and then seating the diaphragm flange on the ring and welding the lip of the flange to the ring (see FIG. 17 for an intermediate stage where one diaphragm has been welded to the ring).
5. Conductor and Terminal
The tubular or hollow terminal is filled with solder to electrically join the terminal and conductors, and the distal ends of the conductors are trimmed off even with the distal end of the terminal (see FIG. 1).
6. Second Terminal and Ring
A metal post (FIG. 1) forming a second electric terminal is screwed into a blind opening (FIG. 14) in the exterior of the ring.
7. The terminals are stabbed through apertures in the elastomeric annular bumper (FIG. 10) having apertures in its sides and the bumper is stretched around the ring and over the lips of the flanges (FIG. 12).
It will be appreciated that variations in the order of performance of the steps is readily possible. Preferably each diaphragm flange is welded to the ring separately. Further details of the method and variations thereof are set forth in the claims.
While a preferred embodiment of the invention has been shown and described, variations thereof can be made by one skilled in the art without departing from the spirit of the invention.
Patent Citations
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Last call: Oedipus El Rey, You Can't Take It with You, Baby with the Bathwater
Jeff Smith 8 a.m., March 26
An internationally renowned modern acrobatic dance company, whose company members are dancers, gymnasts, actors, athletes, and teammates. Under the guidance of Artistic Director Jacques Heim, the Company has developed a reputation for innovative movement on oversized surrealistic sets and everyday structures.
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Outcropping near Sunlight Basin, Montana.
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Author, poet, freelance writer, rescuer of dogs and cats,animal welfare advocate, hookbill owner, occasional wildlife rehabilitator, chaser of bugs who just loves photography.
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By Casey Sowers
Sports correspondent
The Marion County Lady Knights ended their season in the Fifth Region touranament at North Hardin High School by losing the Green County Lady Dragons, 60-50. They ended their season 13-15.
The pomp may have been lower key, but the circumstance was just as important to the seven most recent graduates of the GED program at the Marion County Detention Center.
David Nelson, 36, was the first person at the jail to earn his GED after the implementation of a computer-only testing system.
"It's been 20 years since I dropped out of school. It was not easy," Nelson said.
For him, completing the GED, along with the substance abuse program at the jail, is a new step in his life.
Sunday, the Central Kentucky Bass Club held the first tournament of the 2015 season. Originally, the tournament was scheduled to be held on Spurlington Lake in Taylor County.
But access to launch anything at Spurlington was limited at best. That coupled with the chocolate colored water, which had the consistency of a milk shake, pretty much eliminated the lake for now.
Marion County Judge/Executive David Daugherty has announced a public meeting at 7 p.m. Thursday, March 19, at the Marion County Extension Office about the pipeline issues affecting Marion County.
The extension office is located at 415 Fairground Road in Lebanon.
The Marion County Lady Knights opened their tennis season March 11 by scratching out a victory over the visiting Washington County Lady Commanderettes, 5-4.
According to Marion County Coach Landon Williams, the Lady Knights built a 4-2 lead in singles behind strong efforts by Alyssa Farmer (6-0, 6-0) and Allie Evans (6-0, 6-3).
Evans and Jeni Hall provided Marion County with the decisive point by winning their doubles match, 7-6 (3), 6-1.
Approximately 100 people attended a meeting March 19 at the Marion County Extension Office to discuss natural gas liquids (NGLs).
The Tennessee Gas Pipeline (which is owned by Kinder Morgan) has applied to abandon part of an existing natural gas pipeline with plans to convert it to carry NGLs.
"I am proud to live in a county where we still know the value of land as heritage," said Susan Classen, a co-member of the Loretto Community and one of the panelists at last week's meeting.
Property owners who would like to get copies of the Tennessee Gas Pipeline easements on their land can go to the Marion County Clerk's Office.
However, some people at the March 19 meeting indicated that not all the easements are still on file there. Landowners whose easement agreements are no longer on file were told to contact Kinder Morgan directly.
They were advised to contact Justin Dorman by calling 615-221-1518 or sending an email to email@example.com.
The Marion County Knights were a smashing success in their opening matches of the 2015 tennis season, earning home victories over the Washington County Commanders and the Bardstown Tigers.
Marion County opened its season March 11 with a 9-0 victory over Washington County.
Coach Landon Williams wrote in an email that nerves can be a factor in season-opening matches, but he was pleased with what he saw.
By Casey Sowers
Sports correspondent
The Marion County Aquaknights lose four seniors, Lindsey Buckman, Leah Mudd, Bethany Spalding, and Heather Williams, but they are losing more than just four swimmers, according to Coach Katie Kelien.
"We were so lucky to have such a strong senior presence on the team." Kelien said.
The month of March is Red Cross Appreciation month. As part of the local fund-raising effort, WLSK will host a one-hour telethon from 10 to 11 a.m. March 23. Callers can request a song, dedication, give a shout out to support or recognize a friend or family member or just call to make a donation to support the American Red Cross.
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The Lebanon Enterprise is your source for local news, sports, events, and information in Marion County and Lebanon, KY, and the surrounding area.


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Gustav Deutsch interview and a film concert during the 25 FPS International Experimental Film and Video Festival 2009. Guitar and electronic impromptu by Austrian virtuosos serves as backdrop for a screening of original film archive materials. Laptops, computers and films from the beginning of the century.
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ASK KLAUS!Jul 03, 2008
Klaus Knopper is the creator of Knoppix and co-founder of the LinuxTag expo. He currently works as a teacher, programmer, and consultant. If you have a configuration problem, or if you just want to learn more about how Linux works, send your questions to: klaus@linux-magazine. commore »
Bluetooth Security What your phone vendor didn't tell you about Bluetooth securityJul 02, 2008
Is your address book open to the world? Is your mobile phone calling Russia? Many users don't know how easy it is for an attacker to target Bluetooth.more »
Bluetooth Printing Configuring Bluetooth printing in LinuxJul 02, 2008
Even if your printer vendor doesn't advertise Linux Bluetooth support, there are a few tools that may help you set up your Linux system for Bluetooth printing.more »
Bluetooth Headsets Configuring Linux for a Bluetooth stereo headsetJul 02, 2008
We'll show you how to set up support for a Bluetooth stereo headset.more »
ASK KLAUS!Jun 19, 2008
Klaus Knopper is the creator of Knoppix and co-founder of the LinuxTag expo. He currently works as a teacher, programmer, and consultant. If you have a configuration problem, or if you just want to learn more about how Linux works, send your questions to: klaus@linux-magazine. commore »
Linux Supercomputer Roadrunner Takes Petaflops HurdleJun 11, 2008
The Roadrunner supercomputer developed by IBM for the Department of Energy at the Los Alamos National Laboratory is the first to take the Petaflops hurdle of 1.026 billion operations per second.more »
Open Source Graphics Card for DevelopersMay 28, 2008
The Open Graphics project has released specifications for its first card and will accept orders at a price of US$ 1500.more »
Intel and Wind River: Linux-Based Infotainment for AutomobilesMay 25, 2008
Hardware specialist Intel and embedded systems manufacturer Wind River are aiming to put Linux on wheels. Both enterprises have announced their intention to release a jointly developed Linux platform for the automotive industry.more »
Issue 174/2015
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Microsoft Frees Code for .NET Build Engine
MSBuild is now just another GitHub project as Redmond continues its path to the light.
Researchers Demonstrate Hack by Heat
Malware could pass data and commands between disconnected computers without leaving a trace on the network.
Kernel Developers Adopt Code of Conflict
New rules emphasize collegiality in coding.
Ubuntu Switches to systemd
Upstart lands in the dust bin as a new era begins for Linux.
Old Vulnerabilities Are Kept Alive Through Bad Configuration
HP's annual Cyber Risk report offers a bleak look at the state of IT.
Linus Torvalds Announces Linux 4.0
But what do the big numbers really mean?
Microsoft Frees CoreCLR
.NET Core execution engine is the basis for cross-platform .NET implementations.
New Trojan Attacks Linux Servers
The Xnote trojan hides itself on the target system and will launch a variety of attacks on command.
Cisco Releases Annual Security Report
Spammers go low-volume, and 90% of IE browsers are unpatched.
Zero Day Exploits Target Flash
Adobe scrambles to release patches for vulnerable Flash Player.


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A Murder in a Small Western Town Sets Off a StruggHailed as "toweringly important" (Baltimore Sun), "a work of scrupulous and significant reportage" (E. L. Doctorow), and "an unforgettable historical drama" (Chicago Sun-Times), Big Trouble brings to life the astonishing case that ultimately engaged President Theodore Roosevelt, Supreme Court justice Oliver Wendell Holmes, and the politics and passions of an entire nation at century's turn.After
Reflections on a Secret Life, Private Struggle, and Public Battle to Become the First Openly Gay U.S. AmbassadorThis is the memoir of James C. Hormel—a man who grew up feeling different not only because his family owned the Hormel "empire" and lived in a twenty-six-bedroom house in a small Midwest town, but because he was gay at a time when homosexuality was not discussed or accepted. Outwardly he tried to live up to the life his father wanted for him—he was a successful professional, had married a lovely
The Infamous Invasion of Johnson CountyWyoming attorney John W. Davis retells the story of the West's most notorious range war. Having delved more deeply than previous writers into land and census records, newspapers, and trial transcripts, Davis has produced an all-new interpretation. He looks at the conflict from the perspective of Johnson County residents—those whose home territory was invaded and many of whom the invaders targeted
The Ku Klux Klan in Wood County, OhioThe Ku Klux Klan emerged in Wood County, Ohio, in late 1922, and at its peak, the white supremacist group numbered nearly 1,400 members in the county. Klan members occupied many municipal and county-elected positions, and nearly 40 percent of the Protestant ministers of Wood County joined the group in the 1920s. The Klan engaged in cross burnings, public marches and vigilante activities here
An Autobiography of Black ChicagoFew were more qualified than Dempsey Travis to write the history of African Americans in Chicago, and none would be able to do it with the same command of firsthand sources. This seminal paperback reissue, An Autobiography of Black Chicago, emulates the best works of Studs Terkel - portraying the African American Chicago community through the personal experiences of Dempsey Travis, his family, and
Swallowed Tears is a story of an African American family's courage and perseverance. This story is about one family but there were thousands of unknown individuals and families who daily put their lives on the line to end segregation. Dr. Dupuy H. Anderson was one of these individuals who persisted in spite of numerous threats to his life to change the city of Baton Rouge, Louisiana. He was one of
Bad Hair and Botox on the Road to the White HouseProject President is a hilarious romp through American electoral history.From short, fat, bald John Adams' wig-throwing tantrums during the 1800 election to Abraham Lincoln's decision to grow a beard in 1860; from John F. Kennedy's choice to forgo the fedora at his inauguration to John Kerry's decision to get Botoxed for the 2004 race; from the Golden Age of Facial Hair (1860-1912) to the Age of
The Soiling of Old Glory: The Story of a Photograph That Shocked America
The Story of a Photograph That Shocked AmericaBoston, April 5, 1976. As the city simmered with racial tension over forced school busing, newsman Stanley Forman photographed a white protester outside City Hall assaulting an African American attorney with the American flag. The photo shocked Boston, made front pages across the U.S. and won a Pulitzer Prize. Acclaimed historian Louis P. Masur has done extensive research, including personal
Dime Novel Desperadoes: The Notorious Maxwell BrothersA thrilling true crime narrative and groundbreaking historical account, Dime Novel Desperadoes recovers the long-forgotten story of Ed and Lon Maxwell, the outlaw brothers from Illinois who once rivaled Jesse and Frank James in national notoriety. Growing up hard as the sons of a struggling tenant farmer, the Maxwell brothers started their lawbreaking as robbers and horse thieves in the 1870s,
Lawlessness & Liquor in the Prohibition EraAlbany, New York, experienced massive upheaval when the Volstead Act of 1919 established Prohibition. Crime already proliferated in the capital of the Empire State, with rival political machines stooping to corruption and the mob with their heavy-handed powers of persuasion. As it did nationwide, Prohibition in Albany served merely to force alcohol-related commerce underground and lawlessness and
Murders, Mysteries and History of Crawford County, Pennsylvania 1800 1956Who doesn?t love a good homicide? Murders, Mysteries and History pulls 150 years of forgotten crimes straight from the pages of yesterday?s news and stirs them in a historical mix to produce a book like no other. Get the scoop on more than a hundred real-life murders and unsolved killings. Vics, suspects, perps. Judges and juries. Jails and penitentiaries. Hangings, electrocutions and nothing less


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Article | November 30, 1998
Baldor Electric Company: Motion drive catalog
Baldor Electric Co. (Fort Smith, AR) offers a 127-page motion drive catalog that incorporates Baldor Vector Drives®, Baldor Servo Drives® and Baldor's new MINT(TM) motion control products.
The catalog is divided into four sections each describing technical data dimensions and design characteristics.
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Blog Archive
Featured Stories
Online storage…Is it worth it?
17 September 2014 4:37 PM | No Comments
Recently there has been a massive uproar about online storage security, with celebrities Jennifer Lawrence and Scarlet Johannson to name a couple, suffering nude photo leaks onto the web. It has spawned another debate about how much it costs to maintain your right to have […]Read More
Everything you need to know about the iPhone 6 & 6 Plus
10 September 2014 10:57 AM | No Comments
As you know smartphones need something to set them apart in order for them to do well. Well, Apple have been working on the iPhone 6 & 6 Plus which was official unveiled yesterday. So when we got all the information we started to […]Read More
NVIDIA Shield has an Announcement….
25 July 2014 12:11 PM | No Comments
As we all know NVIDIA have just released the Shield gaming tablet, and we came across this article. Which has the list of new games for the NVIDIA Shield Tablet, which includes Trine 2, War Thunder, Talos Principle, Portal & Half Life 2. We thought this […]Read More
- Online storage…Is it worth it?
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Indie Game of the Week Archive
Indie Game of the Week: The Binding of IsaacPosted on May 11, 2012 | No CommentsIf you paid attention in religious education classes in school, you might be slightly surprised at the name of this week's indie game, whose plot is inspired by a story in the bible where Abraham is asked to sacrifice his son Isaac. One of the […]
Indie Game of the Week: Mari0Posted on March 6, 2012 | No CommentsEver wished a wish that seemed so implausible that even mentioning it to your closest confident was too risky, as it would likely result in prolonged mockery at your expense? As a kid, I once considered who was better out of Mario and Sonic. Nowadays […]
Indie Game of the Week: CulminationPosted on December 19, 2011 | No CommentsIt has been awhile since we looked at an in-browser game for Indie Game of the Week. I guess some might argue that they don't, strictly speaking, fall into the 'indie' bracket but I think for all but a few intents and purposes, these titled […]
Indie Game of the Week: RunescapePosted on August 12, 2011 | No CommentsEveryone has time to engage with an online multiplayer game every now and then, and Runescape is not one to miss. Gaining 156 million accounts in its ten year life-span, Runescape never ceases to impress and we felt it was about time it got a […]


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Blush Silhouette Dinnerware by Lenox
Soft florals, in subtle champagne hues, give this fine porcelain pattern a dreamlike quality. But Blush Silhouette is for real and, even with mica and platinum accents, it is dishwasher safe. The coupe accent plate adds a distinctive touch to this elegant pattern.See Blush Silhouette Individual Pieces
Coffee & Tea Accessories
Blush Silhouette Creamer
$115.00 $79.95 $27.95
*Offer excludes kate spade new york, Marchesa, and Donna Karan merchandise.


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Slashdot videos: Now with more Slashdot!
We've improved Slashdot's video section; now you can view our video interviews, product close-ups and site visits with all the usual Slashdot options to comment, share, etc. No more walled garden! It's a work in progress -- we hope you'll check it out (Learn more about the recent updates).
Comment: It's Easy... (Score 1) 196
Comment: Spock... (Score 1) 411
+ - Adware Privdog worse than Superfish
tl;dr There is an adware called Privdog that gets shipped with software from Comodo. It totally breaks HTTPS security.
From Naked Capitalism's summary:
So here we have the CEO of a Certificate Authority (CA), Comodo, who is also the CEO of Privdog, whose product subverts the certificate authority system. Oh, and Comodo ships that very product with its software. These bottom feeders make Bill Gates look like St. Francis of Assisi. How deep does the rot in the software industry go, anyhow?
I am beginning to believe that Richard Stallman is right, living in freedom means using free and open software."
+ - The cause of the Moon's great crater chains
+ - Credit Card Fraud Could Peak in 2015, as the US Moves To EMV, 10 Years Late
The next time US cardholders receive a new card it will probably be equipped with an EMV chip, and most likely be contactless. The US is finally making the transition to secure cards based on the European EMV standard, mostly because the liability shift imposed by the three big credit card brands — Visa, MasterCard and American Express — will start on October... ten years later than Europe
the European Union, where EMV became standard ten years ago, has the lowest level of credit card fraud in the world, the US accounted for 47.3% of the worldwide payment card fraud losses but generated only 23.5% of total volume."
Comment: Re:Block spoofing. Or charge for that privilege (Score 2) 145
+ - Facebook Is Being Skimmed For Info By Bots
+ - Doomsday Clock is now 3 minutes to midnight!-> 1
Link to Original Source
+ - Classic Rock Concert Website Set to Shut It's Doors
Comment: Re:Try Here (Score 1) 186
+ - Hacked news companies tweet Chinese fired on U.S. warship->
At 1 p.m. ET, the Twitter accounts of both companies reported that the Chinese military had fired a missile on a U.S. warship, sparking a full-blown battle. They also claimed the U.S. Federal Reserve was to make an emergency announcement about interest rates.
The stock markets were unmoved by the fake news reports.
"Give the hackers this much credit, the George Washington is our permanent Pacific based carrier," tweeted John Noonan, spokesman for House Armed Services committee. "They at least did their homework.""
Link to Original Source
Comment: Re:When I was a young squirt (Score 1) 314
Comment: Air Raid Siren Test In San Diego & Sonic Booms (Score 1) 790
Another sound I haven't heard since the 60's are the sonic booms from Miramar NAS.


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Live updates
Conservatives are getting Wales back to work says Cameron
The Prime Minister is expected to tell the Welsh Conservative conference that his government's economic plan is working here in Wales. He'll cite as proof that employment is rising faster in Wales than in any other part of the UK.
On creating new private sector jobs – the plan is well and truly working. Just listen to this. In this past year, we have seen the fastest increase in employment here in Wales than in any other part of the UK. Yes, you heard me right. Wales – which lost out in previous recoveries...Wales – which so often got left behind...Wales has, in the past year, seen a faster increase in employment than any other part of the UK.
Faster than London. Faster than the South East. The UK capital for jobs growth is right here in Wales. That's because we have a serious long-term plan – and that plan is working. So I want everyone here in this hall to hold their head high and be proud to say this: The Conservatives are back in Government...and we are getting Wales back to work.
Welsh Conservative conference begins
Welsh Conservatives are beginning their conference with senior party figures expected to intensify their attacks on Labour's running of public services here in Wales. The Prime Minister and UK Health Secretary will be amongst the main speakers at the conference in Llangollen.
Services are better delivered locally say Tories
The Welsh Conservatives' Shadow Local Government minister, Janet Finch-Saunders has welcomed the Williams Commission report which calls for a cut in the number of local councils here in Wales.
What matters to the vast majority of hardworking families is not the intricate structures of local government, but knowing that services will be delivered in an efficient and cost effective way.
We believe that public services are best delivered locally so taxpayers can hold local representatives to account for what happens in their community.
We welcome the publication of this much-anticipated report, which now paves the way for the Welsh Labour Government and the First Minister to promptly set out their proposals to end this period of limbo and uncertainty in local government.
- Adrian Masters
Senior Welsh Tories fail to hide their differences
David Jones today used his speech at the Conservative Party Conference to criticise Labour for failing to use devolution effectively to deal with Wales' problems.
The Welsh Secretary called on ministers to work more closely with the UK Government.
Meanwhile, Andrew RT Davies has questioned the future of the Secretary of State's role.
Welsh Secretary: Labour failing to use devolution well
The Welsh Secretary has accused Labour of failing to use devolution to deal with Wales' problems.
David Jones told the Conservative Party Conference in Manchester that Welsh ministers must work more closely with the UK Government.
Wales and England's economies should 'align'
The Welsh Secretary is expected to urge ministers in Cardiff Bay to do more to 'align' the economy of Wales with that of England. David Jones is expected to tell the Conservative conference in Manchester that Wales is 'diverging' from England 'for the worse
Tory leader questions Wales Office future
The Welsh Conservative leader has called for a debate on abolishing the Wales Office. Andrew RT Davies says creating a powerful 'Department of the Nations' could give Wales a stronger voice in Westminster than the current set-up.
It's being seen as a veiled criticism of the present Wales Office which is led by a Conservative Secretary of State. Andrew RT Davies says change could prevent Wales being 'marginalised' at a UK level.
Prime Minister refuses to be drawn on Silk report
The Prime Minister has refused to say when there'll be a decision on giving the Welsh Government some tax and borrowing powers. A decision had been expected last Spring but David Cameron says there is now no date planned.
The Tory leader has also repeated his criticism of the Welsh Government's handling of the health service. He's been speaking to our Political Editor Adrian Masters.
Never dismiss Tory activists says Welsh party leader
Welsh Conservative leader Andrew RT Davies has said that 'no-one, but no-one should ever forget' the valuable work activists do for the party. He was responding to reports that a senior aide to the Prime Minister called grassroots Tories 'swivel-eyed loons.'
The Assembly Opposition leader praised 'all the members...who work tirelessly on behalf of our party' and said he not only appreciates the work they do but classes himself as one of them, adding that 'the only I way I sit here is because of their work.'
Tory leader admits Anglesey performance 'not good enough'
Opposition leader Andrew RT Davies has admitted that his party's performance in last week's council elections on Anglesey was 'not good enough.' Conservatives failed to win any seat and picked up just 6% of the vote, behind UKIP which achieved 7%.
Mr Davies said that 'we failed to communicate with the electorate' and that it was 'not good enough' just to have candidates in the field. He said the party would learn from that and added that 'We know where our fault lines lie and they'll be ruthlessly - and I mean ruthlessly - sorted out.'


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Credits & Info
- Uploaded
- May 13, 2005 | 12:10 PM EDT
- Daily Feature May 14, 2005
If you liked this, check these out!
Plenty more like this here!
Author Comments
Rated 4.5 / 5 stars
lol.. very funny. I'm glad this series is sticking to random comedy and funny violence. Anger man's intro, ROFL, that was awesome
Rated 4.5 / 5 stars
Very enjoyable....
Mr.Firth, Very Enjoyable.
Rated 4.5 / 5 stars
this was very good
this was very good and nice bloody shot sceen at the end
Rated 4.5 / 5 stars
Thanks david, keep the good stuff rolling in,
or else!
Rated 4.5 / 5 stars
Great stuff
I love all the ways that they described the smell... burning piss, dead breast, bag of dead kittens, old people (only much worse). I liked the Mega Man reference too. Keep it up! And release another Salad Fingers please!


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Dr. Scott W. Penkoff, MD
Family Medicine
- 333 Thalia St
Laguna Beach, CA 92651
- 2 Locations
- (949) 499-0577
Dr. Scott W. Penkoff graduated from the University of Southern California Keck School of Medicine in 1981. He works in Laguna Beach, CA and 1 other location and specializes in Family Medicine. Dr. Penkoff is affiliated with Placentia Linda Hospital, St Joseph Mission Hospital Laguna Beach and Western Medical Center Santa Ana. He speaks English and Spanish.
Gender: Male
Languages Spoken: English, Spanish
Family Medicine
Medical School: University of Southern California Keck School of Medicine; Graduated 1981
*This physician has multiple office locations. See Office Information for details.


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1. Soak the bean thread noodles in water for 15 minutes.
2. Shred the cabbage, carrots and the mushroom, set aside.
3. In a small bowl beat one egg.
4. In a large bowl combine ground pork with bean thread noodles, mushrooms, carrots, cabbage, sugar, salt and pepper, garlic powder and soy sauce.
5. Crack the one egg and mix everything well, set aside.
6. Place one spring roll wrapper on the work top, add 2 tablespoon of the filling and roll the wrapper half way and then bring the two edges together and continue to roll till the end.
7. Brush the egg on the edges and seal the edges completely, continue doing this until all the filling is over.
8. Preheat the oil in a wok over medium high heat, deep fry the spring rolls and fry it for 8-10 minutes or until golden brown.
9. Once done turn off the heat, place the spring rolls on the strainer and let the excess oil drain out.
10. Serve the spring rolls with sweet chili sauce on the side.


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Photo Galleries
< MyNorthwest
Tuesday in photos
March 19: Traditional dancers, women empowerment in India, kicking the football in front of Big Ben
16 of 18
From left, Adm. James G. Stavridis, U.S. Navy Commander, U.S. European Command and Supreme Allied Commander, Europe; Gen. Charles H. Jacoby, Jr.,Commander, U.S. Northern Command and Commander, North American Aerospace Defense Command; and Gen. John F. Kelly, USMC, Commander, U.S. Southern Command testify on Capitol Hill in Washington, Tuesday, March 19, 2013, before the Senate Armed Services Committee hearing on U.S. European Command, U.S. Northern Command, and U.S. Southern Command in review of the Defense Authorization Request for Fiscal Year 2014. (AP Photo/Molly Riley)
Photo by Molly Riley
Photo by Molly Riley
16 of 18
More Photo Galleries
Amanda Knox and her family celebrate acquittal
Italy's highest court overturned the murder conviction against Amanda Knox and her ex-boyfriend Friday over the 2007 slaying of Knox's roommate, bringing to a definitive end to the high-profile case.
Week in Photos
Photos from around the world this week.
Hundreds gather to commemorate one-year mark of Oso mudslide
A solemn crowd gathered to honor 43 people who lost their lives a year ago in the deadliest landslide in U.S. history.
Photos: Oso one year after deadly mudslide
Sunday is the one-year anniversary of the slide, and although most of the mangled cars and homes have been cleaned up, reminders of loss are everywhere.
Week in photos
Take a look at the best photos of the week from around the world.
Tuesday in photos
St. Patrick's Day, March 17, 2015.
Monday in photos
Monday, March 16, 2015.
Week in photos
Photos from around the world this week.
Friday in photos
The second of three Friday the 13ths in 2015; Friday, March 13, 2015.
Thursday in photos
Thursday, March 12, 2015.


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Circumlocution in a Sentence
10 example sentences for "Circumlocution" - Learn English Vocabulary with Sentences
Circumlocution - Definition
the use of too many words to say something, especially in order to avoid saying something clearly
Use Circumlocution in a sentence
The con man tried to use circumlocution to avoid explaining his real intentions to the wealthy couple.
As a politician, the senator had no problem using circumlocution to make his responses sound honest.
Sneaky people who want others to be fooled by their words often use circumlocution to hide their true purposes.
To sell his company's products, the sly salesman used circumlocution to avoid directly answering the woman's questions.
The student used circumlocution in an attempt to stall his teacher while he completed his homework in class.
Rather than let people know he was losing his memory, Mr. Jones used circumlocution to constantly change the topic of conversation.
I would never vote for a politician who avoids answering questions through the use of circumlocution.
Despite the writer's use of circumlocution in his article, it was still quite evident he knew nothing about his subject.
If only the speaker would stop all the circumlocution and get to the point of his speech!
The lawyer made use of circumlocution to confuse the jury into believing his client's innocence.
Do you know these vocabulary words?
Recuperate: In a Sentence
Simultaneously: In a Sentence
Vexed: In a Sentence
Vying: In a Sentence
Virtue: In a Sentence
Circumlocution synonyms
wordiness, babbling, beating around the bush
Circumlocution antonyms
conciseness, directness, straightforwardness


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Skeleton with cylinder moves Motorcross Bike
This great custom product in forest green from our department Men and T-Shirt category can be printed just for you in the size and style you like. The design Skeleton with cylinder moves Motorcross Bike was created by Quentin1984 and uploaded to Spreadshirt for you to have printed on a T-Shirt. Next to a host of other great customized designs, you can find this Skeleton with cylinder moves Motorcross Bike design in Spreadshirt's Racing category. If you are interested in topics like Skull or bike, then you'll love Skeleton with cylinder moves Motorcross Bike designs by Quentin1984. Spreadshirt also offers a huge selection of custom t-shirts, hoodies and accessories for the category Racing as well as top cross clothing. Quentin1984's designs have already impressed many of our customers, so we are sure that we've got right stuff for you! Spreadshirt is your destination for great designs of all kinds – whether it's Skull, bike or cross. We are sure that you will find something nice in our shop, there are many amazing custom Racing t-shirts, hoodies, or accessories for you to find! Tags: Design ID: 11411194
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Phosphate rock is digested with molten ammonium bisulfate and between 5 and 16 percent by weight of water to form a solid reaction product. The water is added to the mixture of phosphate rock and ammonium bisulfate either before, during or after the digestion reaction between the phosphate rock and molten ammonium bisulfate. Concentrated phosphoric acid is extracted from the ground, solid reaction product with a nonaqueous, polar, oxygen-containing organic solvent having between one and ten carbon atoms. A phosphoric acid compound or in other words a phosphate is then separated from the solvent either in the form of concentrated phosphoric acid by evaporating the solvent, or in the form of a phosphate salt by adding a base to the extract and precipitating the phosphate salt.
Claims available in
Description (OCR text may contain errors)
Unite States Patent Rubin [54] METHOD OF PRODUCING CONCENTRATED PHOSPHORIC ACID COMPOUNDS FROM PHOSPHATE ROCK [72] Inventor: Allen G. Rubin, Walnut Creek, Calif. [73] Assignee: B. D. Dohna & Company, Inc., San Francisco, Calif.
[22] Filed: Dec. 26, 1968 [2]] Appl. No.: 786,877
[52] US. Cl ..23/165, 23/107, 23/109 [51] Int. Cl ..C01b 25/18, COlb 25/28, C01b 25/30, C01b 25/32 [58] Field of Search ..23/165, 165 C, 107, 109; /34, 43
[56] References Cited UNITED STATES PATENTS 1,838,431 12/1931 Milligan ..23/165 2,716,591 8/1955 Thomsen ..23/165 2,880,063 3/1959 Baniel et al.. ..23/165 3,245,777 4/1966 Chang ..71/39 FOREIGN PATENTS OR APPLICATIONS 1,480,633 4/1967 France ..23/l65 Primary Examiner0scar R. Vertiz Assistant Examiner-Gregory A. Heller Attorney-Fryer, Tjensvold, Feix, Phillips & Lempio [57] ABSTRACT Phosphate rock is digested with molten ammonium bisulfate and between 5 and 16 percent by weight of water to form a solid reaction product. The water is added to the mixture of phosphate rock and ammonium bisulfate either before, during or after the digestion reaction between the phosphate rock and molten ammonium bisulfate. Concentrated phosphoric acid is extracted from the ground, solid reaction product with a nonaqueous, polar, oxygen-containing organic solvent having between one and ten carbon atoms. A phosphoric acid compound or in other words a phosphate is then separated from the solvent either in the form of concentrated phosphoric acid by evaporating the solvent, or in the form of a phosphate salt by adding a base to the extract and precipitating the phosphate salt.
7 Claims, 2 Drawing Figum METHOD OF PRODUCING CONCENTRATED PHOSPIIORIC ACID COMPOUNDS FROM PHOSPHATE ROCK BACKGROUND OF THE INVENTION Phosphate rock is a common source of phosphate compounds which are useful in fertilizers, foods, detergents, and in numerous chemical processes. However, the phosphate rock is primarily fluorapatite, CaF -3(PO,,) with minor amounts of organic matter, iron, aluminum and other impurities. Inasmuch as the phosphate in phosphate rock is insoluble in water and in common organic solvents, many processes have been devised in order to convert the phosphate to a soluble form.
In the extensively used so-called wet-process," phosphate rock is decomposed with sulfuric acid to form calcium sulfate and phosphoric acid. However, process difficulties are encountered when the phosphoric acid is separated from the calcium sulfate because of the difficulty and expense of removing the calcium sulfate by filtration. Furthermore, the wet-process yields relatively weak phosphoric acid, on the order of 33% P and contains a large amount of water. In order to concentrate the weak phosphoric acid so that it will be economical to ship, the excess water in the phosphoric acid must be evaporated by the application of large amounts of heat. Furthermore, many impurities are present in phosphoric acid produced by the wet-process, and it is difficult to remove impurities from the acid.
There have been many attempts to overcome the deficiencies in the wet-process treatment of phosphate rock by sulfuric acid. One proposed system involves the use of ammonium bisulfate for treating phosphate rock in the absence of water at elevated pressures and at temperatures above about 350 F. However, this system produces ammonium phosphates and polyphosphates which are difficult to separate from the other products of reaction. Furthermore, the system is not as efficient as is to be desired. It has also been proposed that fertilizer materials may be made of phosphate rock by treating the rock with aqueous solutions of ammonium bisulfate. However, the resultant product in which the phosphate is present predominately as ammonium phosphate, is suitable only for fertilizer because of the impurities which remain after treatment of the rock with the aqueous solution of ammonium bisulfate. Furthermore, the excess of water used to form the solution of ammonium bisulfate results in products which are expensive to ship unless the water is removed by costly evaporation. In addition one of the known systems which utilize ammonium bisulfate as an acidulating agent produce a final product which is substantially pure phosphoric acid. Instead such processes produce varying mixtures in which'the predominant phosphate compounds present are ammonium salts of phosphoric or polyphosphoric acids. It is technically difficult to separate ammonium salts of phosphoric acids from ammonium salts of sulfuric acid.
SUMMARY OF THE INVENTION In accordance with the present invention a concentrated phosphoric acid compound of high purity is obtained from phosphate rock by digesting the rock with molten ammonium bisulfate and a small amount of water to provide a solid reaction product. Between 4 and 9 parts by weight of ammonium bisulfate are employed in the digestion reaction for each part by weight of phosphorous pentoxide in the phosphate rock. An amount of water is utilized sufficient to provide between 5 and 16 percent by weight of water based on the entire weight of the phosphate rock, ammonium bisulfate and water. The digestion of phosphate rock with ammonium bisulfate and water in the specified proportions provides a high yield of solvent-soluble phosphoric acid which is then extracted from the reaction product by an nonaqueous polar oxygen-containing organic solvent having between one and carbon atoms. The phosphoric acid may be separated from the solvent extract by any conventional means such as evaporation of the solvent or by precipitation of the phosphoric acid as a phosphate salt.
Phosphoric acid produced in accordance with this invention has a high P 0 content after removal of the solvent, and it may easily and economically be concentrated to super phosphoric acid of about 72 percent IP 0, by application of heat. As a result the concentrated phosphate is economical to transport. Furthermore, the digestion and extraction process is efficient and cable of providing overall yields of percent of the P 0 in the starting phosphate rock.
The ease of separating the phosphate from the reaction mixture is an important feature of this invention. A reaction mixture composed primarily of ammonium sulfate, phosphoric acid and calcium sulfate is produced by the digestion step, and the phosphoric acid is readily separated from this reaction mixture by the solvent extraction hereof. In prior processes which produce a reaction mixture containing ammonium phosphate or polyphosphate instead of phosphoric acid, it is very difficult and costly to separate the phosphate from the ammonium and calcium sulfate in the reaction mixtures.
As a result of this process, phosphates of high purity are produced. The calcium, iron, aluminum and other compounds present in phosphate rock that would form undesirable waterinsoluble compounds with phosphates when the phosphoric acid is subsequently neutralized are separated from the phosphoric acid in the extraction step because they are not dissolved except in trace quantities in the solvent. Also, a minimum of sulfate and a minimum of ammonia is carried over the final product thereby resulting in a high P 0 content and low level of impurities.
In addition the improved filterability of the solvent slurry of calcium sulfate as compared to the filterability of a water slurry enables the calcium sulfate to be readily removed from the solvent by filtration.
It is also significant that the process of this invention may be conducted at relatively low temperatures and with little input of heat.
Large recycle streams of H PO are: required in conventional processes for the production of phosphoric acid utilizing sulfuric acid as the acidulating agent in order to control the concentration of soluble sulfate ion in the digestion step. If this is not done, formation of CaSO, at the surface of the individual rock particles causes the reaction to stop, thereby reducing yields to uneconomic levels. No such recycle requirements exist in applicants process, thereby resulting in additional savings in the production of phosphates.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph which illustrates the increase in the percent of solvent soluble P 0 obtained as the percent of water in the digestion mass of this invention is increased. The data for the graph is given in example 4.
FIG. II is a graph which illustrates the decrease in the weight ratio of sulfate to ammonia in the solvent extract as the amount of water in the digestion mass is increased until an undesirable high proportion of ammonia is present. The data for the graph is given in example 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS In greater detail phosphate rock is digested with ammonium bisulfate by mixing molten ammonium bisulfate with ground phosphate rock in a suitable vessel. Molten" when used in reference to ammonium bisulfate containing small amounts of water describes mixtures which are two-phase systems until heated to temperatures substantially above room temperature. At these temperatures the mixtures become clear, homogeneous, single-phase liquids having an appearance similar to molten anhydrous ammonium bisulfate. It is believed that such mixtures at these temperatures are true melts rather than satu rated solutions.
Any commercial grind of phosphate rock may be employed in the digestion reaction because the reaction between phosphate rock and molten ammonium bisulfate occurs rapidly. A digestion time of 2 or 3 minutes is generally sufficient to provide a suitable yield, but 10 to 15 minutes will insure complete digestion.
A small but critical amount of water is mixed with the rock and ammonium bisulfate either before, during or after digestion of the rock and ammonium bisulfate. The water provides a high yield of solvent-soluble orthophosphoric acid and prevents formation of substantial amounts of the solvent-insoluble polyphosphates. Preferably water is mixed with ammonium bisulfate before the phosphate rock is digested with ammonium bisulfate in order to permit the digestion to be conducted at lower temperatures.
Molten ammonium bisulfate is employed in the reaction with phosphate rock as distinguished from aqueous solutions of ammonium bisulfate. The temperature at which the reaction between ammonium bisulfate and phosphate rock is conducted is not critical. However, it is only important that the temperature be sufficient to provide molten ammonium bisulfate. Since the melting point of ammonium bisulfate varies depending upon its water content, the temperature at which the reaction between ammonium bisulfate and phosphate rock is conducted depends upon whether water is added before or after the reaction. If water is added to ammonium bisulfate before the reaction with phosphate rock in the amounts specified herein, the reaction between ammonium bisulfate and rock may be conducted at anywhere between about C. and 150 C. because of the effect of water in reducing the melting point of the ammonium bisulfate. Although the mixtures of ammonium bisulfate and water specified herein are not molten at 20 C., the slow reaction between the bisulfate and phosphate rock in the solid mixture is exothermic, and the temperature quickly rises when the compounds are mixed at the ambient temperature until the ammonium bisulfate becomes molten and the reaction with the phosphate rock continues rapidly. At temperatures below about 20 C., the reaction occurs very slowly, and at temperatures above about 150 C. the digestion reaction of ammonium bisulfate, water, and phosphate rock results in a reduced yield of the desirable solvent-soluble phosphate due to formation of polyphosphates and ammonium phosphates.
On the other hand when the reaction between phosphate rock and ammonium bisulfate is conducted without first adding the specified amounts of water, the digestion just be car ried out at higher temperatures in order to provide the molten ammonium bisulfate required for the reaction. Any temperature between 147 C. and 300 C. may be employed when water is not first added to the reaction mixture. Above about 300 C. the final yield of orthophosphoric acid is reduced, and excessive amounts of the relatively solvent-insoluble polyphosphates are obtained.
In order to obtain a high yield of organic solvent-soluble, relatively pure phosphate for efficiency in practicing the process, the amount of ammonium bisulfate reacted with phosphate rock should be between 4 and 9 parts by weight of ammonium bisulfate for each part by weight of phosphorous pentoxide in the phosphate rock. If less than 4 parts by weight of ammonium bisulfate are employed, a low yield of solventsoluble phosphate is obtained. If more than 9 parts by weight of ammonium bisulfate are employed in the reaction with phosphate rock, no significant increase in the yield of the desired phosphate is obtained.
Furthermore, as the amount of ammonium bisulfate is increased above 9 parts by weight based on phosphorous pentoxide in the rock, the amount of sulfate which is extracted by the solvent also increases, thereby necessitating subsequent removal of the sulfate. Accordingly, since it is desirable to obtain as pure a product as possible, and to avoid waste of sulfate, the amount of ammonium bisulfate is preferably kept below the 9 parts by weight of bisulfate for each part by weight of phosphorous pentoxide. In addition an excess of bisulfate above 9 parts by weight increases the solubility of calcium sulfate which is formed in the reaction of ammonium bisulfate and phosphate rock. This is undesirable, since the calcium sulfate and the phosphate compounds are separated by means of solvent extraction and subsequent filtration. If any calcium which is extracted along with the phosphate is not removed, it will form undesirable insoluble calcium phosphate when the phosphate is subsequently neutralized.
It is essential that a small amount of water be incorporated in the mixture of ammonium bisulfate and phosphate rock in order to obtain a high yield of solvent-soluble phosphate compound when the reaction product is extracted with the polar organic solvent. Although the water is not essential to provide a water-soluble phosphate in the reaction between phosphate rock and ammonium bisulfate, water in the specified proportions is essential to give phosphoric acid soluble in the organic solvent used in the practice of this invention. Between 5 and 16 percent by weight water is employed based upon the total weight of the phosphate rock, ammonium bisulfate and water in reaction mixture. Ifless than 5 percent by weight of water is employed, the yield of solvent and water-soluble phosphoric acid extracted from the reaction mixture by the solvent is substantially reduced. Also, formation of solvent-insoluble polyphosphates is promoted. More than 16 percent by weight water does not provide any increase in yield of solvent-soluble phosphate but merely dilutes the acid. Additionally above about 16 percent water, the SOJNH weight ratio in the extract becomes very low indicating the production and extraction of an undesirable amount of ammonium phosphate in place of a portion of the more desirable orthophosphoric acid.
In FIG. I it may be seen that the solvent-soluble yield of P 0 as measured by Soxhlet extraction increases steadily until about 12 to 14 percent water by weight has been added to the digestion mixture after which the yield is substantially constant up to the limits studied. That the maximum yield occurs at about percent rather than I00 percent appears to be due to the formation of impurity phosphate compounds, principally iron and aluminum, which are insoluble in the nonaqueous solvents utilized in the practice of this invention. About 5 percent water in the total digestion mass is required to obtain a yield of solvent-soluble P 0 above about 60 percent. Lower yields than about 60 percent are not commercially practical. It can be seen from FIG. I that the addition of small quantities of water above 5 percent causes a rapid increase in yield above 60 percent, whereas a small decrease in the amount of water below 5 percent causes a rapid decrease in the yield of P 0 From FIG. II it may be seen that the SO.,/NI-I weight ratio in the methanol extract obtained from the above-mentioned Soxhlet extraction decreases with increasing water concentration in the digestion step. In other words the amount of NH, in the extract increases as the percent of water increases. This means that increasing amounts of ammonium phosphates are formed which are difiicult and costly to separate from the desired phosphoric acid. A high-purity phosphoric acid is desired because it gives greater flexibility in arriving at a final commercial product regardless of whether the product is to be phosphoric acid or a salt of phosphoric acid. When more than about I6 percent of water is present in the digestion mixture, the SO /NH ratio decreases below about 4, as shown in FIG. II. It can be seen that such a decrease is rapid below 16 percent water, since this percent falls on the steep part of the curve in FIG. II. Therefore, the shaded areas in FIG. I and FIG. II clearly illustrate the areas in which the percent of water in the digestion mixture is too low (FIG. I) or too high (FIG. II), and thereby establishes the optimum percent of water as between 5 and 16 percent.
Another reason for maintaining the amount of water below about 16 percent based on the weight of the digestion mixture is the desirability of obtaining concentrated phosphoric acid or a concentrated phosphate which can be shipped at a minimum of expense. If too much water is present, it is necessary to add heat to evaporate the excess water and raise the concentration to 54 percent commercial grade or 72 percent super phosphoric acid. Because of the substantial amount of heat required to evaporate water, the cost of the process is therefore unnecessarily increased. By varying the amount of water between the 5 and 16 percent, 54 percent P 0 acid may be produced directly by removal of the solvent or 72 percent super phosphoric acid may be produced by a relatively small additional concentration or dehydration.
invnvn When water is included in the initial reaction mixture of ammonium bisulfate and phosphate rock, the resultant reaction product after the digestion is in the form of a hard mass. The addition of water to the ground hard reaction product after phosphate rock has been digested with molten ammonium bisulfate in the absence of water initially causes evolution of gas. Thereafter the reaction mixture again becomes solid. Regardless of whether the water is added before, during or after the reaction between molten ammonium bisulfate and phosphate rock, the best yields of solvent-soluble phosphoric acid in the extract are obtained if the reaction product is stored, or in other words denned, for at least 6 hours, but preferably up to 48 hours after the addition of water.
Next the reaction or digestion mixture is ground into small particles and extracted with a nonaqueous polar, oxygen-containing organic solvent having between one and carbon atoms. Any well known form of extraction may be employed, such as successive cocurrent extractions or any conventional countercurrent extraction system. Alcohols and ketones are particularly useful as solvents. Examples of suitable solvents include isopropyl alcohol, acetone, n-butanol, sec. butanol, amyl alcohol, methyl ethyl ketone, n'decanol, and cyclopentanone. Particularly good extraction results have been ob tained using methanol as the solvent. When single-stage batch extractions are made solvent to digestate ratios in excess of 3 ml. per gram must be used for maximum extraction but where continuous countercurrent extraction is used ratios of 1 ml. per gram or 0.75 ml. per gram or lower can be used with subsequent higher resulting concentrations of H PO in the extract.
After the digestion product is extracted, the extraction solvent contains dissolved orthophosphoric acid together with small amounts of sulfate and ammonia. The solids remaining in the reaction product after extraction are primarily composed of calcium sulfate and ammonium sulfate with small amounts of the other impurities originally found in the phosphate rock. Any conventional filtration apparatus may be used to separate the solvent containing the phosphoric acid from the solids. lf it is desired to produce a phosphate compound of very high purity, the amount of sulfate in the extract may be reduced by partial evaporation of the solvent or by shilling the solvent. Either of these procedures precipitates ammonium sulfate, ammonium bisulfate, or both in the solvent which may then be removed by further filtration. How ever, since the amount of sulfate in the organic solvent may be very small, this further purification step is not necessarily essential for most purposes.
In order to obtain phosphoric acid from the solvent extract, evaporation of the solvent and recovery for subsequent use is preferred. Upon distillation or evaporation of the solvent, phosphoric acid of a concentration of up to 72 percent P 0 remains after the solvent has been removed by evaporation. The concentration of the phosphoric acid depends upon the amount of water originally added to the reaction mixture. The phosphoric acid may readily be further concentrated by heating the acid to drive off water. Superphosphoric acid, which contains about 72 percent P 0 and is a mixture of orthophosphoric acid with polyphosphon'c acids, is easily produced. This compound contains very little water and is quite economical to ship.
Alternatively, phosphoric acid compounds may be precipitated from the organic extraction solvent as salts. Ammoniation of the solvent after reduction of the sulfate results in the formation of a very pure ammonium phosphate precipitate containing a high concentration of P 0 which may be readily removed by filtration. This water-soluble compound is an extremely valuable fertilizer. Animal feed may be provided by adding a calcium compound to the organic solvent in the form of a base to precipitate calcium phosphate. Also, sodium hydroxide neutralization of the extraction solvent will result in the precipitation of sodium phosphate, which is useful in detergents. Neutralization with potassium compounds such as potassium hydroxide will yield a precipitate of potassium phosphate which is useful fertilizer material. Accordingly, it can be seen that: the phosphoric acid compound is readily separated from the organic extraction solvent either by evaporation, or by precipitation in the form of a salt.
Additional methods such as electrodialysis or ion exchange may be employed. Also aqueous extraction may be used to separate the phosphoric acid from water-immiscible organic extraction solvents. However, this procedure is not usually feasible economically if the resultant product is to be shipped because a dilute product is obtained and. concentration as by evaporation must be resorted to in order to obtain a product of 54 percent P 0 or greater.
Phosphoric acid compounds of high purity are obtained by the process of this invention because the digestion step with the specified proportions of phosphate rock, ammonium bisulfate and water provides a reaction product from which only phosphoric acid with minor amounts of impurities are ex tracted by the organic extraction solvent. Analysis reveals that sulfate to P 0 weight ratios of less than 0.15 are readily and directly obtained with this process. The total amount of other impurities before further purification remaining in the phosphoric acid after the extraction solvent is evaporated is usually less than 1 percent by weight. Therefore very little further purification of the high-purity phosphate compounds produced by this process is required.
The following examples illustrate the method of practicing the invention:
EXAMPLE 1 Twenty-two hundred grams of Florida phosphate rock (34.4% P 0 was reacted with 3,960 g. ammonium bisulfate and 740 parts water in an agitated mixer at 100 C. for 15 minutes. The resulting mixture was transferred into trays, cooled to ambient temperature, and stored for 48 hours.
The cooled digestion-mixture was then crushed so that approximately 95 percent of the mixture passed through a 40 mesh screen.
The screened solids were then introduced into an extractor where these solids were contacted in a countercurrent manner with methanol. One milliliter of methanol was used per gram of solids. After a residence time in the extractor of 90 minutes, the 6,900 ml. of rich extract was polishfiltered and the extracted solid residue was filtered to remove the entrapped methanolic solution. The clarified riclh extract containing 615.4 g. P 0 69.0 g. S0 23.0 g. NH and 555 g. H O was then chilled to 60 F. and filtered, removing a portion of the 50 4)zSO4 by crystallization and producing afinal rich extract containing 615.0 g. P 0 38.2 g. S0 9.9 g. N11 and 555 g. H O.
The final rich extract was then evaporated under vacuum in a stainless-steel still where the methanol and water were removed yielding 854.2 g. of a product analyzing 72 percent P 0 4.5 percent S0 and 1.1 percent N11 The other impurities in this product were SiO 500 ppm, Fe O 1,200 p.p.m., MgO 200 ppm, A1 0, 20 ppm, Cr 0 150 p.p.m., CaO 5.0 ppm, and F 10 ppm.
EXAMPLE 2 One hundred grams of Florida phosphate rock (34.0% P 0 was reacted with 220 g. ofNPLHSO, and 35.5 g. of 11 0 under reflux at C. for 20 minutes with constant agitation. The molten mass was placed in a teflon lined tray, held for 48 hours, and ground with a mortar and pestle. The ground dige state was then mixed with 1,000 ml. of methanol and agitated under reflux for 20 minutes. The solid residue was separated from the methanol extract by vacuum filtration. Two hundred and ninety grams of dry solids were recovered having an analysis of 3.1 percent P 0 The methanol extract consisted of 800 g. containing 3.12 percent P 0 1.57 percent SO, and 0.029 percent NH.,. Then 4.04 g. of N11 gas was passed into the extract which was then cooled and filtered. The residue recovered weighed 15.77 g. and consisted of 15.57 g. (NH SO and 0.2 g. NH H PO The filtrate (795 g.) contained 3.13 percent P 0.16 percent SO. and 0.029 percent NH After filtration, 6.23 g. of NH gas was added to the filtrate and a precipitate weighing 42.43 g. (dry basis) was recovered by filtration, which consisted of 4.1 percent (NH SO., and 95.9 percent NI-I H PO EXAMPLE 3 Twenty-five grams of Florida phosphate rock (34.0% P 0 was reacted with 50 g. of ammonium bisulfate at 200 C. under conditions of constant agitation for 5 minutes. The resulting melt was then cooled and stored for 48 hours, and contained 8.5 g. of P 0 the hard mass was then ground in a mortar so that 100 percent passed through a 40-mesh screen and this ground material was mixed with 8.4 g. of water in a Waring blender and after denning for 48 hours, extracted with 50 ml. of methyl alcohol is a Soxhlet extractor for 4 hours.
The extracted residue was then dried and analyzed. The residue contained 1.7 g. of P 0 and the methanolic extract contained 6.8 g. of P 0 6.0 g. of S0 and 1.2 g. NH Upon evaporation of the methanol a black, syruplike liquid remained which analyzed as 72 percent P 0 phosphoric acid.
The foregoing procedure was repeated using the identical conditions and proportions except that water was not added to the reaction mixture. An analysis of the residue revealed that it contained 3.4 g. of P 0 and the methanolic extract contained 5.1 g. P 0 This reveals that a much lower yield is obtained when water is not added to the reaction mixture of phosphate rock and ammonium bisulfate.
EXAMPLE 4 One hundred grams of Florida phosphate rock containing 34% P 0 was mixed with 200 g. of reagent grade ammonium bisulfate and the amounts of distilled water specified in the tables below in a 500-ml. resin reaction flask maintained at 120 C. by means of an electrical heating mantle. Immediately after introducing the ingredients into the flask, the flask cover was clamped into place. A reflux condenser cooled by tap water was mounted on the cover and a stirrer shaft passed through a teflon packing gland in the cover. A third opening in the cover carried a glass thermometer.
The reaction mass was maintained at 120 C. for minutes under constant agitation. At the end of this time the cover was removed and the entire contents poured onto the surface of a teflon-coated tray in such a way as to leave a very thin film (one-quarter inch or less) of the digested mass. The tray and contents were allowed to cool to ambient temperature and then stored in a polyethylene bag for 48 hours.
Next the solid digested mass was removed from the tray, ground by means of a mortar and pestle and analyzed for a total P 0 The ground digested mass was then extracted with methanol by Soxhlet extractions and the amount of methanolsoluble P 0 was determined by analysis of the residue. The
percent of solvent-soluble P 0 is set forth intable I and plotted in FIG. 1 against the percent of water in the digestion mass.
In order to obtain the data plotted in FIG. 11, tests were made in the same manner as for FIG. I and the solvent extract was analyzed for NH and $0 to establish the SOJNH ratio. The ratio for varying percents of water in the digestion mass are set forth in the following table II and plotted in FIG. 11:
What is claimed is:
l. The method of obtaining concentrated phosphoric acid from phosphate rock which comprises:
digesting a mixture of ground phosphate rock, molten ammonium bisulfate in an amount between about 4 and 9 parts by weight based upon the weight of phosphorous pentoxide in said rock, and water in an amount between about 5 and 16 percent by weight based upon the total weight of said mixture of phosphate rock, ammonium bisulfate and water;
extracting phosphoric acid from the solid product resulting from such digestion by contacting said product with a solvent for phosphoric acid selected from the group consisting of alcohols and ketones having between one and 10 carbon atoms to dissolve such phosphoric acid in said solvent; and
then separating phosphoric acid from said solvent by evaporating said solvent.
2. The method of claim 1 wherein the water is incorporated in the digestion mixture before any substantial reaction has occurred between the phosphate rock and the ammonium bisulfate, and the digestion of such mixture is carried out at a temperature of between about 20 C. and C.
3. The method of claim 1 wherein the phosphate rock and ammonium bisulfate are digested at a temperature between about 147 C. and 300 C., and the water is added to the digestion mixture after reaction between the phosphate rock and ammonium bisulfate.
4. The method of claim 1 wherein methanol is the solvent used to extract phosphoric acid from the ground product resulting from the digestion of phosphate rock, ammonium bisulfate and water.
5. The method of obtaining an inorganic phosphate salt from phosphate rock which comprises:
digesting a mixture of ground phosphate rock, molten ammonium bisulfate in an amount between about 4 and 9 parts by weight based upon the weight of phosphorous pentoxide in said rock, and water in an amount between about 5 and 16 percent by weight based upon the total weight of said mixture of phosphate rock, ammonium bisulfate and water;
extracting phosphoric acid from the solid product resulting from such digestion by contacting said product with a solvent for phosphoric acid selected from the group consisting of alcohols and ketones having between one and 10 carbon atoms to dissolve such phosphoric acid in said solvent; and
then precipitating an inorganic phosphate salt selected from the group consisting of ammonium phosphate, alkali metal phosphates and alkaline earth metal phosphates from the solution of phosphoric acid in said solvent by adding a base having a corresponding cation to said solut1on.
ammonium bisulfate are digested at a temperature between about 147 C. and 300 C., and the water is added to the digestion mixture after reaction between the phosphate rock and ammonium bisulfate.
F0405) UNITED STATES PATENT OFFICE CERTIFICATE F CORRECTION Patent No. 3,635,669 Dated January 18, 1972 Inventor(s) ALLEN G. RUBIN I It is certified that error appears in the above-identified "patent and that said Letters Patent are hereby corrected as shown below:
Col. 1; line 9, change "CaF '3(PO to --caF -3Ca (1 o C01. 1, line 38 "Madeof phosphate" should be made from phosphate Col. 1, line 47 "one of the known" should be"'-- none of the known C01. 2, line 7, change "cable" to canable -e- C01. 3, line #0, change "just" to must.
Col. 5, line #4, change "shi1ling"to chilling Signed and se led this 6th day of June 1972.
(SEAL) Attest:
EDWARD M.FLETCHER,JR. ROBERT 'GOTI'SCHALK attesting Officer Commissioner of Patents
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[9 Mar 2015] An observational study by Sahlgrenska Academy researchers at a large Swedish hospital found 2,393 opportunities for hand disinfection and/or aseptic techniques. Doctors and nurses missed 90% of the opportunities.
[4 Mar 2015] Senior citizens have experienced a considerable improvement in their sex lives since the 1970s. A doctoral thesis by Nils Beckman at Sahlgrenska Academy has found that six out of every ten women and seven out of every ten men over 70 are highly satisfied with their sex lives.
[6 Feb 2015] Based on five-year follow-up of patients in a randomized clinical trial, researchers have concluded that gastric bypass is the preferred treatment for extreme obesity despite the fact that it is not as effective in reducing body weight as duodenal switch.
[29 Jan 2015] Children born prematurely are at risk of being struck by the eye disease ROP, which can cause blindness. Using a new web-based method, doctors can now identify the at-risk children long before the initial symptoms present themselves, which increases the possibility of preventive measures.
[21 Jan 2015] The spontaneous PSA testing that has been applied in Sweden in recent decades has only had a marginal effect on mortality. An organized screening focused on those who have the most to gain would, however, reduce the risk of dying from prostate cancer by over 40 percent. This is shown by studies at the Sahlgrenska Academy.
[20 Jan 2015] Swedish studies show that mice that receive a supplement of the "appetite hormone" ghrelin increase their sexual activity. Whether the hormone has the same impact on humans is unknown - but if it does, the researchers may have found the key to future treatments for sex abuse.
[19 Jan 2015] Researchers at the Sahlgrenska Academy have shown that a weak electric "noise" can improve balance and motor skills in patients with Parkinson´s disease. In cooperation with NASA, the research team has now developed a portable prototype that will be used in long-term studies of Parkinson´s patients in their home environment.
[19 Jan 2015] About eight out of ten persons who suffer from IBS believe that the symptoms are due to diet. A diet that excludes particularly indigestible carbohydrates can provide markedly reduced symptoms, as shown by a thesis at the Sahlgrenska Academy.
[16 Jan 2015] Innovative Medicines Initiative (IMI) is launching first eight projects on Ebola, covering vaccine development and manufacture, vaccine coverage, and diagnostics. The total budget of the eight projects launched is ¿215 million. Researchers from the Sahlgrenska Academy, University of Gothenburg participates in one of the Ebola vaccine projects.
[12 Jan 2015] Men who have recently had a heart attack or angina and whose workplace has a poor psychosocial environment often think that the work environment was a contributing cause of their heart problems. A dissertation from The Sahlgrenska Academy shows this.


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