text:
- About
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Erdogan wants army under president's control after coup: Turkish official
Turkish President Tayyip Erdogan wants the armed forces and national intelligence agency brought under the control of the presidency, a parliamentary official said on Thursday, part of a major overhaul of the military after a failed coup.
Monte dei Paschi scrambles to ready bailout plan by Friday
Italy's Monte dei Paschi di Siena, (BMPS.MI), which is scrambling to put together a privately backed bailout, suffered a setback on Thursday when three banks turned down a request to back a planned 5 billion euro ($5.5 bln) cash call.
China says to hold drills with Russia in South China Sea
China and Russia will hold "routine" naval exercises in the South China Sea in September, China's Defence Ministry said on Thursday, adding that the drills were aimed at strengthening their cooperation and were not aimed at any other country.
U.S. says backs resumption of China-Philippines talks on South China Sea
U.S. Secretary of State John Kerry said on Tuesday he supported the resumption of talks between China and the Philippines over the South China Sea, following an international court ruling against Beijing over the dispute earlier this month.
Turkey cancels research director's license over report on coup attempt
Turkey's Capital Markets Board on Wednesday canceled the license of the head of research at brokerage AK Investment and called for him to face charges over a report he wrote analyzing the July 15 coup attempt.
Olympic ban on Russian athletes result of political campaign
President Vladimir Putin on Wednesday blamed a shadowy campaign for unfairly stripping some Russian sports people of the right to compete at the Rio Olympics over doping allegations, hitting out at what he called short-sighted political schemers.
South Korea warns citizens against attack, abduction by North
South Korea warned its citizens in China and Southeast Asia on Tuesday of the risk of "dangerous acts" by North Korea after news reports said North Korea may have sent agents to those places to harm or abduct South Koreans.
Kerry hopes to work with Russia on Syria, U.N. aims to restart talks
The United States said on Tuesday it hoped to announce in early August details of planned military cooperation and intelligence sharing with Russia on Syria, and a U.N. envoy said he would also aim to resume peace talks next month.


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2,532 vehicles matched;
Now showing page 137 of 254. 10 results per page.
Listed by Private Seller
1971 Cadillac Eldorado Convertible. A/C, PS, Disc PB, Elect Seats, tilt and telescopic steering wheel, Electric Windows and
Listed by Fusion Luxury Motors
California Black Plate original Z28 Camaro. Fathom Green. X77 car built the 4th week of March 1969. 302 DZ engine,
Listed by Coast Corvette
This is a very nice, great looking, running, and driving 1959 Corvette. This car has a NOM 327 engine, 4-speed
Listed by Fraser Dante
MUSTANG 1966 'A' CODE GT CONVERTIBLE, A REAL 1966 GT Mustang Convertible in just beautiful Tahoe Turquoise with extremely nice
Listed by Private Seller
All matching numbers car. Off the frame restoration 2011. Only 15 miles since restoration. Garage kept with car cover on.
Listed by Gateway Classic Cars
Gateway Classic Cars of Tampa, Florida is very proud to offer this fully restored 1969 Ford Mustang Mach 1. With
Listed by Bill Kay Corvettes And Classics
2016 Chevrolet Corvette Stingray Z51. Set down the mouse because this rousing Corvette is the Coupe you've been looking
Listed by MJC Classic Cars
Just arrived, an very rare example of a Daimler Saloon. An eight year
restoration was just completed and scored 99.2
Listed by 24 Hour Recreational Storage LLC
An original 138 V.I.N.code,complete rust free 1968 Chevy Chevelle S.S. 1000's of dollars worth of Billet aluminum upgrades throughout this
Listed by Triple F Automotive
Custom "Black Widow" tribute convertible. Options include a 327 C.I. V8 with 1963 Corvette fuel injection system, 4 speed manual

subset: commoncrawl


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It's a fall frolic at St. Juliana's
St. Juliana Falconieri Church in Fullerton hosted its annual fall festival over the weekend, featuring food, games, rides and raffles for the whole family.
Live performances included music from Last Call, HSO, 2Fifths, Katie Stump, the Resouls, the Noble Ones, Matt Shokley and the Servite High School jazz band.
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text:
Galaxy GeForce GT 220 1GB Video Card
Far Cry 2
Version and / or Patch Used: 1.01
Timedemo or Level Used: Ranch Long
Developer Homepage: http://www.ubi.com/
Product Homepage: http://www.farcry2.com/
Buy It Here
The Dunia Engine was built specifically for Far Cry 2 by the award-winning Ubisoft Montreal development team. It delivers the most realistic destructible environments, amazing special effects such as dynamic fire propagation and storm effects, real-time night-and-day cycle, dynamic music system, non-scripted enemy A.I. and so much more.
In the benchmark program built into FarCry 2 the lowest preset we can go to is high, so with our settings moved there and 1280 x 1024 added to the mix we see that the card is again struggling to break the 30 FPS minimum.
PRICING: You can find products similar to this one for sale below.
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Canada: Find other tech and computer products like this over at Amazon Canada's website.
- Page 1 [Introduction]
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- Page 4 [Benchmarks - PT Boats: Knights of the Sea]
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- The Heart of Our Lives
- Amoris Laetitia 108: God's Forgiveness
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Daily Archives: 23 November 2008
Peace Out
Not out, exactly, but peace moved. The AP picks up the story. Pope Benedict is reportedly consulting bishops before making a final decision on moving the Rite of Peace, probably to the end of the Liturgy of the Word. Some progressives have … Continue reading
Posted in Liturgy 15 Comments
PCS 111-114: Anointing Outside of Mass, Introduction
The next twenty sections of Pastoral Care of the Sick are devoted to anointing outside of Mass. Fittingly enough, we have another introduction, four sections in which we are prepared for the sixteen ritual sections that follow. The rite outside of … Continue reading


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The outdoor area around the hotel and the pool. Of course the cookies were fantastic!
Great view of Mount Le Conte. Above, and away from all the activity in Gatlinburg. Very friendly, and helpful staff. Clean, comfortable rooms.The restaurant was very nice; good service, good food. We would stay here again in a heartbeat. And the cookies at the front desk!
We stayed for a week, most people/families don't, which means that there are a lot of rooms to turn over every day. House keeping has more than they can handle, and on two occasions our room was not cleaned until 5:00 P.M. Check in appears to take a while (that wasn't the case for us), not sure why.
We liked the location. It was within walking distance to almost everything. Loved to restaurant and the outdoor eating by the river. Service was poor but the atmosphere was worth it. Room was clean and spacious. Great view of the mountains.
I would return again even though the pool was a disappointment.
The pool was so dirty that we couldn't even swim in it. My granddaughter threw a swim stick in and we couldn't even find it. At night when the pool lights were shining, you could see bits of white floating all over.
Nice Location
Pretty view
Value for the money
A little dated
Pillows were flat
The mountains
Air conditioner broke two times spilling water on the floor, and they never brought us toilet paper after two days of calling.
Breakfast was delicious with many options. Staff was great and had toothpaste (which I forgot). Fantastic location. Less than a five minute walk to the aquarium and the strip is one block over with easy access. The hotel is on a very quiet street and there is a really nice sitting area down by the river.
The only complaints I have are minor. The parking garage has some weird parts to it. It's clearly conformed to the mountain behind the hotel. Also the lamps between the beds didn't work, but the staff probably would have fixed it if I had let them know. Also there were plenty of other lights in the room.
You can walk to everything in gatlinburg. It's a perfect place to stay if you don't need a very romantic get away.
The refrigerator made a noise all night. The heater was either burning hot or off which made it a icebox.
This is an absolutely adorable hotel in a prime location. It had an almost retro feel to it, reminding me of a place my family would have stayed at when I was a kid growing up in the 70s. The rooms were fairly updated and very clean. My only gripe is that the walls are pretty thin but it didn't ruin our stay.
Didn't love the size of the rooms. Very small. No room at all for my toddler to run around and play. The grounds were very nice and family friendly so it did help that situation.
Great value for the money. Comfortable king beds, good breakfast. Nice pool. Jet tub, fireplace in our room. Seems well maintained and friendly staff.
condition of hotel
Comfortable beds with clean warm pillows, blankets and sheets. Nice room with all the usual amenities. breakfast was just adequate.
Could have been a bit more quite and clean. This is an older, slightly run-down motel.
it reminded me of Gatlinburg when I was growing up. Simple, clean motel. Off the parkway so it was nice and quiet, but still just a short walk to the main drag. AMAZING pool!!! Unbeatable price, and super friendly staff. We will be back!
The location and the indoor pool were great.
Our room was very small and smelled like mildew/mold. The hotel is very outdated and not very clean. The Wifi did not work most of the time and the shower water kept going from scalding hot to cold without touching anything. We also were put in a "pet friendly" room, which I would NEVER stay in again. If I had known that part of the hotel was "pet friendly" I would have never booked there. We will never stay at this hotel again.
Room was clean, staff was very friendly and helpful, and the hotel was within walking distance of where we wanted to go.
It was close to town.
The beds were very uncomfortable, bathroom was in bad shape, plugs didn't work and the room had a bad oder.
Everything was great except a very small toilet.
Going up to gatlinburg for a girls weekend in October was a bit crazy as the whole place was packed. But this hotel more than made up for the craziness. When you first hear motor lodge inn you think "um can this be any more dated?" But the rooms were thoughtfully updated and the rooms balcony hangs over the river so you get into how nice the place is really quickly.
The toilet was really low and we made the trip way too short
Close to the Smoky National Park. Easy walk to downtown. Cheap place to stay.
We enjoyed the location to download Gatlinburg and scenic view of river from balcony. Walking distance to our favorite place to visit - Hillbilly Golf - was great, but also great walking distance to download Gatlinburg since it was extremely busy during the weekend we stayed. Satisfied.
The only good thing was location, as its right when you get into Gatlinburg from the north.
Everything about the room was bad, the comforter was as thin as a sheet there was a stain on the actual sheet. The bathroom was so small you were sitting against the wall. Add in the fact of water stains and worn out wood trim we felt like this was an extended stay motel or something. It will never be worth the price, it needs remodeling oh and as you sleep on the first level any and all plumbing above you, you get to hear all night. As for a Days Inn this might be my worst experience ever.
The rooms were sizeable, the water was hot, the location is great whether you're checking out Gatlinburg's tourist district or catching the trolley to Dollywood. Although we didn't go for a swim, the indoor pool looks amazing and I'm sure it's fun regardless of the season. I did note plenty of young families enjoying it while we were there and the air doesn't overwhelm with chlorine.
We arrived late at night, after 2am, and there was no one at the check in counter, only a sign saying "be back soon". After sitting in the lobby for more than half an hour whole the security guard stated at me and at his phone, a desk clerk finally arrived to check us in. Parking was limited, but they were accommodating by basically not enforcing any parking rules as long as we were not blocking someone in. They put us in a handicap room, which wasn't a problem in itself, but the bathroom door slides open and shut for ease of access and unfortunately it wasn't well oiled so we weren't able to ever fully open or close the door. I did report the problem, but don't know if it was ever fixed as we were only there 2 nights.
No coffee in lobby
The walk to the 3rd floor was horrible my mom had to walk it when I said I needed a bottom floor room she is 85 and the rooms are not what's pictured on the booking site I was very disappointed when I arrived and seen the place!!
We stayed for the week of national Quartet convention, and they were very kind, helpful, clean, and took care of any problems that arise. I would definitely stay again.
Kind of run down room.
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text:
At 48, I'm GLAD I've become an invisible woman...
Too old for the builders to wolf-whistle at you? Count your blessings!
The other day I passed a building site. I was wearing a summer dress and the scaffolding was full of 20-something, half-naked builders. So what happened? Absolutely nothing. Nada. Zilch. No wolf-whistles, no catcalls, not even a 'cheer up, love, it might never happen'. Did I feel invisible? Yes, I did. And guess what, I loved it.
At 48, I'm two years past the age when, according to a recent study, women become tragically invisible to unknown men. Apparently, our spreading middles, crow's feet, grey hairs and — gasp! — reading specs act like Harry Potter's Invisibility Cloak, rendering us able to sneak about without being spotted by even the most eagle-eyed chap.
One forty-something, who dubs herself The Plankton, has even taken to the internet to bewail her terrible plight. She is 'plankton' apparently because she is barely visible and 'at the bottom of the food chain' when it comes to men.
Rejoice: Leah Hardy is reveling in the fact that she has become invisible to unknown men over recent years
Oh, leave off! Like The Plankton, I, too, have found I get far fewer wolf-whistles, leers and comments from random men as I've sailed into middle-age. These days, when I go shopping with my gorgeous, flame-haired 19-year-old stepdaughter, I see every young male eye on her, not me.
But I'll let you into a secret. I think being invisible is like having a fabulous superpower. There is nothing like the glorious peace of walking down the street thinking my own thoughts without being yelled at, pestered or even molested by strange men.
It is so relaxing to have a conversation or transaction with a bloke without feeling as if he's just trying to look down my top, and to have a drink with a female friend without fat, sweaty businessmen thinking they are doing us a favour by joining us.
Yes, I might have put on a few pounds and the odd wrinkle, but I've also gained a wonderful sense of freedom. And I know I'm not alone in revelling in the peace and privacy of being invisible.
'Being stared at all the time when I was younger made me feel permanently self-conscious,' says my friend Kate. 'But now I'm nearly 50, I can walk tall, make eye contact in the street without being leered at and generally be treated with far more respect. I'm seen as a human being first, and a woman second, and I love it.'
When younger, things were so different. I didn't look like a supermodel, didn't walk around in a bikini, yet, simply because I was a young woman, I found myself stared at and harassed by men wherever I went. I was treated like a piece of meat to be assessed and commented on.
I found passing building sites on my way to work an ordeal. My shoulders would go up, my head would go down. After a while, the workmen, riled by my refusal to respond to their leers, started to resort to cruder comments about my appearance, and one morning, actually threw stones at me to get my attention.
The truth is, there is a fine line between 'hello, gorgeous' and 'nice legs, shame about the face' when it comes to comments from strange men. On parenting website Mumsnet, women have shared their experiences of being catcalled, often in obscene ways, when pregnant or with their young children, and how 'sullied' 'self-conscious' and 'dirty' this made them feel.
I, too, remember the awfulness of having my body commented on while I was with my toddler son, and feeling nothing but impotent rage, as my tiny boy said: 'Why did that man say that to you, Mummy?'
Even putting these horrible kinds of
attention aside, one of the worst things about being a visible woman was
how it spoiled one of life's pleasures: walking alone, daydreaming.
So it is wonderful now that I can stroll about, happily planning, say, how I'll spend my (non-existent) Lottery winnings, or what I'll have for dinner, without being bothered.
Sense of freedom: Leah feels more confident now than she did in her twenties
In the study on female invisibility,
middle-aged women claimed men stopped being chivalrous — holding doors
open and so on.
The main difference I have found is that men have
stopped being so patronising. They feel less obliged to 'flirt' by
telling me how silly I am.
with 'plankton' female friends is hugely enhanced by our invisibility.
The other evening I met an old school friend for cocktails and we spent a
happy, giggly evening together.
Twenty years ago this was rarely possible without a fat, sweaty businessman lurching over, slurring: 'Would you ladies mind if I joined you?' before plonking himself down at our table with an air of entitlement, as if he were a Christmas present we were dying to unwrap.
'I'd almost forgotten that particular
horror,' laughed my 47-year-old friend Lucy. 'It would be so tricky to
get rid of them as they were always so sure that two women laughing
their heads off together were desperate for a man, any man.'
Another friend, Lisa, 48, says: 'Being "plankton" these days means I no longer have to do a mental edit of every outfit I wear out of the house to assess what message I'm sending out and whether it might attract unwanted attention. I now dress entirely to please myself.'
As it happens, Lisa looks fantastic, and I, like most of my friends, still enjoy fashion, make-up, and have a head full of expensive highlights, rather than grey hairs.
So yes, we might be now invisible to rude scaffolders, drunks and perverts, but surely that's an advantage? Think of it as an in-built idiot filter. In my experience, a cheerful woman with intelligence, charm and experience can make herself entirely visible to the right sort of man when she chooses, even if she is over 45.
A third of middle-aged women are annoyed that their partners are aging better than they are
'I still enjoy catching the eye of an attractive man my own age,' says my friend Sarah, 48. 'But it's a more subtle form of flirting, more sophisticated.'
Another friend, Robyn, who is approaching 60, is divorced, but always has an urbane boyfriend on her arm.
'The kind of men I date are usually about five years older than me and they would hate to date a young woman who wanted children or to go clubbing,' she laughs. Now, when a man pays me a compliment, I find they are rather sweeter and less predatory than the crude comments of my youth.
'You look beautiful,' a man told me the other day as I walked down the street, and the handsome chap in the antique shop definitely flirted as we haggled over a chandelier.
But as I left, I saw a gorgeous young women, hunched over and red faced with embarrassment as a fat man shouted at her from his white van. I felt sorry for her, as I clutched my invisibility cloak just a little closer, and strode off, happily lost in my own thoughts.
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October 26, 2009 11:19:00 AM
The public is invited to join MPR at Vickburg''s Duff Green Mansion (1856), the source of many tales of benign paranormal activity. The investigation begins at 4 p.m. and extends beyond midnight. After brief seminars on basic investigation and a social hour, participants will be given a tour of the home, help set up equipment and later take part in the actual investigation.
Cost to participate is $60 per person and includes an owner-guided tour of the mansion, MPR T-shirt and more. Rooms ($135 plus tax) at Duff Green are available and include happy hour and Sunday morning breakfast.
To register, contact Danny Holland at email@example.com, or contact MPR at 1-888-716-9490.
Jan Swoope is the Lifestyles Editor for The Commercial Dispatch.
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Opening Times
Wednesday, Saturday, Sunday and most Bank Holidays: March to October – 9am to 5pm | November to February – 9am to 4pm
The Visitor Centre is open from 10am until 4pm throughout the year.
Wednesday, Saturday, Sunday and most Bank Holidays: March to October – 9am to 5pm | November to February – 9am to 4pm
The Visitor Centre is open from 10am until 4pm throughout the year.
Created on a floodplain in Kirkstall Valley, a recognised 'flyway' for wildfowl and waders on migration, the wetland habitats constructed here complement the nearby River Aire and the Leeds and Liverpool Canal.
The content within this website is varied and of interest to all ages and walks of life – fun activities for the young, information of latest sightings on the reserve, forthcoming events, newsletters, educational resources and information on how you can become a volunteer or friend of Rodley Nature Reserve.
RT @carefreelee62: @RodleyNR You didn't let me down today :-) https://t.co/yrHd6JAyTO
RT @carefreelee62: @RodleyNR Am coming down to see you today, be prepared for some photos this evening :-)
RT @meanwoodrambler: @YorksWildlife @RodleyNR Have really enjoyed walks around your Reserves in 2016 - many thanks! See my blog at https://…
Beautiful asset in Leeds – so quiet and peaceful…
A hidden gem. Brilliant!
Rodley Nature Reserve is a haven for people as well as wildlife. Thank you.
What a wonderful place! We saw our first Kingfisher and it made our day!
Excellent! Rodley is a top nature reserve – the best visited so far!
Relaxing, peaceful place – will visit again…
This was our first time here. I can't believe it's been under our noses all along. What a lovely escape!
We didn't realise this was here. What a gem! We wish we had come earlier in the summer.
We had a fantastic day and loved the pond dipping. It was a real treat to be here.


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Crazy Substitute Teachers
Enjoy, NG4.05 / 5.00 1,520 Views
Vacuum Salesman
This dude and his Megazord vacuum cleaner3.98 / 5.00 2,432 Views
Markiplier Animated | Mark Of The Survey Corps
This took far too long to make...3.90 / 5.00 3,984 Views
So gross
Had to see dicks lol that was kinda wrong but it was funny nontheless and also like the Don Imus thing hahaha
ahahahahahah lol lmao rotfl but ew dicks
ewww dicks but lolololol lmao ahahahhahahahhahaha most funniest thing ever
it was alright, it was funny when he kicked him in the dick
Really funny
The humor and the graphics were top but the voices reminded me too much of tank me :/. Couldn't you have tried to make them sound more like the spartans in the movie?
Once again...
Another great flash by Johnny Utah. Just fucking morbid and weird. I can't believe the effort that went into this.
Do something epic awesome. That doesn't involve penises or homosexuals. I mean, don't you have have to scream "not homo" when submitting something homosexual, so whatever it is doesn't brand you as gay?
Anyway, good job.
yea im done with gayness for awhile.


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Girl, 6, suffers as Wisconsin lawmakers drag feet on medical marijuana
It's starting to look like Wisconsin will be bringing up the rear when it comes to legalizing marijuana for medical use.
Some 20 states have already done so, and others are moving in that direction. Meanwhile, in Madison, the third attempt to pass a sensibly worded bill is going nowhere again this legislative session.
Sally Schaeffer needs us to hurry up. Her 6-year-old daughter, Lydia, has a rare seizure disorder that occurs mostly in her sleep but occasionally during the day. She is on powerful anti-convulsant drugs that come with various side effects and eventually lose effectiveness. Brain surgery looks way too risky.
People started telling Schaeffer, of Burlington, about Colorado and how children out there with similar disorders have seen dramatic improvement by ingesting cannabis oil which has been stripped of most THC, the chemical that produces the high people get from pot.
One Colorado child, Charlotte Figi, was featured in a 2013 documentary by physician and CNN medical correspondent Sanjay Gupta, who has turned 180 degrees in favor of medical marijuana.
The 5-year-old girl was suffering 300 seizures a week and now is down to two or three a month thanks to the oil from a cannabis strain low in THC and high in CBD, or cannabidiol, which packs the medically beneficial punch. They're calling it Charlotte's Web.
Schaeffer called out to Denver and talked to physician Alan Shackelford, a strong proponent of using marijuana as medicine. He has been involved in Charlotte's care.
"He said there's 30 families a month moving out to Colorado. We talked about that option for my family," said Schaeffer, who along with her husband, Tom, has two other children, Devin, 9, and Grant, 3.
"But my family, my support system, my job, my husband's business, it's all located in Wisconsin. Do I drop all of that?"
She would rather see her home state legalize the medical use of marijuana, or at least this one form of the drug that would help her daughter and other children like her.
But first she has to figure out a way to get it past Republican Sen. Leah Vukmir of Wauwatosa, who chairs the Committee on Health and Human Services where the bill is languishing. As time grows short in this legislative session, Schaeffer is urging her supporters to call the senator, who has refused to allow a public hearing.
In a statement Thursday, Vukmir said she believes the federal Food and Drug Administration, and not the Legislature, is the proper entity to approve new drugs. She added that the Wisconsin Medical Society doesn't support the bill, and that even a Democratic majority couldn't get it passed.
"The bill is supported by the vocal minority in our state," Vukmir said.
I question her definition of minority. A Fox News poll last year found 85% support for medical marijuana, including 80% of Republicans. Other surveys support those big numbers. Even generalized legalization of pot is gaining traction. A Marquette Law School poll from last year found 50% in favor in Wisconsin.
Even the feds have backed off enforcement in states allowing medical marijuana. It's becoming increasingly clear that the expensive and ineffective drug war, at least when it comes to marijuana, has been worse than the effects of the drug itself. It's been a full employment policy for jails and prisons, where racial minorities make up a disproportionate share of inmates.
Democratic Sen. Jon Erpenbach of Middleton, who reintroduced the bill last fall along with Democratic Rep. Chris Taylor of Madison, said, "This has pretty much always been an issue where the Legislature is way behind the curve when it comes to public opinion. Way, way behind."
"My position," Erpenbach told me Thursday, "stems from dealing with people who swear they benefit by it, and dealing with people who are otherwise law-abiding citizens whose mom or dad or brother or sister is dealing with cancer and the only way they can manage the pain and manage the treatment of cancer is to use marijuana, whether it's smoked or ingested or however they use it.
"I dare any legislator to look those people in the eye and say, 'Sorry, you can't have this.'"
The bill covers cancer, AIDS and other serious illnesses. It sets a maximum amount of marijuana a patient could possess and grow, and it calls for tightly regulated distribution of the drug. Patients would need a prescription from a doctor and an ID card from the Department of Health Services.
In case you're wondering, Sally Schaeffer's endgame is not to make it rain legal weed across Wisconsin. She says she has never once used the drug. She is fighting for her child's life and trying to get access to the best treatment.
"Here is this natural substance, and it really is natural, and there is no psychotropic high that these children get by using this," she said. "I'm sure once people know about these children with seizures and the possibility to help them, you would have a boatload of other parents stepping up."
Schaeffer has created a Facebook page: Support the Cure - Stop Pediatric Seizures
Call Jim Stingl at (414) 224-2017 or email at email@example.com
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Original Penang Kayu Nasi Kandar
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Broadcast Pix has announced the availability of its new Version 3.5 software, which adds a number of enhancements to its Mica and Granite systems.
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Beyond automated graphics, V3.5 connects any system to any cloud-based resource for access to animations, clips and databases during live productions. Using Fluent Watch-Folders, Broadcast Pix's built-in ingest and content management system, V3.5 allows access to files from Dropbox, Google Drive, Microsoft SkyDrive Drive, or any cloud-based content resource — even during the middle of a live production. The system operator is alerted when a file arrives, the file's thumbnail appears on the system monitor, and the file name appears on the control panel's button.
Other V3.5 features include enhanced PixMaster file management software to view and manage file metadata, such as setting files to auto-start when taken into the live show. Plus, all 1M/E control panels can now provide control for 2 M/E systems. The new software also delivers enhanced Sony camera control and advanced audio-follow-video functionality.
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Plastic Pail, Green, Cap 5.4 Gal, w/Handle
- Item# 1TMC8
- Mfr. Model# PAIL-54-PGS
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Technical Specs
- Item Plastic Pail
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|Publication number
|Publication type
|Application number
|Publication date
|Nov 25, 1980
|Filing date
|Mar 29, 1979
|Priority date
|Mar 29, 1979
|Also published as
|Publication number
|Johann G. D. Schulz, Jaroslav Zajac
|Original Assignee
|Gulf Research & Development Company
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (6), Non-Patent Citations (1), Referenced by (17), Classifications (9)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
This invention relates to (I) a drilling fluid containing a new composition of matter resulting from the reaction of (1) substantially water-insoluble polycyclic, polycarboxylic acids obtained as a result of the oxidation of coal with (2) a base and (II) said new composition of matter.
2. Description of the Prior Art
Rotary drilling is a technique that has been commonly used to drill a hole into the earth for the purpose of reaching a gas or oil formation. During this process a drilling fluid is passed downwardly through a rotating drill pipe and through the nozzles of a bit at its lower end, flowed upwardly in the annulus between said drill pipe and the borehole wall and then returned to the surface. The drilling fluid must possess (1) satisfactory viscosity and yield value to rapidly lift drilled formation cuttings to the surface, (2) the ability to plaster effectively the wall of the borehole to minimize drilling fluid leakage into the formation and (3) gel strength sufficient to permit effective suspension of drilled formation cuttings when drilling fluid circulation is interrupted or ceases. Since it is now common to reach formation depths wherein temperatures can be as high as about 150� C., and even higher, it is imperative that drilling fluids be heat stable in order to maintain their desired effectiveness.
A drilling fluid that has been extensively used for a long period of time contains water and a clay, such as bentonite, attapulgite or sepiolite. However, since these drilling fluids are deficient in one or more of the necessary properties enumerated above, it has been the custom to chemically treat such drilling fluids by incorporating therein specific additives to overcome specific deficiencies. Although the treatment of drilling fluids with one or more specific additives can improve some specific properties thereof, such additives can affect other properties of the drilling fluids, requiring the additional incorporation therein of still more additives. Through such development, however, complex mixtures of clay minerals with a large number of interacting chemicals have been produced. Therefore, it has become difficult economically to control the physical and chemical properties of clay-based drilling fluids.
Among the additives that have been suggested for incorporation in aqueous clay-based drilling fluids are the water-soluble alkali metal salts of carboxylated benzene or substituted alkyl benzene, wherein the benzene carries from three to six carboxyl groups, in U.S. Pat. No. 2,545,169 to Salathiel. Crowley et al, in U.S. Pat. No. 2,813,826, subjects a lignitic material to partial oxidation in an aqueous alkaline media, and can incorporate the total product, or the total liquid product, with or without some or all of the water removed therefrom or portions of the liquid product extractable with a strong mineral acid, a low-boiling ether or an alcohol or ketone, in an aqueous clay-based drilling fluid.
Instead of incorporating a large number of additives in an aqueous clay-based drilling fluid, it would be desirable to prepare a simpler drilling fluid containing little or no clay.
We have discovered unique compositions of matter resulting from the reaction of (1) a mixture of substantially water-insoluble polycyclic, polycarboxylic acids obtained as a result of the oxidation of coal with (2) a base. We have unexpectedly found that these new compositions can be added to water, fresh or salt water, and the resulting compositions obtained from these components are heat-stable drilling fluids possessing satisfactory range of plastic viscosity, yield value and gel strength, the ability to substantially reduce or minimize drilling fluid leakage in a formation and the additional ability to emulsify oil in the drilling fluid when, for example, an oil is present as a lubricant.
The substantially water-insoluble polycyclic, polycarboxylic acids employed in the reaction with a base herein can be obtained by any conventional or suitable procedure for the oxidation of coal. Bituminous and subbituminous coals, lignitic materials and other types of coal products are exemplary of coals that are suitable herein. Some of these coals in their raw state will contain relatively large amounts of water. These can be dried prior to use and preferably can be ground in a suitable attrition machine, such as a hammermill, to a size such that at least about 50 percent of the coal will pass through a 40-mesh (U.S. Series) sieve. The carbon and hydrogen content of the coal are believed to reside primarily in multi-ring aromatic and non-aromatic compounds (condensed and/or uncondensed), heterocyclic compounds, etc. On a moisture-free, ash-free basis the coal can have the following composition:
TABLE I______________________________________ Weight Percent Broad Range Preferred Range______________________________________Carbon 45-95 60-85Hydrogen 2.2-8 5-7Oxygen 2-46 8-40Nitrogen 0.7-3 1-2Sulfur 0.1-10 0.2-5______________________________________
Any conventional or suitable oxidation procedure can be used to convert the coal to the desired substantially water-insoluble polycyclic, polycarboxylic acids. For example, a stirred aqueous slurry containing coal in particulate form, with or without a catalyst, such as cobalt, manganese, vanadium, or their compounds, can be subjected to a temperature of about 60� to about 225� C. and an oxygen pressure of about atmospheric (ambient) to about 2000 pounds per square inch gauge (about atmospheric to about 13.8 MPa) for about one to about 20 hours. The product so obtained can then be subjected to mechanical separation, for example filtration, and solid residue can be washed with water, if desired, and dried. The solid product remaining will be the desired mixture of substantially water-insoluble polycyclic, polycarboxylic acids, hereinafter referred to as "coal carboxylate". A preferred procedure for preparing the desired coal carboxylate involves subjecting a slurry containing coal in particulate form to oxidation with nitric acid. An exemplary procedure for so converting coal to coal carboxylate is disclosed, for example, in U.S. Pat. No. 4,052,448 to Schulz et al. Thus, a slurry containing coal can be subjected to reaction with aqueous nitric acid having a concentration of about one to about 90 percent, preferably about three to about 70 percent, at a temperature of about 15� to about 200� C., preferably about 25� to about 100� C., and a pressure of about atmospheric to about 2000 pounds per square inch gauge (about atmospheric to about 13.8 MPa), preferably about atmospheric to about 500 pounds per square inch gauge (about atmospheric to about 3.5 MPa), for about five minutes to about 15 hours, preferably about two to about six hours. The resulting product is then subjected to mechanical separation, for example filtration, and the solid residue can be washed with water, if desired, and dried to produce the desired coal carboxylate. Although the entire mixture of substantially water-insoluble polycyclic, polycarboxylic acids obtained in the oxidation of coal can be used in the reaction with the base herein, in an embodiment that portion of the mixture, non-extractable or extractable with an organic polar solvent, such as acetone or methylethylketone, can be used separately. In a preferred embodiment the oxidation reactions are so controlled that the coal carboxylate obtained for reaction with the base will contain from about 10 to about 95 weight percent, or even higher, preferably about 50 to about 95 weight percent, insoluble in an organic polar solvent, with the rest, obviously, being soluble in the polar solvent.
The individual components of the coal carboxylate are believed to be composed of condensed and/or non-condensed aromatic and non-aromatic rings, with an average number of such rings in the individual molecules ranging from about two to about 10, but generally from about three to about eight. On the average it is believed the number of carboxyl groups carried by the individual molecules will range from about four to about 10, generally from about six to about eight. The average molecular weight can range from about 600 to about 3000, but generally can be from about 1000 to about 3000 and the average neutral equivalent from about 200 to about 1000, generally from about 300 to about 800. A typical analysis of the coal carboxylates on a moisture-free and ash-free basis that will be reacted with the base herein is set forth below in Table II.
TABLE II______________________________________ Weight Percent Broad Range Preferred Range______________________________________Carbon 48-75 53-69Hydrogen 3-7 2.2-6Nitrogen 1-4.9 2-3.9Oxygen 20-40 26-37Sulfur 0.1-1.0 0.1-0.8______________________________________
Any base or basic salt, organic or inorganic, that can react with an acid can be used herein to react with the coal carboxylate. Thus, hydroxides of the elements of Group IA and Group IIA of the Periodic Table can be used. Of these we prefer to use potassium, sodium or calcium hydroxide. In addition ammonium hydroxide can also be used. Among the organic bases that can be used are aliphatic amines having from one to 12 carbon atoms, preferably from one to six carbon atoms, such as methylamine, ethylamine, ethanolamine and hexamethylenediamine, aromatic amines having from six to 60 carbon atoms, preferably from six to 30 carbon atoms, such as aniline and naphthalamine, aromatic structures carrying nitrogen as a ring constituent, such as pyridine and quinoline, etc. By "basic salt" we mean to include salts whose aqueous solutions exhibit a pH in the basic region, such as potassium carbonate, sodium metasilicate, calcium acetate, barium formate, etc.
The reaction between the coal carboxylate and the base is easily effected. The amounts of reactants are so correlated that the amount of base used is at least that amount stoichiometrically required to react with all, or a portion (for example, at least about 10 percent, preferably at least about 50 percent), of the carboxyl groups present in the coal carboxylate. This can be done, for example, by dispersing the coal carboxylate in an aqueous medium, such as water, noting the initial pH thereof, adding base thereto while stirring and continuing such addition while noting the pH of the resulting mixture. Such addition can be stopped anytime. In the preferred embodiment wherein a large portion or substantially all of the carboxyl groups are desirably reacted with the base, addition of base is continued until a stable pH reading is obtained. The reactions can be varied over a wide range, for example, using a temperature of about 5� to about 150� C., preferably about 15� to about 90� C., and a pressure of about atmospheric to about 75 pounds per square inch gauge (about atmospheric to about 0.5 MPa), preferably about atmospheric (about 0.1 MPa). The resulting product can then be subjected, for example, to a temperature of about 20� to about 200� C. under vacuum to about 100 pounds per square inch gauge (under vacuum to about 0.69 MPa) for the removal of water therefrom. However, if desired the water need not be removed from the total reaction product and the total reaction product, or after removal of a portion of the water therefrom, can be used to prepare a drilling fluid as taught herein. The solid product remaining is the novel reaction product of (1) a mixture of substantially water-insoluble polycyclic, polycarboxylic acids (coal carboxylate) and (2) a base.
We have found that the above reaction product can be added to water to form heat-stable drilling fluids possessing a broad range of satisfactory plastic viscosity, yield value and gel strength, the excellent ability to reduce or minimize drilling fluid leakage in a formation and the additional ability to emulsify oil in the drilling fluid when, for example, oils are present as lubricants. Therefore, the chemical treatment with thinners or dispersants, fluid loss additives and emulsifiers, usually employed in conventional clay-based drilling fluids are not required for a satisfactory performance for the drilling fluids claimed herein.
These drilling fluids are easily prepared. Thus they can be admixed with water using any suitable means, for example stirring, until the final drilling fluid contains from about one to about 25 weight percent, preferably about five to about 15 weight percent of the reaction product defined above. Although the drilling fluid can be prepared at any suitable temperature and pressure, for example, a temperature of about 5� to about 90� C. and atmospheric pressure over a period of about 12 to about 24 hours, it is preferred that they be prepared at ambient temperature and ambient pressure. If desired, additives that are often incorporated into drilling fluids for a particular purpose, for example, electrolytes, such as potassium chloride or sodium chloride to enhance the inhibitive property of the drilling fluid toward clay cuttings (for example, about one to about 30 weight percent of the drilling fluid), weighting agents, such as barite (for example, amounts sufficient to obtain a density in the drilling fluid upto about 2.16 grams/cm3), oil lubricants (for example, about three to about 20 volume percent of the drilling fluid), pH adjustment compounds, such as sodium hydroxide, potassium hydroxide or calcium hydroxide, can also be added to the drilling fluid at the time of its preparation or at any time thereafter.
The following properties of a number of drilling fluids were determined by the standard procedures recommended by the American Petroleum Institute, API-RP-13B, 4th Edition, November, 1972: plastic viscosity, yield value (point), 10-second and 10-minute gel strength and fluid losses at elevated temperature of 93� C. and 149� C. and a pressure of 500 pounds per square inch gauge (3.5 MPa). Testing for fluid loss was carried out in the Baroid Filter Press No. 387, which has a filter area of 22.6 square centimeters. Since this is one-half of the API filtration area, all filtrate volumes were multiplied by two to correlate with API specifications.
Experience has shown that drilling fluids tend to deteriorate at increasing bottom hole temperatures during drilling. This thermal instability of drilling fluids, referred to as drilling or heat aging, was simulated in the laboratory by placing some of the drilling fluids in a pressure cell and rotating the latter in an oven for selected periods of time at a temperature of 149� C.
The data obtained were evaluated as follows. Required plastic viscosity values are a function of drilling fluid weights. We believe an effective aqueous drilling fluid having a weighting from about 1.01 to about 1.56 grams per cubic centimeters should have a plastic viscosity of about 3 to about 25 centipoises. The yield value relates to the flowing property of the drilling fluid effective to provide good lifting properties for cuttings at minimum viscosity; a satisfactory yield value will have a numeral value in relationship to the plastic viscosity falling within the range of about 1:1 to about 1:3, preferably about 1:1 to about 1:2. 10-second and 10-minute gel strengths of about one to about eight pounds per 100 square feet (about 48 to about 383 Pa), and about one to about 29 pounds per square feet (about 48 to about 1389 Pa), respectively, are satisfactory. To ensure effective fluid loss control while drilling, API values at 93� C. should be less than about 20 milliliters per 30 minutes and at 149� C. should be less than about 30 milliliters per 30 minutes after heat aging for 24 hours or more at 149� C.
A number of mixtures of substantially water-insoluble polycyclic, polycarboxylic acids (coal carboxylate) was prepared as follows. One of the coals used in these preparations was a North Dakota lignite analyzing as follows, on a moisture-free basis: 67.19 weight percent carbon, 3.85 weight percent hydrogen, 22.73 weight percent oxygen, 0.55 weight percent sulfur, 1.03 weight percent nitrogen and 4.65 weight percent metals. The ash was further analyzed and found to contain 43 weight percent oxygen, 7.8 weight percent sulfur, and the remainder metals. In one preparation a subbituminous Big Horn coal from Wyoming analyzing as follows, on a moisture-free basis, was used: 73.09 weight percent carbon, 4.35 weight percent hydrogen, 1.24 weight percent nitrogen, 17.42 weight percent oxygen, 0.85 weight percent sulfur and 3.05 weight percent metals.
Into a two-liter stirred autoclave containing a slurry composed of 800 grams of dried powdered lignite and 640 milliliters of water at 80� C. there was added 130 milliliters of 70 percent aqueous nitric acid over a period of 60 minutes. After the addition was complete the mixture was maintained in the autoclave for an additional 240 minutes. During the entire period of time the temperature was maintained at 80� C. and atmospheric pressure (ambient pressure). At the end of the reaction, the resulting reaction mixture was subjected to filtration and the resulting solids were dried in a vacuum oven to obtain a mixture of substantially water-insoluble polycyclic, polycarboxylic acids. To determine the amount of polar solvent soluble material present in such mixture, the same was subjected to extraction with methylethylketone (MEK). Two additional similar runs were made. The data obtained are set forth below in Table III.
TABLE III__________________________________________________________________________ MEK Soluble Addi- Hold- Coal in Coal Nitric tion ing Carbox- Carbox- Slurry Acid, Temper- Time, Time, ylate ylateRun Coal, Water, Milli- ature, Min- Min- Ob- WeightNo. Grams Grams liters �C. utes utes tained Percent__________________________________________________________________________I 800 640 130 80 60 240 A 7II 800 640 195 80 85 210 B 8III 800 640 260 80 120 180 C 10__________________________________________________________________________
Into a five-gallon stirred autoclave there was charged 3000 grams of water and 890 milliliters of 70 percent aqueous nitric acid. The mixture was heated to 80� C. at atmospheric pressure. To this mixture there was added a slurry containing 1500 grams of powdered North Dakota lignite and 1500 grams of water over a period of 30 minutes. There was then added to the autoclave 445 milliliters of 70 percent aqueous nitric acid at a rate of 20 milliliters per minute. An additional 3000 grams of slurry containing lignite and water, similar to the above, was added to the autoclave over a period of 30 minutes. The autoclave was held at 80� C. for a period of four hours from the initial addition of slurry thereto. The contents of the autoclave were cooled to ambient temperature, filtered and the resulting solids, composed of a mixture of substantially water-insoluble polycyclic, polycarboxylic acids (coal carboxylates), were dried as before and analyzed for their MEK-soluble content. The product obtained is identified in Table IV as Coal Carboxylate D. Two additional runs were carried out to prepare Coal Carboxylates E and F similar to the above except that the batches of coal slurry were added to the autoclave in twenty-minute periods and the coal carboxylates obtained were not dried. In preparing Coal Carboxylate E and total holding time was two hours instead of four. An additional Coal Carboxylate G was prepared as follows: Into a one-gallon stirred glass autoclave there was charged 320 milliliters of water and 100 milliliters of 70 percent aqueous nitric acid. The mixture was heated to 80� C. at ambient pressure. Concurrently there were added two streams over a period of 180 minutes: one containing 800 grams of the subbituminous coal defined above and a second composed of a mixture of 640 milliliters of water and 100 milliliters of 70 percent aqueous nitric acid. After addition was complete the contents of the autoclave were held at 80� C. for an additional 60 minutes. The reaction mixture was filtered and the solid product remaining, a mixture of substantially water-insoluble polycyclic, polycarboxylic acids (coal carboxylate), was dried in a vacuum oven and was found to contain 16.0 weight percent acids soluble in methylethyl ketone. The results of the above runs are summarized below in Table IV.
TABLE IV__________________________________________________________________________ MEK Solubles In Coal Total Coal Total Coal Carbox- Total Nitric Temper- Addition Reaction Carbox- ylate,Run Coal, Water, Acid, ature, Time, Time, ylate WeightNo. Grams Grams Grams �C. Minutes Minutes Obtained Percent__________________________________________________________________________IV 3000 6000 1335 80 60 240 D 25.5V 3000 6000 1335 80 40 120 E 37.1VI 3000 6000 1335 80 40 240 F 15.6VII 800 960 200 80 180 240 G 16.0__________________________________________________________________________
Drilling fluids were prepared as follows. 165 grams of Coal Carboxylate Mixture B were added to 44.9 grams of potassium hydroxide dissolved in 800 milliliters of distilled water and the mixture was mixed in a Waring blender. When gelling became apparent, the sample was transferred to a high-pressure shearing device (sonolator) and diluted with hard water (containing 300 parts per million of calcium ions and 20 parts per million of magnesium ions) to 1650 milliliters. The sonolator is used to simulate the effect of high pressure on shear degradation of the coal oxidate mixture. Since water used in preparing drilling is usually a hard water containing calcium and magnesium ions, a simulated hard water was used in the dilution. The resulting suspension was sheared in the sonolator for 40 minutes at 700 pounds per square inch gauge (4.8 MPa). 420 milliliters of the above suspension was diluted with an additional 280 milliliters of hard water to obtain a drilling fluid containing six weight percent of the reaction product of the coal carboxylate and potassium hydroxide. The concentration of calcium and magnesium ions in the drilling fluid was about 200 parts per million and 13 parts per million, respectively. The resulting drilling fluid had a pH of 9.7. This drilling fluid was then tested for its plastic viscosity, yield value, gel strength and fluid loss. To the drilling fluid so tested there was then added three weight percent potassium chloride to check the effect of electrolytes thereon. After the drilling fluid was again tested, it was aged at 149� C. for 24 hours and again tested.
A drilling fluid was prepared following the procedure of Example I except that the mixture used in reaction with potassium hydroxide contained Coal Carboxylate A and Coal Carboxylate C. The drilling fluid tested also contained potassium chloride and was aged at 149� C. for 24 hours. Testing for fluid loss was carried out at 149� C.
The drilling fluid prepared and tested herein following the procedure of Example II except that the mixture used in reaction with potassium hydroxide contained Coal Carboxylate A and Coal Carboxylate B.
The drilling fluid prepared herein followed the procedure of Example II except that the mixture used in the reaction with potassium hydroxide contained Coal Carboxylate D and was not sonolated. The sample was tested at 149� C. for 24 hours. After testing the sample was aged for an additional 64 hours at 149� C. and again tested. Thus the total time of aging for the latter sample was 88 hours.
The data obtained are tabulated below in Table V.
TABLE V__________________________________________________________________________ HT-HP API Fluid Loss Reaction Yield at 500 PSIAging Product, Value Fann Gels (3.5 MPa)at Weight Percent, KCl, Plastic Pounds/100 10 Sec. 10 Min. 93� C. 149� C.149� C., (Coal Carboxylate) Weight Viscosity, Sq.Ft. Pounds/100 Sq. Ft. Ml/ Ml/ExampleHours, Mixture Used) Percent cp (Pa) (Pa) pH 30 Min. 30__________________________________________________________________________ Min.I A -- 6.0 (B) -- 4 4(192) 1(48) 1(48) 9.7 17 --I B -- 6.0 (B) 3 11 13(622) 6(287) 16(766) 9.8 14 --I C 24 6.0 (B) 3 10 8(383) 8(383) 9(431) 8.5 -- 19II 24 7.0 3 13 5(239) 3(144) 5(239) 9.3 -- 29 (2.6 Percent from A) (4.4 Percent from C)III 24 7.0 3 10 11(527) 8(383) 12(575) 9.1 -- 19 (2.6 Percent from A) (4.4 Percent from B)IV A 24 8.0 (D) 3 17 12(575) 4(192) 10(479) 8.6 -- 15IV B 88 8.0 (D) 3 13 12(575) 4(192) 8(383) 8.5 -- 23__________________________________________________________________________
The data in Table V clearly show that excellent aqueous drilling fluids are prepared using the novel reaction product resulting from the reaction of coal carboxylates obtained as a result of the oxidation of coal with a base. The plastic viscosity of 4 cp in the basic drilling fluid of Example I indicates that it is satisfactory for a non-weighted drilling fluid. Since in many cases drilling fluids are prepared using sea water or contain alkali chlorides to inhibit shale hydration, it is interesting to note that the presence of potassium chloride in the drilling fluid of Example IB improves the desired qualities of the same. Since the viscosities and yield values and their ratios are excellent, this drilling fluid can be weighted, for example with barite, if desired. The reduction in fluid loss at 93� C. is remarkable and indicates that if an aggregrated structure was responsible for the viscosity increase the filtration properties were not adversely affected thereby. The results obtained in Example IC indicate that the drilling fluids claimed herein are thermally stable and do not undergo the thermal degradation typical of many drilling fluids treated with organic polymeric colloids. Thus, the rheological properties of the drilling fluids remain almost unchanged; a slight decrease in yield value makes the gel-forming tendency less time dependent. The fluid loss determined at 149� C. is excellent and is a direct measure of the thermal stability of the reaction product of the coal acids with a base.
Since the performance of a drilling fluid is enhanced if the same is thermally stable, testing of heat-aged samples is needed for the ultimate evaluation of a drilling fluid formulation. Therefore the remaining tests in Table V were all made on aged drilling fluid samples. The data obtained in Examples II, III and IV show that even though the composition of the coal carboxylates used herein is varied, as evidenced by the varying content of the methyl ethyl ketone-solubles therein, and the process for obtaining such acid mixture is also varied, the drilling fluids prepared using the reaction product of coal carboxylates with a base are excellent. These data further indicate that following the dictates herein a drilling fluid can be tailored to fit the desired requirements in a particular drilling environment.
An additional series of runs was carried out wherein the effect of diesel oil addition and pH adjustment in the drilling fluids claimed herein was determined. These runs were carried out following the procedure of Example II using selected mixtures of substantially water-insoluble polycyclic, polycarboxylic acids. Diesel oil was incorporated in a selected number of drilling fluids. The pH of the drilling fluid was varied by the addition thereof of potassium hydroxide. The data obtained are tabulated below in Table VI.
TABLE VI__________________________________________________________________________ Reaction Product, HT-HP API Weight Diesel Yield Fluid Loss Percent Oil In Value at 500 PSIAging (Coal Drilling Pounds/ Fann Gels (3.5 MPa)at Carbox- KCl, Fluid, Plastic 100 10 Sec. 10 Min. 93� C. 149� C.149� C., ylate Weight Volume Viscosity Sq. Ft. Pounds/100 Sq. Ft. Ml/ Ml/ExampleHours Used) Percent Percent cp (Pa) (Pa) pH 30 Min. 30 Min.__________________________________________________________________________V A 64 8.0 (E) 3.0 -- 13 9(431) 4(192) 11(527) 9.0 -- 23V B 64 8.0 (E) 2.7 10 18 24(1149) 13(622) 30(1436) 7.5 -- --V C 64 8.0 (E) 2.7 10 15 15(718) 5(239) 18(862) 9.5 -- 16VI A 64 8.0 (F) 3.0 -- 17 16(766) 6(287) 23(1101) 9.1 -- 20VI B 24 7.3 (F) 2.7 10 20 21(1005) 7(335) 26(1245) 8.8 -- 14VII A-- 7.0 (G) 3.0 10 12 9(431) 3(144) 5(239) 8.3 13 --VII B24 8.0 (G) 3.0 10 14 5(239) 3(144) 5(239) 8.2 -- 28__________________________________________________________________________
The incorporation of an oil in a drilling fluid is not conceived as a chemical treatment. Since the oil is a lubricant, its primary functions are for the purpose of reducing the amount of torque on the drill pipe, to lengthen the bit-bearing life and to decrease the amount of wear in drilling fluid pumps. The purpose of the above runs was to determine the effect of a lubricant on the drilling fluid claimed herein. The rheological and fluid loss properties of the drilling fluid of Example VA are good. The addition of diesel oil to the drilling fluid in Example VB improved the plastic viscosity and yield values of the drilling fluid, but the gel strength values were marginal. However, as Example VC shows, increasing the pH of the drilling fluid from 7.5 to 9.5 resulted in a drilling fluid having excellent rheological properties and low fluid loss values. Examples VIA and VIB show that although the concentrations of the reaction product of coal acids with potassium hydroxide is reduced by the addition of the diesel oil thereto, the emulsified oil improves the rheological and filtration characteristics of the resulting drilling fluid. Moreover, the data show that the emulsion is stable at 149� C. after 24 hours of heat aging. This is remarkable considering that no emulsifier was added to the drilling fluid. It is apparent, therefore, that the presence of the defined novel reaction products in the drilling fluid performs three functions: they help to control the viscosity and the filtration properties of the drilling fluid and emulsify the oil. While in Example VB the diesel oil was incorporated in the initial stages of drilling fluid formulation, it was admixtured in the sample of Example VIB after heat aging for 64 hours at 149� C. in order to simulate drilling fluid maintenance during drilling aging. The data show that the emulsifying capability of coal carboxylates was not lost after 64 hours of heat aging, and an improvement of the rheological and filtration characteristics is apparent even after additional 24-hour aging. Considering the excellent ratio of plastic viscosity to yield value this drilling fluid could be weighted with barite to a density of 1.56 grams/cm3. Examples VII A and B indicate that feeds used can be extended to coals other than lignite. The flowing and static properties and filtration characteristics of drilling fluids formulated with coal carboxylates derived from subbituminous coals are satisfactory and comparable in their performances to the drilling fluids prepared using carboxylates derived from lignite.
The application of clay-water drilling fluids poses a variety of problems connected with flow behavior, gelling and filtration characteristics, particularly in the presence of electrolytes and at increased temperatures. Since numerous and pertinent studies merely present data which emphasize the successful empirical approaches sufficient to remedy a specific problem, there is no good general and concise description of the basic clay-water behavior relevant for drilling fluid application that could be referred to for comparison. Accordingly, comparative tests were made with clay-water suspensions comparable to those prepared hereinabove.
Bentonite suspensions were prepared by prehydrating 49.7 grams of bentonite in 280 milliliters of distilled fresh water overnight, after which the slurries were diluted with hard water to a total of 830 milliliters. To some of these suspensions there was added 24.9 grams of potassium chloride. The suspensions so prepared were sheared for one hour in a Waring blender. Additional suspensions were similarly prepared using 44.4 grams of attapulgite or sepiolite prehydrated in 162 milliliters of distilled water overnight. The slurries were diluted to 740 milliliters with hard water and 22.2 grams of potassium chloride were dissolved therein. These slurries were similarly sheared for one hour in a Waring blender. Each of the suspensions so prepared was tested with the results indicated in Table VII.
TABLE VII__________________________________________________________________________ HT-HP API Yield Fluid Loss Value at 500 PSIAging Bento- Atta- Sepio- Plastic Pounds/ Fann Gels (3.5 MPa)at nite, pulgite, lite, KCl, Vis- 100 10 Sec. 10 Min. 93� C. 149� C.149� C., Weight Weight Weight Weight cosity, Sq. Ft. Pounds/100 Sq. Ft. Ml/ Ml/ExampleHours Percent Percent Percent Percent cp (Pa) (Pa) pH 30 30__________________________________________________________________________ Min.VIII A-- 6.0 -- -- -- 8 5(239) -- 2(96) 9.4 32 --VIII B-- 6.0 -- -- 3.0 36 69(3304) 69(3304) 73(3495) 9.0 55 --VIII C65 6.0 -- -- -- 48 72(3447) 10(479) 10(479) 9.1 -- 46VIII D65 6.0 -- -- 3.0 18 232(11108) 94(4501) 108(5171) 9.2 -- 129VIII E-- -- 6.0 -- 3.0 6 43(2059) 25(1197) 25(1197) 9.2 * --VIII F65 -- 6.0 -- 3.0 6 13(622) 9(431) 10(479) 8.8 -- *VIII G-- -- -- 6.0 3.0 11 119(5698) 53(2538) 57(2729) 9.2 192 --VIII H-- -- -- 6.0 3.0 6 55(2633) 49(2346) 51(2442) 9.2 -- *__________________________________________________________________________ *Denotes no shut off; that is, a thick, permeable cake formed which would not provide resistance to flow of filtrate into a formation.
The data in Table VII describing the behavior of the clay suspensions indicate that the electrolyte adversely affects the rheology and the filtration characteristics of these suspensions. Therefore it would appear imperative to treat chemically these suspensions prior to using them as drilling fluids. Such chemicals include inorganic salts or organic compounds. However, chemical treatment can serve to retard, rather than to eliminate, the viscosifying and gelling of treated drilling fluids in use. This is because the chemicals used can undergo a thermal and shear degradation.
The data in Table VII also show that heat aging is synergestic with the electrolytic effect and substantiallydestroys the rheological and/or filtration properties of the drilling fluid. It appears that bentonite and sepiolite undergo hydrothermal breakdown and their suspensions are thereby converted into worthless gels, which then require treatment with thinners. However, thinners have a detrimental effect on mud rheology because of their ability to disperse drilled shale and clay cuttings and thereby incorporate them into the drilling fluid. Because of this the total amount of colloidal clay solids in the drilling fluid is increased, its viscosity rises, and the drilling fluid must be diluted and weighted to only retard the subsequent gelling cycle. Thus, in many cases clay-based drilling fluids must be treated with protective colloids or polymers which beneficiate the bentonite while drilling through shale formations. The needle-like particles of attapulgite form a deflocculated structure after heat aging. Since the swelling and hydration of attapulgite are low, its suspension, on one hand, must be treated with one additive to improve the rheology and, on the other hand, with an additive of polymeric nature to reduce the fluid loss. Although sepiolite-based drilling fluids are recommended for drilling in deep holes, the data indicate that its suspensions have the deficiencies typical of both bentonite and attapulgite suspensions and therefore require a heavy chemical treatment. A comparison of the data in Table VII with that of the drilling fluids claimed herein, as exemplified, for example, in Table VI, clearly shows the technical and commercial superiority of the drilling fluids claimed herein since they do not require chemical treatment for the same specified conditions.
The following exemplifies the deficiencies of an aqueous drilling fluid containing lignite.
The lignite used herein is a North Dakota lignite analyzing as follows, on a moisture-free basis: 67.19 weight percent carbon, 3.85 weight percent hydrogen, 22.73 weight percent oxygen, 0.55 weight percent sulfur, 1.03 weight percent nitrogen and 4.65 weight percent metals. The ash was further analyzed and found to contain 43 weight percent oxygen, 7.8 weight percent sulfur and the remainder metals. 248 grams of ground dry lignite were treated with 44.9 grams of potassium hydroxide dissolved in 800 milliliters of water and mixed in a Waring blender for 30 minutes, after which mixing was discontinued and the resulting suspension kept at rest overnight. The sample was transferred to a high pressure shearing device (sonolator), diluted with hard water to 3100 milliliters and sheared for 20 minutes at 700 pounds per square inch gauge (4.8 MPa). 1300 milliliters of an eight weight percent lignite suspension was sampled for testing. Another portion was diluted with 600 milliliters of hard water to 2400 milliliters, sheared and 1300 milliliters of a six weight percent lignite suspension was sampled for testing. The remainder was diluted with 550 milliliters sheared and 1300 milliliters of a four weight percent lignite suspension was sampled for testing. Some samples contained three weight percent potassium chloride. The rheology of each of the suspensions was determined, after which the samples were aged for 24 hours at 149� C. The samples for fluid loss testing were set aside for six days at ambient temperature. During this period, the aged samples separated in two phases, with the lignite settling in the lower phase. However, all the samples were thoroughly mixed prior to fluid loss testing. The data are tabulated below in Table VIII.
TABLE VIII__________________________________________________________________________ HT-HP API Yield Fluid Loss North Value at 500 PSIAging Dakota Pounds/ Fann Gels (3.5 MPa)at Lignite, KCl, Plastic 100 10 Sec. 10 Min. 93� C. 149� C.149� C., Weight Weight Viscosity, Sq. Ft. Pounds/100 Sq. Ft. Ml/ Ml/ExampleHours Percent Percent cp (Pa) (Pa) pH 30 Min. 30 Min.__________________________________________________________________________IX A -- 8.0 -- 5 4(192) 4(192) 5(239) 8.9 34 --IX B -- 8.0 3.0 4 4(192) 4(192) 5(239) 8.5 160 --IX C 24 8.0 3.0 2 1(48) 1(48) 2(96) 8.5 -- 400IX D -- 6.0 -- 3 3(144) 2(96) 4(192) 8.6 46 --IX E -- 6.0 3.0 2 3(144) 3(144) 3(144) 8.5 182 --IX F 24 6.0 3.0 2 1(48) 1(48) 1(48) 8.5 -- 396IX G -- 4.0 -- 2 1(48) 1(48) 1(48) 8.5 50 --IX H -- 4.0 3.0 2 1(48) 1(48) 1(48) 8.5 -- *__________________________________________________________________________ *Denotes no shut off.
The data in Table VIII amply show that suspensions prepared with lignite possess poor rheological properties and unacceptably high fluid loss characteristics, particularly in the presence of electrolyte and/or when they have been subjected to heat aging. Thus, it is not possible to formulate a simple lignite (coal) based drilling fluid.
We have found that the novel drilling fluids claimed herein possess the following rheological properties which are significant for efficient drilling: necessary time-dependent thixotropic behavior and shear thinning behavior. A mixture containing 50 volume percent of each of the drilling fluids used in Examples IB and IC were subjected to evaluation in a Haake-Roto Viscometer. The shear stress-shear rate data of the uprun were measured on the fluid continuously broken until the point of highest shear rate. Immediately after the completion of the uprun, the shear stresses of the downrun were determined at the descending shear rates. The time interval to break down the structure in the uprun and to stabilize the structure in the downrun was three minutes. The data obtained in the uprun and downrun cycles are set forth below in Table IX.
TABLE IX______________________________________UprunShear Rate, Sec.-1 Shear Stress, Dyne/Cm2______________________________________1.1 7.72.2 9.95.4 1611 1922 2143 2586 29173 36345 44689 53976 --______________________________________DownrunShear Rate, Sec.-1 Shear Stress, Dyne/Cm2______________________________________689 49345 32173 2286 1543 1122 911 75.4 5.92.2 4.51.1 4.3______________________________________Shear Rate, Sec.-1 Apparent Viscosity, cp______________________________________173 21345 13689 8______________________________________
The difference between the shear stresses of the uprun and the downrun illustrates the structure/shear relationship referred to as a thixotropic loop. The apparent viscosity computed for the shear rate range of the annular and drill pipe flow shows a considerable thinning from 21 cp to 8 cp. Extrapolating these values to a shear rate range of 105 sec-1 in a bit nozzle, the drilling fluid will thus provide a water-thin consistency of a few centipoises and thereby improve the drilling rate.
If a drilling fluid is inhibited and substantially non-dispersed, it minimizes osmotic hydration and suppresses shale clay swelling in borehole walls and in shale cuttings. This will appreciably suppress distintegration of shale cuttings and shale sloughing when drilling in shale formation. A qualitative evaluation of the inhibitive and non-dispersive characteristics was made by placing Upper Cody shale cuttings containing from 50 to 60 weight percent montmorillonite in (1) tap ater, (2) a three percent aqueous potassium chloride solution, (3) a drilling fluid, such as that of Example VB, and (4) the filtrate obtained from previous tests of said reaction products. The shale cuttings disintegrated in water within a few minutes, in the three weight percent potassium chloride solution within 24 hours, but no apparent change in the size of the cuttings in the drilling fluid and in the filtrate was found after three weeks. The cuttings were dried and were found to be encapsulated by a dark red film of the reaction product of the coal acid mixture and base.
In addition to the advantages, disclosed and illustrated above, possessed by our novel drilling fluids, the novel reaction product present therein can be crosslinked by hydrogen bonding in the presence of hydrated cations of amphoteric elements, such as zinc, aluminum, iron and chromium, to form a three-dimensional complex including the novel reaction product and such cations. The resulting compounds can also be used in drilling fluids to enhance the rheological properties and stability. If it becomes desirable to reduce the concentratration of the coal carboxylates or to enhance the viscosifying effects at a given concentration of the coal carboxylates in a drilling fluid, a small addition of heat-stable polymeric additives, such as polysacharides (biopolymers) can also be incorporated in the drilling fluid.
Obviously, many modifications and variations of the invention, as hereinabove set forth, can be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.
|Cited Patent
|Filing date
|Publication date
|Sep 14, 1949
|Mar 13, 1951
|Standard Oil Dev Co
|Process for treating weighted muds for viscosity reduction
|Dec 29, 1953
|Nov 19, 1957
|Gulf Research Development Co
|Preparation and use of drilling fluid treating agents
|Aug 16, 1966
|Sep 23, 1969
|Canadian Patents Dev
|Continuous nitric acid oxidation of coal
|Oct 9, 1968
|Jan 9, 1973
|American Hydrocarbon Co
|Oxidation process employing nitric acid catalysis for the preparation of humates from coal
|Jun 16, 1976
|Oct 4, 1977
|Gulf Research & Development Company
|Organic acids and process for preparing same
|Jul 5, 1977
|Apr 3, 1979
|Gulf Research & Development Company
|Organic acids and process for preparing same
|Rogers, Composition and Properties of Oil Well Drilling Fluids, Third Edition, Pub. 1963, pp. 531, 544-546, 555.
|Citing Patent
|Filing date
|Publication date
|Jan 9, 1980
|Jun 1, 1982
|Gulf Research & Development Company
|Hydrocarbon emulsions
|Jan 9, 1980
|Jul 13, 1982
|Gulf Research & Development Company
|Bituminous emulsions
|Jun 4, 1984
|Nov 6, 1984
|Hughes Tool Company
|Viscosifier for oil base drilling fluids
|Mar 23, 1984
|Feb 25, 1986
|Japan Metals And Chemicals Co., Ltd.
|Drilling fluid additives
|Dec 6, 1984
|Jun 10, 1986
|Japan Metals And Chemicals Co., Ltd.
|Drilling fluid additives
|May 9, 1988
|Oct 2, 1990
|Salk Institute Biotechnology/Industrial Associates, Inc.
|Enzymatic depolymerization of coal
|Sep 21, 1990
|Jul 30, 1991
|The Salk Institute Biotechnology/Industrial Associates, Inc.
|Aqueous-soluble polymeric coal substrate for depolymerization by a lignin peroxidase
|May 2, 1996
|Dec 16, 1997
|Carney; Leroy Lloyd
|Drilling fluid process
|Feb 11, 2004
|Aug 31, 2010
|Halliburton Energy Services, Inc.
|Drilling fluids with improved shale inhibition and methods of drilling in subterranean formations
|Nov 16, 2010
|Halliburton Energy Services Inc.
|Treatment fluids with improved shale inhibition and methods of use in subterranean operations
|Mar 15, 2011
|Halliburton Energy Services Inc.
|Methods of using a polymeric precipitate to reduce the loss of fluid to a subterranean formation
|May 17, 2011
|Halliburton Energy Services Inc.
|Wellbore treatment kits for forming a polymeric precipitate to reduce the loss of fluid to a subterranean formation
|Oct 2, 2012
|Baker Hughes Incorporated
|Nano-sized particles for stabilizing viscoelastic surfactant fluids
|Jun 4, 2013
|Halliburton Energy Services, Inc.
|Treatment fluids with improved shale inhibition and methods of use in subterranean operations
|Feb 11, 2004
|Oct 14, 2004
|Colin Temple
|Drilling fluids with improved shale inhibition and methods of drilling in subterranean formations
|Sep 4, 2007
|Feb 28, 2008
|Baker Hughes Incorporated
|Nano-Sized Particles for Stabilizing Viscoelastic Surfactant Fluids
|Jan 25, 2010
|Sep 24, 2014
|Clay-free low-density oil-based drilling fluid
|U.S. Classification
|507/103, 507/107, 562/410
|International Classification
|Cooperative Classification
|European Classification


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I loved this movie with Tom Arnold, Linda Hamilton, appearances by Arnold S and Jamie Lee Curtis. This is one of those films that make you feel good. It shows that no matter what obstacles you may appear to have, you can accomplish anything if you put your mind to it. I think it's a great movie with good acting. I've seen this movie many times and will watch it many times more.
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I was skeptical when my son wanted to rent this movie, and though there are a few adult themed jokes, we ended up liking the movie. And my son likes to watch it so much, I bought it. Yes, the boy in the movie has cerebral palsy and he is funny and does a great job in this film. Great attitude. I wouldn't go to the theater to see it but, it is a good rental for young teens.
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I read a review of "The Kid and I" posted by someone on [...] entitled, "Forrest Gump goes to Hollywood" When I read that title I was a little upset. Having heard that the star of "The Kid I" actually had cerebral palsy I assumed the author of that review was just another member of the public who ignorantly assumed that cerebral palsy and mental retardation went hand-in-hand. I have endured a lifetime of dealing with this insulting misconception and I have a very strong resentment towards government agencies lumping the two together as well. After viewing "The Kid and I," however I really can't blame anyone who would come out of this particular film with that misconception firmly reinforced. There is a scene in the film in which Aaron (the seventeen year-old kid with cerebral palsy) tells Tom Arnold that the neighborhood bully calls him retarded. Mr. Arnold tells him that "it's not nice, and it's not true." I took that to mean that he had no mental disabilities. Yet, you'd never know it from the things Mr. Arnold forces him to say in his lame-brained script. In a scene directly on-point with the person who made the Gump comparison Aaron naively believes that Tom Arnold has punched his assistant in preparation for a scene. In the middle of joining in the slap-stick fun Aaron announces he has to pee (just like Gump.) Aaron is ambulatory and apparently needs no assistance... That's not all, while writing the script for the movie-within-the movie Arnold begins to rip-off "Rain Man." Both of these scenes are well before the one in which we are led to believe Aaron is not mentally-handicapped and even afterwards Arnold casts suspicion, such as the scene where Aaron (he's nearly 18, remember.) asks Arnold to rub his head while sick.Read more ›
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