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Hi Sencha & The Community!
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text:
2915 A2(4+1) - Palit
From $68 / night
Description from the manager
Description from the manager
Bedrooms: 2/
Bathrooms: 2/
Sleeps: 5/
Type: Apt. / Condo
BASIC INFORMATION: Type of property: apartments. Check in: 14 Check out: 10
FACILITIES AND EQUIPMENT: free parking within the property, common terrace for all guest in the property, courtyard, garden.
ADDITIONAL SERVICES: laundry service with surcharge at the owners place, baby bed on request with surcharge, free use of barbecue, berth for boat with surcharge (only with obligatory previous notice), breakfast with surcharge.
BEACHES CLOSE TO THE PROPERTY: pebble beach, concrete beach.
DISTANCES: The distance to the closest beach is 150 meter. The distance to the sea is 150 metar. The distance to the town center is 300 metar. Grocery store - 200 ...Read more
About the manager
About the manager
To Islands Travel Ltd.
About the owner
To Islands Travel Ltd.
- Response rate: 75%
- Response time: Within a day
- Calendar updated: 2 days ago
Overall rating:

subset: commoncrawl


text:
Tri-Coastal Design
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Nagios Jobs in Bath, Somerset
Jobs 1 to 1 of 1
3rd Line Support Engineer
A confident 3rd Line Support Engineer is required for an initial 6 month contract. This contract is working for a good organisation that often extends its contractors. You will need to have proven 3rd line support experience in a corporate environment. The initial focus of the contract will be active...
Bath -
People Source Consulting
Rate: £275 - £300 per dayPosted: 14 days ago
Nagios Jobs in Bath


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Tool Boxes & Cabinets and Benches
Weather Guard NV High Roof Ladder Rack Mounting Kit 2506$334.90
Nissan NV mounting kit for the EZ-Glide System.Learn More
Delta JOBOX 755980 24-in Long Heavy-Gauge Aluminum Underbed Box - ClearCoat$336.97
- Features:
- 3/8-in heavy-duty aluminum hinge
- Wide, surround rain gutter with auto-style bulb weather stripping Three-point locking system
- Reinforced high-strength door provides superior strength and security
- Commercial rotating T-handle
- Aircraft cable door supports
- Heavy-duty EPDM closed cell bulb weather stripping surrounds door opening to seal out moisture
- Reinforcing cross-hatch pattern Learn More
Weather Guard NV Standard Roof Ladder Rack Mounting Kit 2507$334.90
Nissan NV Standard Roof Mounting Brackets for the EZ-Glide System.Learn More
Delta PRO 407000 24-in Long Aluminum Underbed Box - Bright$333.97
Delta PRO Aluminum and Steel Underbed Boxes are built for protecting heavy tools and equipment in the toughest conditions. An extended rain gutter channels water around the outside of the door opening. Durable weather stripping forms a tight seal to prevent moisture from entering. 3-Point locking system draws the door tight against the weather stripping surrounding the door opening. It locks the door at the top and on both sides. Aluminum Underbed Boxes are made of high-strength .100-gauge tread plate aluminum.
- Features:
- High-strength hinges stand up to heavy use and attempted break-ins
- 3/4-in wide rain gutter surrounds the door opening to channel moisture away from the interior to protect the contents
- 3-point locking System locks the door at the top and on both sides for greater strength and security
- Extra heavy-duty construction withstands the toughest conditions for long-term use
- Rotating stainless steel handle is leak-proof to prevent moisture from entering
- Plastic coated galvanized steel aircraft cable door supports are mounted on stainless steel shoulder rivets to prevent twisting; opened door will support a 300 lbs. load Learn More
UWS TBC-42-W-BLK Chest Box Wedge$336.97
Chest Box; Wedge; L 42 in. x W 20 in. x H 17.25 in. Designed To Fit Against Back Of Cab. Stainless Steel Lock Handles For Strength/Security. Aluminum Lid Supports Heavy Loads. Self Closing Struts. MicroSeal Stripping Seals Out Moisture. Lid Opens 90 Degree For Easy Loading. Aluminum One Piece Tub and Lid. Patented Fully Foamed Lid.Learn More
Weather Guard Cover for 165-3-01 7887-3$332.97
Fits Side Box model 165-3-01.
- #11 in Picture
- Includes Weather Strip,Striker Loop Plate, Wireform Striker, Bolt Kit, Taptite® Screws, Hinge, and Instruction Sheet.
Delta PRO PSN1451000 47-1/2-in Long Steel Innerside Box - White$336.97
Delta PRO Steel Innersides utilize the same Gear-Lock system, self-centering latch pin, reinforced lid and high-strength body Design as the Crossovers. They mount on the top of the bed side walls and are ideal for storing longer tools and equipment. Innersides help keep the bed free for storing bulky items. Combine Innersides with a Crossover to create a wrap-around storage system.
- Features:
- Gear-Lock dual rotary locking system operates like a ratchet to lock the lid down tighter
- Self-aligning latch pin pivots from side-to-side to engage with the Gear-Lock System; no adjustments required
- 3-Layer Laminated RSL Rigid Structural Lid has a reverse beveled edge liner and an inner layer of rigid foam insulation to create the most rigid, strongest aluminum lid we've tested
- Reinforced high-strength body resists cargo damage and protects lock system
- Heavy-duty, reliable Posi-Lift gas springs automatically opens the lid for easier, faster access
- Full-length storage bin provides quick and easy access to hand tools and parts
- Full weather stripping creates a tight seal against moisture and dust
- Built-in full-length storage compartment for small tools and parts
- All models available with diamond black finish Learn More
Kargo Master L01000 Leg and Cross Bar Kit for Stdrd Cab Etc.$332.97
Extended Cab And Crew Cab Trucks With Long Or Short Bed - No Camper Or Utility Shell On Truck - 13 Ga - Marine-grade Powder Coat Finish - Load Capacity 1700 LbLearn More
Delta CHAMPION Aluminum Long-Bed Fullsize Chest with Gearlock - Bright 1-350000$336.97
- Patented Gear-Lock Latch on the stainless steel paddle handle provides premium security and weather resistance when the lid is latched shut
- 3-Layer Laminated RSL Rigid Structural Lid has a reverse beveled edge liner and an inner layer of rigid foam insulation to create the most rigid, strongest aluminum lid that Delta's ever made
- Adjustable lid strikers lock the lid down tight for superior security
- Reinforced body resists cargo damage and protects the lock system
- Gas spring lid lifts raise the lid when unlatched for easier access
- Leak-proof stainless steel paddle handles prevent moisture from entering
- Full weather stripping creates a tight, moisture resistant seal
- Available with black finish (model number 1-350002)
Montezuma Professional Red Portable Tool Box Small (22 1/2" x 13") SM200R$339.97
- Dimensions: 22½"W x14"H x 13"D
- Weight: 42lbs
- Warranty: 5 Year Limited Warranty
- Paint Type: Powder Coated
- Powder coat finish
- Holds either metric or S.A.E. tools
- Lid secures tools in position when closed
- Locking latch secures tools from unauthorized use
- Lock cylinder has double-cut keys for easier locking and unlocking
- Weather stripping creates a tight seal against dust and moisture
- Gas spring raises lid when unlatched for easy tool access
- Sturdy side handles make moving easy
- Tool inventory at a glance
- 5 Year Limited Warranty


text:
Soldier's widow thanks country, military for support in a dark hour
The Canadian Press
Published Friday, May 23, 2014 6:32AM EDT
Last Updated Friday, May 23, 2014 2:24PM EDT
PETAWAWA, Ont. -- The family of a Canadian Forces soldier who died when his light armoured vehicle rolled over is thanking the country for its sympathy and support.
Lt. Col. Dan Bobbitt's widow Monica says her husband was a soldier who loved his work.
She says he was deeply honoured to command the 2nd Regiment, Royal Canadian Horse Artillery, based in Petawawa, Ont.
Bobbitt was killed and four soldiers were injured Wednesday when their vehicle, known as a LAV III, rolled over during a training exercise at CFB Wainwright in Alberta.
Monica Bobbitt says the family is grateful for what she says is an incredible outpouring of support from family, friends, the military and the country.
Military officials have not released many details about the accident, but are investigating.
Bobbitt began his military career in Nova Scotia. He served in Bosnia, Afghanistan and worked as a liaison officer during the floods in Manitoba in 1997.
"Dan was a loving and devoted husband, father, son, brother and friend," his widow said at a brief news conference outside regimental headquarters.
"A proud Nova Scotian, Canadian and soldier, Dan died doing the job he loved."
The rollover has raised fresh concerns about the LAV III, an eight-wheeled, heavily armed and armoured utility vehicle that served as the backbone of Canada's war in Afghanistan.
There were a number of similar rollover incidents during the Afghan mission.
The Wainwright accident comes with the LAV III fleet in the process of a $1-billion upgrade to improve the vehicle's stability, armour and electronics.
More News from Canada
- Examine police behaviour in missing, murdered women inquiry: advocates
- 'Diefenbaby' dies: George Dryden, likely son of former PM, dead at 47
- 'An awful story': Boy, 7, struck and killed by rolling truck
- RCMP changes 'outdated' recruitment process; permanent residents can apply
- B.C. teen who killed Reena Virk asks for parole


text:
Check with Moore Funeral Home about which type of funeral services and products the funeral home, mortuary or memorial chapel provide at their Donalsonville, Georgia location.
Contact the Moore Funeral Home Funeral Director to ensure the services they provide match your personal needs. Call the Funeral Director at (229) 524-2465.
If there is a religious preference, make sure that Moore Funeral Home can accommodate your religious practices before, during and after the funeral ceremony and at any graveside service.
Dallas Moseley, age six, of Blakely, Ga., 39823, died Sunday, Dec. 13, 2015, in the emergency room at Tallahassee Memorial Hospital in Tallahassee, Fla. Dallas was born March 4, 2009, in Donalsonville ... Moore, 8275 Hwy. 27 South, Blakely. Funeral ... (Early County News)
Blakely-Dallas Fulton Moseley, age 6, of 17937 Cedar Springs ... from 6 Until 8 PM at Manry-Jordan-Hodges Funeral Home. Dallas was born on March 4, 2009 in Donalsonville, GA to his parents: John F. "Trip" Moseley, III and Haley Temples Moseley of ... (Albany Herald)
James Daniel North Sr., age 74, of Lithia Springs, Georgia passed away Sunday, July 12, 2015. He was born December 16, 1940 in Donalsonville ... The family will receive friends at Jones-Wynn Funeral Home in Douglasville, Thursday, July 16, 2015 from ... (Douglas County Sentinel)
Our thoughts and prayers go out to the Marshal family. Dave was a very likable person, who got along well with everyone, especially as a group leader for many years at Fram . Dave will be missed. Rhonda and family. I am so sorry to hear of Davids' passing ... (legacy.com)
Mark Moore and ... of Conyers, Ga., and Susie Gardner of Donalsonville; four grandchildren; nine great-grandchildren; one great-great-grandchild; and several nieces and nephews. The family will receive guests at Tom Stutts and Son Funeral Home, Franklin ... (The Randolph Leader)
"For many people, their obituary may be just about the only thing that is ever written about them in their whole life and death. The obituary can be the defining statement about that person for the family, friends, and community. An obituary can be read now, and saved for generations. All the more r...
"Hold faithfulness and sincerity as first principles."- Confucius, The Analects When someone you love loses a loved one, your first instinct is to comfort. Follow that instinct. If you are sincere, your heartfelt words and expressions of love are always welcome. There are a few suggestions I woul...


text:
Season 4, Episode 15 The Long Way Home
First Aired: March 18, 2000
While Rachel is on the trail of a serial kidnapper she once prosecuted, she's also concerned about her brother (Raphael Sbarge), who's run away from rehab. Capobianco: Harry Groener. Kim Doyle: Judith Moreland. Karen Archer: Erin Gray. Tom Arquette: Joe Flanigan. Coach Mahoney: Jack Kyle. Barbara: Kady Cole. Faith Cleary: Kayla Ewell. Rachel: Jamie Luner. Bailey: Robert Davi. John: Julian McMahon.
Guest Cast
Joe Flanigan Tom Arquette
Kayla Ewell Faith Cleary
Judith Moreland Judith Moreland Kim Doyle
Harry Groener Harry Groener Capobianco
Raphael Sbarge Danny
Cast & Details See all »
- Premiered: September 21, 1996
- Rating: TV-14
- Premise: A forensic psychologist experiences detailed flashbacks of crimes when she probes homicide scenes in this grim paranormal cop saga. Dr. Sam Waters' unsettling gift enables her to see the events from the perspective of victims and killers alike. Her most pe… (more)
Trending TonightSee all »
The Flash8:00 pm | CWI'll Watch421 Watching
Person of Interest10:00 pm | CBSI'll Watch346 Watching
NCIS8:00 pm | CBSI'll Watch329 Watching
Profiler - Season 2
By National Broadcasting Company (NBC)Buy New: $85.98
The Profiler: My Life Hunting Serial Killers and Psychopaths
By Hachette BooksBuy New: $21.23
Careers: Profiler
By CreateSpace Independent Publishing PlatformBuy New: $9.99
Popular Shows
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text:
The Commerce Club
Main Number: 864.232.5600
Our Story
Fri, May 13 1 Events
Wine Tasting7:00pm
Wine Tasting[ X ]
Date: Fri, May 13, 2016
Time: 7:00pm
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Wine Tasting
Friday, May 13th
Join us for a wine tasting, featuring all French wines!
$30++ per person
RSVP to 864.232.5600. 48 cancellation policy.
Find us on
Home > Our Story > Calendar > Wine Tasting
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Commerce Club55 Beattie Place, 17th FL.
One Liberty Square Building 17th Floor
Greenville, SC 29601
Copyright ©2016 by ClubCorp. All Rights Reserved.


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Join FREE | Login
+ Celebrations
+ How-To
+ Deals
Grab & Go Eggs
Cheesy Florentine Biscuit Cups
Creamy Sausage Casserole with Biscuits
Sausage, Egg and Cheese Breakfast Roll-Ups
Sausage and Egg Biscuit Bake
Mexican Breakfast Casserole
Overnight egg bakes are convenient and delicious--and usually too large for a twosome. Try a scaled-down version!
Omit the Canadian bacon for a veggie version, and try pepper Jack cheese to spice it up.
© 2016 ®/TM General Mills All Rights Reserved


text:
All over the country, and here in Southern California, there are many high income areas that thrive and tells us how some people live there.
Architect and
Inside, Las Casitas feels chaotic, messy and unpredictable. But there are residents like Navia Ortiz who have found a haven there. Navia came to Newbury Park, Calif., from a rural village in Guatemala eighteen years ago. She used to rent a piece of floor in a living room in Las Casitas. Today, she is on the lease, pays $1,300 and rents to eight recently arrived immigrants. This past decade, her apartment has been the first step to 70 or 80 immigrants. She says it's her life's purpose to give recent arrivals a home during their first months and years in the U.S.
For decades Las Casitas has been stigmatized as the 'bad' neighborhood in the Thousand Oaks area. It had its share of tensions in the early 2000s, but in reality, it's just an immigrant neighborhood. Most people in Las Casitas are from rural villages in Mexico and Central America. They come to the area to work.
As chaotic as it is from the inside, the outside stays picture perfect. America Yeresma Villanueva Nava tells us why. And former City Manager of Ventura, Rick Cole gives us some context.


text:
...I enjoy tutoring at all levels of high school chemistry: from introductory classes to the I.B., AP and SAT Subject Test. I can help anyone--from those who need remedial help to those who are on an accelerated track. Through problem solving, homework support, test prep and review of test results, I try to help students to feel confident in their understanding of the material.
Owings Mills, MDView Tutor
...There were also youth who ranged in severity on the autism spectrum. When working with individuals with Aspergers, it is especially important to identify their special interests and their triggers. Special interests can be utilized to help students excel in academic areas and to shine within the classroom.
Reisterstown, MDView Tutor
...John taught extensively during his PhD program and was recognized for his quality instruction with a departmental teaching award. While a Cancer Prevention Fellow with the National Cancer Institute, John earned his Master of Public Health degree from Johns Hopkins Bloomberg School of Public Heal...
Ellicott City, MDView Tutor
I am from Beijing, China, so I speak perfect Mandarin Chinese without any accent. I have completed my education in China including elementary school, middle school, high school, and I got my bachelor degree in 1984. I have been tutoring students in Chinese for 15 years in Maryland, my youngest student was 5 years old, my oldest student is 68 years old.
Elkridge, MDView Tutor
...I am also Orton Gillingham certified and have been taking a training in LETRS. I am a Kindergarten teacher in Baltimore County Public Schools. I am certified in Orton Gillingham.
Reisterstown, MDView Tutor


text:
worked great
Reviewed By Kevin B (CARY, IL) Reviewed for a 1998 Toyota Celica —1/31/2016 6:41 AM
Easy to install dont squeek very nice
Reviewed By Martin & (Richmond, VA) Reviewed for a 2006 Honda Pilot —5/2/2016 6:52 AM
I have been working on cars since the 1970's and in the past 10 years have only been using Green pads on all my family's vehicles. Love them, lower dust, great breaking, and quiet. A product I trust.


text:
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Home > Press > Green Earth Technologies Announces New Chief Financial Officer
Green Earth Technologies, Inc. (Pink Sheets:GETG), a manufacturer and marketer of environmentally friendly consumer products, today appointed Greg D. Adams, 47, as its Chief Financial Officer, succeeding Gordon Donovan, who has chosen not to relocate to Company headquarters in Connecticut.
From 1999 to 2007, Mr. Adams served as Chief Financial Officer of EDGAR Online Inc. (NASDAQ: EDGR), a leading provider of business information. In January 2003, he added the responsibilities of Chief Operating Officer and in 2004 was appointed as a member of the Company's Board of Directors.
Green Earth President and CEO Jeff Marshall said, "We are very pleased to have Greg join the Company as its new Chief Financial Officer. This is a pivotal role for Green Earth and Greg brings to the company the financial, accounting and strategic experience necessary to help us reach our ambitious strategic goals. I would like to thank Gordon for his service during an important time in our development and wish him well in his future endeavors."
Mr. Adams brings extensive SEC and compliance experience to the company, having served for 11 years at KPMG in the audit and advisory services group. He also was CFO of PRT Group Inc., a technology and solutions company, based in New York and the Blenheim Group. Mr. Adams is a Certified Public Accountant, a member of the New York State Society of Certified Public Accountants and the American Institute of Certified Public Accountants, and serves as Vice Chairman of Financial Executives International committee on finance and information technology. He received a B.B.A. degree in Accounting from the College of William & Mary.
Commenting on his appointment, Greg Adams said, "I look forward to building the financial infrastructure that will allow Green Earth Technologies to achieve its near- and long-term objectives. The company is just beginning to generate revenues, so I am thrilled to be a part of the team that will put the Company on the map in terms of innovative non-petroleum solutions to key industries as well as consumers at large."
About Green Earth Technologies, Inc.
Green Earth Technologies produces "G" - Branded superior performing totally green products made with American-grown base oils that utilize the power of nanotechnology to deliver environmentally friendly products with no compromise...meaning, consumers can now "do their part" without having to give up performance or value - Save the Earth - Sacrifice Nothing. The G-Brand family of products include G-OILЩ, G-WASHЩ, G-GLASSЩ, G-SCENTЩ , G-WHEELЩ and G-TIREЩ, and are offered in a wide range of automotive categories including performance & appearance chemicals.
Certain statements in this release regarding future events and developments, future performance, management's expectations, beliefs, plans, or projections are "forward looking statements" within the meaning of the federal securities laws. Such statements are subject to a number of risks and uncertainties, and are based on the Company's current expectations, and speak only as of the date of such statements. Actual Company results may differ materially from any forward-looking statements due to such risks and uncertainties.
For more information, please click here
ICR Inc.
Brian Ruby
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text:
|Publication number
|Publication type
|Application number
|Publication date
|May 24, 2011
|Filing date
|Aug 28, 2008
|Priority date
|Aug 29, 2007
|Fee status
|Also published as
|Publication number
|Khodadad Nazari, Hosein Rahimi, Ramin Khodafarin, Mohammad Kameli, Hosein Brijanian
|Original Assignee
|Research Institute Of Petroleum Industry (Ripi)
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (17), Non-Patent Citations (5), Referenced by (9), Classifications (11), Legal Events (2)
|External Links: USPTO, USPTO Assignment, Espacenet
The present application claims the benefit of EP 07 115 239.1, filed on Aug. 29, 2007, whose content is incorporated by reference herein in its entirety.
The present invention relates to the filed of gas stabilization and storage.
Gas hydrates are ice-like non-stoichiometric crystalline compounds. These are cages of water molecules, formed around guest molecules, which are simply called hydrates in gas and oil industries.
The conditions necessary for the formation of hydrates include the presence of water or ice, the presence of a non-polar gas or liquid or a gas or liquid of low polarity and of course proper temperatures and pressures. Water molecules form cages around the guest molecule, as a result of their hydrogen bonding, however they form no chemical bonds with the guest. The gaseous guest molecules are actually compressed and trapped in this porous structure, giving it the potential for storing gas compounds and for their transportation [Sloan, Jr. D., "Fundamental Principles and Applications of Natural Gas Hydrates", Nature, 246(6964), 353-359 (2003).].
Hydrates of interest in industries, especially in the production and processing of natural gas and oil, are composed of water and guest molecules, such as for example methane, ethane, propane, iso-butane, normal butane, nitrogen, carbon dioxide, hydrogen sulfide and/or hydrogen [Sloan, Jr. D., "Fundamental Principles and Applications of Natural Gas Hydrates", Nature, 246(6964), 353-359 (2003).]. Other guest species like for example ethylene, N2O, acetylene, vinyl chloride, methane halides, ethane halides, cyclo-propane, methyl mercaptanes, sulfur dioxide, Ir, Ar, Xe, oxygen, trimethylene oxide etc. can also form hydrate clathrates.
Additives having different properties can be used during the formation of gas hydrates. Compounds prohibiting the formation of such structures are so called hydrate inhibitors. One may distinguish between two groups of thermodynamic inhibitors, such as for example methanol, glycols and others that avoid the formation of hydrates by shifting the phase diagram of the system and kinetic inhibitors, such as for example polyvinyl pyrrolidone, which postpone the formation of hydrates up to some days.
Other types of additives having a rather opposite effects are also known and are so called hydrate promoters, such as for example sodium dodecyl sulfate promoting the formation of hydrates.
The major problem with the application of natural gas as a fuel is its transportation, because of its low density, i.e. small amounts of natural gas have high volumes. One solution to this problem is the high-pressure storage of natural gas, which is performed in two distinct methods of liquefied natural gas (LNG) and compressed natural gas (CNG), depending on the transportation systems used. LNG is very expensive from a process equipment and transportation equipment point of view. CNG on the other hand, is not a suitable method for gas transportation due to the high volume of the compressed gas.
Conversion of methane to methanol, which is a liquid and easily transportable fuel, might be an alternative but it is not a proper method due to the high costs and the required operations loosing of up to 47% of the heat value of natural gas.
The production of hydrates for storing the hydrocarbon gases can be another alternative. This will be a less costly method with higher levels of safety and will require less energy and equipment for forming the hydrate and dissociating it at the final destination. It is also safer than the traditional methods of LNG and CNG, which always accompany the risk of explosion, especially in the case of accidents.
The major problems of using hydrates for the purpose of making gases transportable is the high pressure necessary for forming, storing, and transporting the hydrates. Numerous efforts have been made to solve this problem and one solution proposed is the application of slurry hydrates that are formed by gradual addition of gases to water, suggested in U.S. Pat. No. 6,082,118. This method however, suffers drawbacks including a low final gas content that make it expensive and not economic.
Stern L. A, et al (Energy and Fuels 15(2), 2001, 499-501) and Tse (J. Supramol. Chem., 2, 2002, 467-472) reported that decreasing the pressure over the hydrates leads to their decomposition, and because this is an endothermic process, the molten layer of the hydrate converts to ice, protecting the remaining hydrate, which is entitled the self-preservation phenomenon. Stern L. A. paid specific attention to the stabilization of methane hydrates in 50-75� over the equilibrium temperature (193 K) and under atmospheric pressure, using pressure release methods.
Satoshi T., (J. Phys. Chem. A, 105(42), 2001, 9756-9759) reported that the bigger the size of the hydrate particles is, the higher the probability of keeping hydrates under higher temperatures will be. For example, they mentioned that for hydrate particles of 1000-1400 μm in dimension, a low gas content of only about 20% (v/v) of methane can be achieved in 263 K and 1 atm.
Stern et al, (Energy & Fuels, 15 (2), 2001, 499-501), Tse, et al., (J Supramol. Chem., 2, 2002, 467-472), and Kush et al., (Phys Chem. Chem. Phys., 6(27), 2004, 4917-4920) suggested using the self-preservation property of hydrates. This method suffers disadvantages, like low stability, conversion of hydrate to ice, and their low gas content.
U.S. Pat. No. 3,975,167 describes a method for forming hydrates by a special process and apparatus, which provide the temperature and pressure for the formation the hydrate in a suitable depth of the sea. According to this invention hydrates are formed using proper cooling systems and through providing the required pressure by choosing the proper depth in water. The gas is released in the destination by bringing the hydrate to the surface and heating it. However, also expensive equipment is necessary for such processes.
U.S. Pat. No. 5,536,893 describes a method for forming and transportation of hydrates. This patent discloses the details of the system and process of production of hydrates from water and gas. The method is based on spraying water and cooled gas, which is followed by hydrate formation, its removal from the reactor, its agglomeration, increasing its density, saturation of its pores with the gas and finally its storage or transportation.
But this method is used under very difficult-to-achieve adiabatic conditions. The hydrate storage is performed outside the thermodynamic hydrate stabilization area shown in
The recovered gas, in addition, is only 20-70% of what is initially stored, which is not directly mentioned in the patent, but is actually expected to be very low due to the inevitable hydrate storage conditions.
U.S. Pat. No. 6,082,118 storage and transportation of slurry hydrates suspended in liquid hydrocarbons under metastable conditions are disclosed. The hydrates formed in this invention, however, have low gas contents.
The stability of hydrates is defined by their inherent phase diagrams. Gas hydrates have high stabilities at high pressures (e.g. 150 bar) and low temperatures (e.g. 4� C.). It should also be noted that the pressure should be adjusted with using the same gases as for the desired hydrates in order not to disrupt the thermodynamic equilibrium of the existing phases. Given that the phase boundary curves of gas hydrates are of exponential nature, the so-called hydrate formation zone is much wider at higher pressures.
For instance, taking 0� C. as the reference temperature the methane hydrates formed under a pressure of 100 bar will be stable in a temperature range of from 0-13� C., while if the pressure is reduced to 50 bar, methane hydrate will be stable only in the range of 0 to 5.8� C., as described in
Temperatures below 0� C. bear the risk of ice-formation, which leads to the release of the gases stored in the primary hydrate structure. The advantage of high pressures is that by adjusting the system composition in a way that water is the limiting reactant, all of the water can be converted to hydrates that are highly saturated with gas molecules. But even at high pressures (e.g. 150 bar for CH4), and in particular at low pressures, the hydrate pores are not filled with the gas molecules, and the gas content of the hydrate is not high. Additional tests also show that hydrates formed through the above-mentioned methods known in the art suffer disadvantages, like low gas-contents, low mechanical stability, low yield, and long equilibrium times in the hydrate formation process.
On the other hand, although the formation of hydrates at high pressures and low temperatures (e.g. 250 bar, and 4� C.) is favorable, transportation of gases in hydrates under such high pressures can be highly dangerous.
Many efforts have been made to use the hydrate self-preservation phenomenon in order to make it possible to store hydrates under milder conditions, like atmospheric pressure up to 30 bar. In order for the storage pressure to be 1 bar, the system temperature must be reduced to −20� C. or lower (e.g. −40� C.), which is very costly, and also causes the disadvantage of the ice-formation, as well as the fact that the formed hydrates will have low gas contents.
In general the storage pressure and gas content of hydrates are important factors in storage conditions. It is noteworthy that the higher the gas content of a hydrate is, the faster its dissociation will be.
One would also realize that, although the hydrate self-preservation is a fully understood phenomenon, there is no data available on the long-term stabilization of hydrates in or out of the thermodynamic stability conditions of hydrates.
Hydrates start to change to ice at temperatures below zero (0� C.), especially between 0 to minus 33� C. This has been proved by neutron diffraction spectroscopy [Kush. W F, et al, Phys. Chem. Phys. 6(21), 2004, 4917-49201]. The ice particles formed in the temperature range of from 0 to minus 33� C. are of hexagonal (Ih) crystalline structure, and their agglomeration prohibits the gas from leaving the hydrate structure. Below −33� C., cubic ice (IC) is formed, which has far less agglomeration, and hence a far less ability of blocking the gases, and the hydrates are hence gradually dissociated.
There exists a strong need to prepare hydrates with high gas contents and achieve good stability allowing their transportation at conditions that are relatively "mild", such as for example low pressure. Also, further drawbacks described above according to the prior art should be resolved.
In one embodiment, the present invention provides a composition for increasing stability and gas content of gas hydrates comprising:
a. water;
b. a gas;
c. a stabilizer that is an organic compound (which can be in the form of a polymer) having both hydrophillic and hydro-phobic portions, wherein the stabilizer results in an increase in at least one of stability or gas content of the gas hydrate.
The composition can further comprise a hydrate promoter, such as sodium dodecyl sulphate. The composition can further comprise a hydrate inhibitor, such as polyvinylpyrroli-done. The hydrate stabilizer can be selected from the group consisting of cellulosic ethers, polyalkylene glycols, polyamines, polyvinylpyrroli-done, polyamides, polypeptides, ethoxylated fatty amines, ethoxylated fatty acids; sulphonated, phosphonated or ethoxylated water soluble polymers and mixtures thereof. The hydrate stabilizer can be selected from the group consisting of hydroxy allyl cellulose derivative, polypropylene glycol, polyethylene glycol, polyethylene amine, polypropylene amine, polyaniline, ethoxylated polyamines, polyaminoacids, and combinations thereof. The hydrate stabilizer can be selected from the group consisting of hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethylcellulose and combinations thereof. The stabilizer can be a cellulosic ether. The stabilizer can be a hydroxyalkyl cellu-lose. The stabilizer can be hydroxyethyl cellulose and/or hydroxypropyl methylcellulose. The stabilizer can have a molecular weight of 5,000 to 1,000,000. The stabilizer can be present in an amount of 0.1 to 1% by weight in relation to the amount of water, or in an amount of 0.3 to 0.8% by weight in relation to the amount of water, or in an amount of 0.5% by weight in relation to the amount of water. The hydrate stabilizer can be cellulose ether. The hydrate stabilizer can be a polyalkylene glycol.
The hydrate stabilizer can be poly-ethylene glycol. The hydrate stabilizer can be a polyalkylene glycol having a molecular weight of 300 to 300,000. The hydrate stabilizer can be a polyalkylene glycol and be present in an amount of 0.3 to 1.2% by weight, or 0.4 to 0.9% by weight, or 0.6% by weight in relation to the amount of water. The hydrate stabilizer can be a polylysine. The hydrate stabilizer can be a mixture of polyeth-ylene glycol, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose, wherein the concentration of hydroxyethyl cellulose is 0.1%-0.4% by weight, the concentration of hydroxypropyl cellulose is 0.1%-0.2% by weight, the concentration of hydroxypropyl methyl cellulose is 0.1%-0.3% by weight and the concentration of polyethylene glycol is 0.1% to 0.4% by weight in relation to the amount of water.
Preferably, the concentration of hydroxyethyl cel-lulose is 0.2% by weight, the concentration of hydroxypropyl cellulose is 0.1% by weight, the concentration of hydroxypropyl methyl cellulose is 0.1% by weight and the concentration of polyethylene glycol is 0.2% by weight in relation to the amount of water. The stabilizer can comprise 0.1 to 1.2% by weight of polyalkylene glycols in relation to the amount of water. Or 0.4 to 0.9% by weight in relation to the amount of water, or 0.6% by weight of polyalkylen glycol in relation to the amount of water. The gas can be selected from the group consisting of methane, ethane, propane, iso-butane, acetylene, ethyl-ene, cyclopropane, natural gases or any other mixtures of hydrocarbons or other volatile compounds like O2, N2, CO2, SO2, SO3, noble gases, H2S, ni-trogen oxides and H2 and mixtures thereof.
30. The composition according to claim 1, wherein the gas is selected from the group consisting of hydrocarbons, natural gases, hydrogen, noble gases and carbon oxides and mixtures thereof. The gas can be methane. The gas can be carbon dioxide. The gas can be natural gas.
In one embodiment, the present invention provides a process for production of gas hydrates comprising the steps of
a. dissolving the stabilizer in distilled water,
b. mixing the stabilizer solution with a gas to obtain a mixture,
c. pressurizing said mixture with the same gas,
d. reducing temperature to 1-4� C. to form hydrates,
e. adjusting the temperature to (−10� C.)-(+5� C.),
f. reducing the pressure to a desired storage pressure.
The gas can be methane or natural gas and the storage pressure is 13 bar. The gas can be methane or natural gas and hydrate formation can take place at 120 bar. The gas can be carbon dioxide and the storage pressure can be 7 bar.
The gas can be carbon dioxide and hydrate formation can take place at 50 bar.
In one embodiment, the present invention provides a method of stabilizing gas hydrates, wherein a stabilizer is added to the mixture selected from the group of cellulosic ethers (e.g. hydroxyethyl cellu-lose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethylcellulose), hydroxy alkyl cellulose derivatives, polyalkylene glycols (e.g. polypropylene glycol, polyethylene glycol), polyamines (e.g. polyethyl-ene amine, polypropylene amine, polyamines, polyamides, polyaniline, eth-oxylated polyamines), polyvinylpyrroli-done, polypeptides (e.g. polylysine), ethoxylated fatty amines, ethoxylated fatty acids; sulphonated, phospho-nated or ethoxylated water soluble polymers or mixtures of the above men-tioned compounds.
In one embodiment, the present invention provides a method for the stabilization of gas hydrates comprising the steps of
a. dissolving a hydrate promoter in water,
b. applying high gas pressure to the solution until hydrate forming has finished,
c. adding a solution of a hydrate inhibitor.
e. adjusting the temperature to (−10� C.)-(+5� C.),
f. reducing the pressure to the suitable storage pressure.
The hydrate promoter can be sodium dodecyl sulphate. The hydrate inhibitor can be polyvinylpyrrolidone.
The present invention solves the above problems since it has now been found that drawbacks, for example occurring in connection with slurry and self-preservation methods, can be avoided with use of low dose hydrate stabilizers.
According to an embodiment of the present invention the high gas-content hydrates are kept and stored in their thermodynamic stability zone and can be used to transport different gases or gas mixtures of different compositions (e.g. in the case of natural gas) under relatively mild operating conditions. The pressures according to the present invention, under which the hydrates are transported, are preferred to be in the range of 8-16 bar, but any other temperature and pressure condition, under which hydrates prepared according to the present invention can be stored and kept with an acceptable level of stability, are also within the scope of the invention.
In order to store the gases efficiently and safely by means of hydrates, chemical substances and formulations are used that prohibit the dissociation of hydrates. The substances are herein referred to as "low dose hydrate stabilizers". The compounds increase the gas content of hydrates through increasing the gas solubility, and also have the ability to avoid the dissociation of hydrates under operational conditions close to the phase boundary curve which is equivalent to the hydrate thermodynamic stability zone (a bit to the left of the phase boundary curve). High concentrations of these stabilizers (mostly 1% or higher for example for cellulosic ethers) form viscous solutions, disrupting the diffusion of gas into the solution and the consequent hydrate-formation.
That is the reason why according to the present invention these compounds are preferably used in concentrations of less than 1% w/w, however if the high-viscosity problem is solved in some way, the compounds can also be used in relatively higher concentrations up to 5% without the formation of a gel phase.
Some of the properties of compounds used as low dose hydrate stabilizers according to the invention are the following:
1—They stabilize hydrates at low pressures and prevent their dissociation.
2—They increase the gas solubility in comparison to conventional hydrate formation systems.
3—They have no inhibition effects or their inhibition effects are negligible, or in case they have a so-called inhibition effect they should be used together with a suitable promoter.
4—These compounds are completely water soluble, or have relatively high water solubility.
5—They are chemically stable in the operating temperature range, do not dissociate considerably and can be recycled and used repeatedly.
6—Their presence, preferably at low doses, leads to the stabilization and preferably does not considerably change the thermodynamic behavior of hydrates.
7—These compounds are preferred to be environmental friendly.
Some of the compounds having the above mentioned properties, and showing the desired effects, according to the desired subject matter of the invention are mentioned below.
The "low dose hydrate stabilizers" according to the invention used to stabilize hydrates are selected from cellulosic ethers (e.g. hydroxy alkyl cellulose derivatives, like for example hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethylcellulose), polyalkylene glycols (e.g. polypropylene glycol, polyethylene glycol), polyamines (e.g. polyethylene amine, polypropylene amine, polyaniline, ethoxylated polyamines), polyvinylpyrrolidone, polyamides, polypeptides (e.g. polyaminoacids like for example polylysine), ethoxylated fatty amines, ethoxylated fatty acids; sulphonated, phosphonated or ethoxylated water soluble polymers or mixtures of the above mentioned compounds. Optionally a low-dose hydrate promoter can also be present.
These organic compound tend to have both hydrophillic and hydrophobic portions, which allows them to interact with both the water and the gas, particularly when the gas a hydrocarbon.
In case cellulosic ethers are used as stabilizers, a molecular weight of 5,000 to 1,000,000 is preferred.
In case polyalkylene glycols are used as stabilizers, a molecular weight of 300 to 300,000 is preferred.
The invention may further comprise a hydrate promoter like for example sodium dodecyl sulphate.
The present invention further relates to a process for the formation and stabilization of hydrates of different gases and volatile compounds (e.g. methane, ethane, propane, iso-butane, acetylene, ethylene, cyclopropane, natural gases or any other mixtures of hydrocarbons or other volatile compounds like O2, N2, CO2, SO2, SO3, noble gases, H2S, nitrogen oxides and H2 or mixtures thereof).
The process according to the invention uses high to medium pressures of gases (the hydrate of which is desired) over aqueous solutions and alternatively solutions in other organic or inorganic solvents comprising one or more of the mentioned stabilizers in a suitable dose.
The formation pressure may vary depending on the type of the gas (e.g. 120 bar for natural gas). The hydrates formed in this way can be stored under relatively mild temperature and pressure conditions. The hydrate formation temperature depends on the type and nature of the gases and the phase diagrams thereof, and is preferably about 4� C. for almost all of the gases.
Hydrate inhibitors like Polyvinyl pyrrolidone (PVP) and derivatives thereof, or other hydrate inhibitors leading to the very slow formation of the desired gas hydrates are also applicable as hydrate stabilizers, in case they are used together with a suitable hydrate promoter (e.g. Sodium dodecyl sulfate) that compensates the reduction of the hydrate formation rate.
The stabilization and storage of the hydrates can be performed under different pressures of 8 to 15 bar, depending on the nature of the gas or the composition of the gas mixtures (e.g. 15 bar in the case of methane and natural gas hydrates, and 7 bar for carbon dioxide hydrate). The stabilization and storage temperatures are in the range of from minus 5 to minus 10� C. depending on similar conditions.
The most preferred stabilizers are hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose and/or polyethylene glycol or any mixtures thereof.
The concentration of low dose stabilizers in aqueous solutions is 0.1-1.0% (W/V), preferably 0.3-0.8% (W/V) and most preferably 0.5% (W/V). So one of the most preferred composition contains at least 0.5% of hydroxyalkylcellulose.
The preferred concentrations of polyalkylene glycol stabilizers are 0.3% to 1.2% by weight, preferably 0.4% to 0.9% by weight and most preferably 0.6% wt of polyethylene glycol.
In formulations and mixtures of stabilizers the sum of the concentrations of cellulosic ethers including hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methylcellulose is about 0.3% to 0.9% wt, preferably 0.4% to 0.7% wt and most preferably 0.5% wt.
In formulations and mixtures of the stabilizers the concentration of polyalkylene glycols is about 0.1% to 0.5% wt, preferably 0.1% to 0.3% wt and most preferably 0.2% wt.
In formulations and mixtures of hydroxyethyl cellulose stabilizers the concentration of this species is 0.1% to 0.4% wt, preferably 0.2% wt, the concentration of hydroxypropyl cellulose is 0.1% to 0.2% wt and preferably 0.1% wt, and the concentration of hydroxypropyl methyl cellulose is 0.1% to 0.3% wt and preferably 0.1% wt, and the concentration of polyethylene glycol is 0.1% to 0.4% wt and preferably 0.2% wt.
It is noteworthy that the higher the molecular weight of the polymers is, the lower its preferred weight percent will be in the used formulation. For instance the optimum amount of hydroxypropyl cellulose with a molecular weight of 1,000,000 Daltons is required to have a concentration of 0.1% wt in the formulation, while in case the molecular weight is 100,000 Daltons, the required concentration should be around 0.2% wt.
The low dose stabilizers of the present invention do not only increase the lifetime of the hydrates, but they also considerably increase the gas content of the hydrates.
After the formation of the gas hydrates (of e.g. methane, natural gas and carbon dioxide hydrates), and according to the preferred method of the present invention, the temperature is initially decreased to temperatures lower than the melting point of ice (i.e. minus 5 to minus 10� C.), and the pressure is then reduced (depending on the nature and composition of the gas mixtures) reversibly or irreversibly, preferably in a reversible manner (e.g. to 12-15 bar and preferably 5 bar for methane and/or natural gas, 7-9 bar and preferably 8 bar for carbon dioxide). The pressure release is most preferred to be performed in a reversible manner.
The hydrates formed according the above-mentioned method of the present invention or any variation thereof can be easily stored in the mentioned thermal and pressure conditions. It should of course be noted that the pressure drop should be such that the operational conditions do not reach those outside the stability zone of the hydrate. In such a case (e.g. 12 bar and minus 5� C. for methane and/or natural gas hydrates), hydrates will not be thermodynamically stable.
Using very low temperatures (e.g. −30� C.) will also increase the amount of ice-phase and also the rate of hydrate to ice conversion.
The experimental results prove that in the absence of stabilizers according to the invention dissociation of hydrates and their conversion of all or a part of them to ice occur. In such cases (after the establishment of equilibrium and stabilization of the system pressure) the formed hydrates will have very low gas contents (this can be observed regarding the fact that such hydrates does not burn). Hence, the clear advantages of the invention can be proved.
The low dose stabilizers of the present invention not only stabilize the hydrates but also increase the gas content of hydrates. The mentioned stabilizers make it possible to store the formed hydrates at relatively higher temperatures and lower pressures (see
In fact these stabilizers induce the ability that hydrates that are formed under severe temperature and pressure conditions, be kept in milder temperatures and pressures, near the phase diagram conditions (the dashed sections in
The stabilizers of the present invention also lead to an increase in the density of CO2 hydrates, which provides the opportunity to keep the hydrates of this gas under mild operational conditions under low depths of water in pools, lakes, seas, and oceans (under depths the exerted pressure of which is equivalent to 13 bar). By doing so, it will become possible to eliminated and store this greenhouse gas in the form of hydrates.
The stability conditions of CO2 hydrates in the presence of the mentioned stabilizers is 8 bar and −10� C. The so-stored CO2 can also be restored and used if necessary.
Regarding the fact that the mentioned stabilizers do not change the phase diagram of the hydrates, their effect should be based on the kinetics of the said hydrate formation and dissociation processes.
Based on this fact, one should distinguish between the low dose hydrate stabilizers of the present invention and kinetic hydrate promoters (unlike the so-called promoters), the stabilizers of the present invention do neither facilitate the formation of hydrates, nor do they have a considerable kinetic inhibition effect on the formation of hydrates. In fact the major function of these compounds is the long-term (practically infinite) stabilization of the formed hydrates and the considerable slowing of the hydrate dissociation in a range of −10-+10� C. and even outside the stability zone of hydrates. As a result the mentioned cultrate hydrate stabilizers can be used in the following cases:
a) Stabilization of different hydrate structures of I, II, H in the stability and metastability zones, b) Formation of hydrates of higher gas contents of gases, or hydrocarbons forming the hydrates, c) Increasing the density and physical stability of hydrates, d) storing CO2 in the form of stable hydrates, e) decreasing the dissociation rate of hydrates at conditions out of their stability region, outside the hydrate stability zone, or in any other applications or effects in the field of hydrates.
The hydrates formed according to the method, using the formulations of present invention, dissociate rapidly in a temperature range of 30-35� C., completely releasing their gas content, for further applications, and the stabilizer solutions can be recovered and used for virtually unlimited runs.
The dashed elliptical zone in
The method for the application of the low dose stabilizers is as follows:
The solution of the stabilizer in distilled water is first entered into a high pressure reactor, where it is mixed with the gases of desire and pressurized with the same gas to reach the optimum pressure (depending the nature and chemical composition of the gas, e.g. 120 bar for methane and 50 bar for CO2).
The hydrate memory (i.e. the hydrogen bond content of water, caused due to the hydrophobic interactions between the gas molecules and the polar water molecules) can also be taken advantage of, since this property facilitates the formation of hydrates and reduces the over pressure. However the method and formulations of the present invention do not depend on the presence of hydrate memory effect as a pre-requirement.
The next step includes the reduction of the system temperature down to 1-4� C. (point b in
In a next step, the system temperature is reduced to (−10)-(+5)� C., preferably to −10� C. and the pressure is reduced down to 6-14 bar (depending on the nature and composition of the gas; e.g. 13 bar for methane and/or natural gas and 7 bar for CO2) in a reversible way and preferably with a rate of 15-20 psia/min. The hydrates formed through the proposed method prove to have the mentioned superiorities over the conventionally formed hydrates.
The most preferred stabilizers comprise hydroxyethyl cellulose (M.W=5000-200,000 Daltons) hydroxypropyl cellulose (M.W=100,000-1000,000 Daltons) hydroxypropyl methylcellulose, carboxymethyl cellulose and polyethylene glycol (M.W=300-30,000 Daltons) or any mixtures thereof in a composition range of 0.1% to 1% (W/V).
The preferable aqueous formulation comprises hydroxyethyl cellulose (0.1-0.4% (W/V)), hydroxypropyl cellulose (I.W=100,000, 0.1-0.3% (W/V)) hydroxypropyl methylcellulose (M.W=200,000, 0.1-0.3% (W/V)) and poly ethylene glycol (M.W=30,000, 0.1-0.4% (W/V)).
The most preferable composition comprises, hydroxyethyl cellulose (0.2% (W/V)), hydroxypropyl cellulose (0.1% W/V), hydroxypropyl methylcellulose (0.1% (W/V)) and polyethylene glycol (0.2% (W/V)).
The hydrates formed in the presence of the hydrate stabilizers of the present invention, especially cellulosic ether stabilizers, have very good physical properties, and cannot easily be broken, which is a virtue in the storage procedures.
The hydrates can be formed in the shape of cubes or spheres of different dimensions. The dimensions of the structures can be in the range of 10 to 20 cm in the case of cubic structures or 15-30 ml in the case of spheres. The shaping is performed after the hydrate slurry becomes paste like, or in the case of production of powder hydrates a pelletizer performs it.
In case of storing spherical hydrates, it is preferred to use spheres of two dimensions. The small spheres, in this case can fill the empty spaces between the large ones.
We mention some examples to indicate the applicability of the embodiments of the invention. However the gist of the present invention is by no means limited to the examples below.
100 milliliters of distilled water was entered into a 300 ml high pressure reactor (Parr Instruments, HC. 276), and the pressure was then increased up to 120 bar, using methane gas (In this case the hydrate memory is removed at 34� C. for 4 hours [This is done just to show the efficiency of the method; and is not necessary in real-time experiments, knowing that the hydrate memory effect may also facilitate the process]). The system temperature is then reduced down to 4� C. with a rate of 1� C./min. The pressure-time, temperature-time and pressure-temperature changes are stored in a computer throughout the process. After the formation and completion of the hydrates, the system temperature is reduced to −10� C., and its pressure is preferably reversibly reduced down to 13 bar (with a rate of 1.5 bar/min).
The hydrates produced in this way can be stored for 2-3 weeks under the storage conditions. For the purpose of releasing the gases (in this example methane), the system temperature is increased to 30� C. (The gas content of the hydrate can be calculated by measuring the amount of the released gas).
A mixture of 100 ml of distilled water containing 0.5% (W/V) of hydroxyethyl cellulose (HEC), as a preferred low dose stabilizer, was prepared by stirring the solution for 20 hours prior to use, to completely homogenize the solution. The solution was entered into the same reactor as the example above and it was pressurized up to 110 bar using methane. The other steps were followed according to the example above. The formed hydrate proved to be much more stable than that of the above comparative example (even after 20 weeks).
This figure shows that the gas content of the hydrate is more than that of the above comparative example.
Next, it is seen that the hydrate is stable even after long periods of time (Here after 20 weeks) even after reversibly reducing the pressure down to 13 bar. This proves the application of the hydrates in gas transportation to be economic, especially due to their stability under relatively milder temperature and pressure conditions.
In fact the presence of a hydrate stabilizer (which is HEC in the present example), increases the gas content of the hydrates up to 61% (under operation formation conditions of p=110 bar, T=4� C., and storage conditions of −10� C. and 15 bar and the methane volume to the hydrate volume is increased from 31% to 105% (V/V). The maximum theoretic gas content for structure I is taken to be about 172 m3/volume unit of hydrate, and the compressibility factor (z) is calculated using the Peng-Robinson equation.
Composition of natural gas used in the experiment
Volume %
All the steps were followed accordingly (P=110 bar, T=4� C. for formation) and (P=14 bar, T=−10� C. for storage), and comparing with the same conditions of example 1 for natural gas, the gas content of the hydrate was found to be increased up to 3.5 times (from 31.4% (V/V) in the absence of the hydrate stabilizer (under P=82 bar, and T=4� C.) to 110% (V/V)).
A solution of 80 ml of distilled water containing 500 ppm sodium n-dodecyl sulfate (SDS), as the promoter for hydrate formation, was entered into the same reactor as the example 1 and it was pressurized up to 100 bar using methane. After cooling to 4� C. and consuming methane (due to hydrate formation), system pressure reached to 45 bar. Then, 20 ml of hydroxyethyl cellulose (HEC) solution (2.5% W/W) was inserted into the stirring reactor by means of methane forward pressure so that the system was again pressurized up to 90 bar (in order to increase the gas content and completing the hydrate). The other steps were followed according to example 1. Results showed that the gas content of the hydrate is more than that of example 1. It was observed that the hydrate is stable for long periods of time (here after 20 weeks) even after reversibly reducing the pressure down to 15 bar.
In fact in the presence of both of the hydrate promoter (which is SDS in the present invention) and the hydrate stabilizer (which is HEC in the present invention), the rate of hydrate formation increases about 30 times (in comparison to example 1), the gas content of the hydrate increases up to 76% (under operation formation conditions of p=100 bar, T=4� C., and storage conditions of −10� C. and 15 bar) and the stored methane volume per hydrate volume is increased up to 130.
Polyvinyl pyrrolidone (PVP) is well known as hydrate kinetic inhibitor, however once the hydrate is formed, the compound is found to have a much higher stabilizing effect on the formed hydrate which is the reason behind the great desire to use it as a hydrate stabilizer and trying to overcome its inhibition effects. It is found that using sodium dodecyl sulfate (SDS) as the effective promoter, not only is it possible to overcome the inhibiting effects of PVP, but it can also be used as a very good hydrate stabilizer to be applied as an efficient low-dose hydrate stabilizer.
A solution of 80 ml of distilled water containing 500 ppm (0.05% W/W) of sodium n-dodecyl sulfate (SDS) as the promoter for hydrate formation, was entered into the same reactor as the example 4 and it was pressurized up to 115 bar using methane. After cooling to 4� C. and consuming methane (due to hydrate formation), system pressure reached 41.5 bar (after about 15 hrs). Then, 20 ml of polyvinyl pyrrolidone (PVP, average MW˜1300000) solution (2.5% W/W) was inserted into the stirring reactor by means of methane forward pressure so that the system was again pressurized up to 82 bars (in order to increase the gas content and completing the hydrate). The other steps were followed according to the example 1. Results showed that a rigid hydrate was produced and its mechanical resistance was much better than the hydrate of Example 3. Furthermore, gas content of the hydrate is 47% (operation conditions: P=100 bar, T=4� C., storage condition: −10� C., 15 bar). It was observed that the hydrate is stable even after long periods of time (here after 20 weeks) even after reversibly reducing the pressure down to 15 bar. One should, however, note that in the case of application of PVP (a well-known kinetic hydrate inhibitor), which normally leads to the very low rates of hydrate formation, together with SDS (a well-known hydrate promoter) the formed hydrate is very rigid and stable after the formation, while the gas content is 47%.
The following table compares the results of control experiments with the main experiments.
P after
Time for
P initial
P at
at 35.0� C.
of hydrate
~3 hrs
>6 days
very hard
and rigid
>2 days
~5 hrs
*PVP Average M.W~1,300,000, The solution of SDS and PVP was prepared and used directly at the start of experiment.
#HEC, Average M.W~200,000, the solution of SDS and HEC was prepared and used directly at the start of experiment.
In fact the presence of a hydrate promoter (which is SDS in the present invention) and the hydrate stabilizer (which is PVP in the present invention), the rate of hydrate formation increases about 38 times (in comparison to the control experiment i.e. in the absence of SDS promoter). Furthermore, gas content of the hydrate was about 47% (under operation formation conditions of p=100 bar, T=4� C., and storage conditions of −10� C. and 15 bar).
|Cited Patent
|Filing date
|Publication date
|Apr 2, 1975
|Aug 17, 1976
|Chevron Research Company
|Transportation of natural gas as a hydrate
|Dec 23, 1988
|Apr 10, 1990
|Institut Francais Du Petrole
|Method of transporting a hydrate forming fluid
|Jan 7, 1994
|Jul 16, 1996
|Gudmundsson; Jon S.
|Method for production of gas hydrates for transportation and storage
|May 25, 1994
|Mar 9, 1999
|Colorado School Of Mines
|Method for controlling clathrate hydrates in fluid systems
|Dec 19, 1997
|Mar 14, 2000
|Petroleo Brasileiro S.A.-Petrobras
|Process for the thermo-hydraulic control of gas hydrates
|Jul 7, 1998
|Jul 4, 2000
|Mobil Oil Corporation
|Storage and transport of gas hydrates as a slurry suspenion under metastable conditions
|May 15, 2001
|Jun 29, 2004
|Bj Services Company
|Well service composition and method
|Jul 11, 2000
|Mar 15, 2005
|Basf Aktiengesellschaft
|Grafted polymers as gas hydrate inhibitors
|Jun 28, 2004
|Jun 27, 2006
|Bj Services Company
|Well stimulation compositions
|Nov 7, 2002
|Jul 10, 2003
|Mitsubishi Rayon Co., Ltd.
|Process for producing amphipathic polymers
|Apr 5, 2005
|Oct 5, 2006
|Bj Services Company
|Method of completing a well with hydrate inhibitors
|Apr 21, 2006
|Nov 2, 2006
|Air Products and Chemicals, Inc.
|Amine-based gas hydrate inhibitors
|Title not available
|Title not available
|Jul 8, 1991
|Jan 21, 1993
|Jon Steinar Gudmundsson
|Method for production of gas hydrates for transportation and storage
|Oct 1, 1996
|Apr 17, 1997
|Bj Services Company, Inc.
|Method for controlling gas hydrates in fluid mixtures
|Jun 23, 2000
|Jan 4, 2001
|Metasource Pty Ltd
|Natural gas hydrate and method for producing same
|Kuhs et al., "Ice Perfection and Onset of Anomalous Presevation of Gas Hydrates." Phys Chem. Chem. Phys., 6, 2004, 4917-4920.
|Satoshi et al., "In Situ X-Ray Diffraction Measurements of the Self-Preservation Effect of CH4 Hydrate." J. Phys. Chem A, 105, 2001, 9756-9759.
|Sloan Jr, "Fundamental Principles and Applications of Natural Gas Hydrates." Nature, vol. 426, Nov. 20, 2003, pp. 353-359.
|Stern et al., "Preservation of Methane Hydrate at 1 Atm." Energy and Fuels, 15, 2001, pp. 499-501.
|Tse et al., "Formation and Decomposition Mechanisms for Clathrate Hydrates." Journal of Supramolecular Chemistry, 2, 2002, pp. 467- 472.
|Citing Patent
|Filing date
|Publication date
|Dec 18, 2012
|Water Generating Systems LLC
|Accelerated hydrate formation and dissociation
|Jan 15, 2013
|U.S. Department Of Energy
|Rapid gas hydrate formation process
|Aug 21, 2008
|Apr 30, 2013
|Exxonmobil Upstream Research Company
|Method for managing hydrates in subsea production line
|Feb 22, 2007
|May 7, 2013
|Exxonmobil Upstream Research Company
|Method of generating a non-plugging hydrate slurry
|Jan 25, 2010
|Oct 6, 2015
|Stx Offshore & Shipbuilding Co., Ltd.
|Method for the fast formation of a gas hydrate
|Feb 22, 2007
|Mar 26, 2009
|Talley Larry D
|Method of Generating a Non-Plugging Hydrate Slurry
|Oct 29, 2009
|May 6, 2010
|Osegovic John P
|Accelerated hydrate formation and dissociation
|Aug 21, 2008
|Aug 5, 2010
|Stoisits Richard F
|Method For Managing Hydrates In Subsea Production Line
|Jan 25, 2010
|Oct 18, 2012
|Stx Offshore & Shipbuilding Co., Ltd.
|Method for the fast formation of a gas hydrate
|U.S. Classification
|585/15, 137/13
|International Classification
|Cooperative Classification
|European Classification
|Mar 24, 2009
Owner name: RESEARCH INSTITUTE OF PETROLEUM INDUSTRY (RIPI), I
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NAZARI, KHODADAD;RAHIMI, HOSEIN;KHODAFARIN, RAMIN;AND OTHERS;REEL/FRAME:022443/0237
Effective date: 20080910
|Nov 18, 2014
|Fee payment
Year of fee payment: 4


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Feb. 19, 2015
Rating: 0
The general has very little presence. he keeps surprising catherine...
Zombie Derby
Jan. 20, 2015
Rating: 3
why does my 1st cars wheel keep falling off midway after the first jump in 2nd stage???
its normally.. So conceived, the truth is not obvious. We'll think about it.
Dec. 16, 2014
Rating: 1
is there a place in game where i can view my hangers cuz i have no memory of where my suff are T_T
hmmm... lemme know if you have a better idea, but how about a little icon indicator over the stations that show if you have a ship docked, and or hangar space. then in the galaxy view, and on the overview panel. i'll put this in build 56.
Alien Attack Team 2
Dec. 14, 2014
Rating: -2
robot weps suck and explosive weps do very little if any splash damage :/
Raze 3
Dec. 11, 2014
Rating: 14
giving prem weps to bots....
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Nov. 28, 2014
Rating: -9
it seems to get slow at gold collecting after reaching a few trillion gold without plenty of DK
Rogue Legend: Tame the Wild
Nov. 13, 2014
ah this rune factory-ish feel <3
Monster Clicker
no offline gains?
Nov. 01, 2014
My market gives me more gold than their entire country... could invading be cheaper?
Intruder Combat Training 2X
Oct. 24, 2014
grenades could be a little bigger cant see where that little speck of a grenade went....
Sky Quest
Oct. 23, 2014
the upgrades dun do much at lvl 999 and neither does light heavy and medium make much of a difference :/
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Oct. 18, 2014
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shift stops u moving while u attack
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well no need to sell since u can just click on shop items and then click on drop button for free items.
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How do u sell??
DPS Idle
Aug. 04, 2014
Were these treasure boxes made by nokia? And why did i lose money?
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iHerb カスタマーレビュー
のセーブ: ¥17 (3 % オフ)
just cherries
Reviewer2445419により Apr 07, 2016 に掲載
taste good
nice crispy or soften n chewy
Theeagleloverにより Sep 06, 2015 に掲載
nice to flavour n colour yr plain vodka the organic one seems mo flavourful - mayb its my mind playing tricks ?
So YUMMY
Minna2theMaxにより Nov 27, 2014 に掲載
My husband and I devoured a whole bag of these in about five minutes. I am going to wait a month or two before ordering these again b/c they're a bit expensive, but knowing how much cherries cost, I believe the price is fair. Great product -- oh, and beautifully tart! I adore tart cherries, so this was a great find!
5582565908912214198により Nov 24, 2014 に掲載
These are fantastic, highly recommended. They are crispy, sweet and sour at the same time. they're a good snack by themselves. Guaranteed to buy again. It should perhaps be added that I am very fond of cherries.
Tart and delicious
Umbridgeにより Nov 19, 2014 に掲載
I loved these. They are light and crunchy, and have that nice tart cherry flavour. Way better than dried cherries that they sweeten, and a great bargain.
I love these!
Reviewer1470517により Oct 22, 2012 に掲載
They are a bit hard and a bit sour, but sooo good:-) Will buy again:-)
I wish the price is lower
5175465689580336478により May 27, 2012 に掲載
It is good... Sour sour...
sour cherries
Reviewer2414122により Apr 09, 2012 に掲載
find those cherries a bit puffy and sour, guess they're a good snack when you get the munchies, better in yoghurt, porridge or muesli than by themselves
Just Cherries
Reviewer2869993により Feb 21, 2012 に掲載
The only reason I gave these cherries four stars instead of five is because I bought these at the same time as a bag of the organic version to see if there actually was a difference. And it was. These taste a bit less than the organic ones so I had to take away a star. But they're just as crunchy as the other ones, and I like to use them in homemade chocolate and other snacks.
Reviewer3076723により Feb 08, 2012 に掲載
The real Tart Cherry, so rare, and so delicious. This is for tart cherry lovers obviously. They are so good, they remind me of my childhood. Packed with antioxydants and melatonin. A bit expensive, but worth a healthy snack !


text:
Home > Sport
Friday, 23 May 2014 | MYT 4:31 PM
by k. rajan
Muhammad Haimin Robert will be representing Perlis at Sukma after he was dropped from Sabah's track and field team as they had more than enough team members.
KANGAR: Sprinter Muhammad Haimin Robert reckons that reaching the 100m sprint final at the Perlis Sukma is achievable although he has only trained for the blue riband event for less than six months.
The Sandakan local, who had been competing regularly in the hurdles event, switched to the 100m earlier this year although he showed more promise in hurdles.
He also won the 200m hurdles gold at the 2012 Little Athlete competition in Singapore in 25.25 record. The following year he bettered the time to 25.05.
"My coaches feel that I will be at a disadvantage going against much bigger boys in the hurdles event so they advised me to focus on the 100m in Sukma. My target is to run 10.7-10.9 here and enter the final.
"I clocked 11.00 at the Federal Territory Open athletics meet in March but I have also dipped below the 11.00 mark several times during training," said Haimin.
The Sandakan lad's Sukma debut nearly came to an end before it even started.
He was dropped from Sabah's track and field team as they had more than enough team members. Thankfully, he was given a lifeline by hosts Perlis to represent them.
"I just want to run and compete ... I don't care which event or which state I represent. I just want to do my best here," said Haimin, who is a Form Four student at the Tunku Mahkota Ismail Sports School.
The Sukma track and fields events will be held at the Utama Stadium from May 29-June 1.
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How many times can you break your own record? It's five for Jackie
Khairil walks away with 20km title in Malacca athletics meet
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Amazing Grace shines as athletics team emerge overall champ
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Store's farewell sale attracts thousands
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Samsung is working on a standalone VR headset
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text:
A New Way To Wear Your Short-Sleeve Oxford Shirts
Starting off any morning on the right foot requires more than some Earl Grey tea and actually frizz-free hair. (Although, that's a pretty good start.) Emerging from your slumber knowing exactly what to wear is the instant relaxer you need to brace for your jam-packed schedule. That, and probably a second cup of tea. Okay, espresso. This light and airy pick from Creatures of the Wind's spring '14 runway feels just put-together enough where you'll feel like a boss, but easy-breezy enough that it won't feel like a job in and of itself to wear. Simply team your white pencil skirt with a grid-pattern top and then layer on a short-sleeve oxford — be sure to let those buttons hang loose. Keep comfy in snakeskin flats and that's it: You're ready to take on everything coming your way.
Photo: MCV Photo.
Steven Alan Oversized Stand Collar Shirt, $215, available at Steven Alan; Mango Check Ponte Top, $39.99, available at Mango; Zara Pencil Skirt, $79.90, available at Zara; Nicholas Kirkwood Pointed-Toe Snakeskin Loafers, $650, available at Moda Operandi; Wanderluster Papatya Studs, $120, available at Wanderluster New York.
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My mom is one stylish woman — she reads Refinery29, shops at Everlane and AYR, and her leather moto jacket is her go-to. She also has a knack for spotting a Zara floral from a mile away, which is something I (and everyone else who is kind of obsessed with Zara) was dying to learn more about. Zara's spring edit, named "...
Alyssa Coscarelli
May 3, 2016
All The Spring Pieces We're Buying From Zara
There are a few things that signal spring's arrival: The sun starts setting later again, your allergies unavoidably kick in, you find yourself wanting an entirely new selection of swimsuits — oh, and Zara gets stocked with new, seasonally appropriate arrivals. It's that first trip to a Zara, filled with on-trend open-...
Alyssa Coscarelli
May 2, 2016


text:
Atlanta-based Crawford Communications, which consolidated tapeless origination of 37 channels on the companies' systems, as well as PBS member station Connecticut Public Television (CPTV) and members of the PBS ACE consortium, have all installed the integrated systems.
Within the architecture engineered by the system, the ingest of tape-based material is controlled by OmniBus automation, which allows for quality checking even as material is ingested. MassTech Group's MassStore media lifecycle management system moves the digital asset into the appropriate storage device for archiving, editing or playout. When a playlist is loaded onto the automation system, the OmniBus and Masstech systems pull the content back from storage, route it to the playout server, and then transmit the media for broadcast.
For more information, visit www.omnibus.tv and www.masstechgroup.com.
Back to the top
FCC's Wheeler Has Majority for Charter-TWC Merger
LPTVs, FCC Square Off in Court
FCC in Settlement Talks With Videohouse
CTA, Others Suggest Presidential Tech Platform
Wheeler Has Majority for Charter-TWC: Source
Netflix Greenlights 'Dear White People' Series
BBC drama names acting head of drama
Arena launches 4K trucks with Grass Valley
OTT accounts for 42 per cent of TV time
Life as Art: 'Mapplethorpe: Look at the Pictures' Follows the Photographer's Gaze
Take a Tour of Sony's NAB Booth
This Profile Piece Just Might Inspire You to Leave Your Desk Job


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List all words starting with selvas
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New keys, same cold
With temperatures regularly dipping well below zero overnight, getting locked out in the cold is a scary prospect – particularly as Carls, burdened with end-of-term assignments, stagger home later and later at night.
Club Tennis serves Valley City for Natl. Bid
Last weekend the Carleton Club Tennis team traveled to Lakeville, MN to attend sectionals, that would deteremine which teams would advance ton Nationals.
Petition circulates to give students free break housing
Kathleen George '16 started a petition on change.org that asked Carleton to provide housing to students who do not have a safe home over break.
As president elect, Foster to reform drug policy
When CSA polls closed Sunday night, Marielle Foster '16 became the CSA's next president-elect. Succeeding Becca Giles '15, she is the second consecutive female CSA president, and the second vice-president to ever ascend to the presidency.
Bon App. pleads ignorance on bawdy ads
A woman's rear end, clad only in a translucent white bikini bottom, hung seductively about mid-frame. A QR code rested in the small of her back. "Stop staring and take her picture," read the bolded caption under the photo.
One year later, memorials aim to "Light the Darkness"
Last year on February 28 the Carleton community mourned the loss and celebrated the lives of Michael Goodgame, Paxton Harvieux, and James Adams, members of the Class of 2015.
Project passes despite majority opposition
This weekend Carleton students voted in the CSA 2015 Winter election to allocate funds to create an outdoor basketball court. 440 students were in favor, and 656 were in opposition.
After vote, CSA will spend $30k on b-ball court
After last week's CSA election, confusion rippled through the student body; why would the referendum for a proposed outdoor basketball court pass if 440 students voted yes and 656 voted no?
Northfield ramps up for skate park project
Skateboard savants, enthusiasts, and dabblers, your week just got a whole lot better. As early as September, there will be a skatepark in Northfield.
Bon Appetit worker shortage plagues dining halls
Because four Bon Appetit staff members left over winter break, the dining halls and Sayles have been understaffed for the entire term.
Mock Trial presses suit to championships
In the Regionals of the annual American Mock Trial competition hosted by Hamline University in Saint Paul Friday, Jan. 30 to Sunday, Feb. 1, the Carleton mock trial team won third place and qualified to continue to the opening round championships over spring break.
MHAC Event a Success
This past Tuesday Carls gathered in the Chapel to take part in the second annual Break the Silence, organized by The Mental Health Awareness Collective (MHAC).


text:
Recent Pocologan Reviews
My husband and I recently spent the week here for a family vacation which included our teens and our parents (and dog) and were all very pleased with the entire package. The house was exceptionally clean, neat and equipped with everything your could possibly need. The privacy and yard was fantastic, large enough to play volleyball and badminton (we brought) and the VIEW was amazing. All of the bedrooms face the ocean side which is the BEST lullaby ever with the windows open at night!! Loved that fact there isn't TV and Wifi which really added to the quality of family time. We were prepared with puzzles and books but found a great selection of games, books, puzzles and movies at the cottage to use. The only things that could have made our stay better would have been a second week and shorter drive as we live in Ontario. We highly recommend this for the ultimate place to unwind, relax and go old school with family time.


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Associate - Associate Director Environmental impact assessment's, various locations in the South East. Your new company The company is a national...
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This role would suit a qualitative researcher who wants to step into the limelight and make a real difference.
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This is an exceptional opportunity to play a vital role in driving forward some of the most pioneering cancer research taking place in the world today
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AECOM are currently looking to recruit an experienced Equality Impact Assessment Consultant at either Associate or Technical Director level.
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Hubby an I are trying to plan a trip for our five year anniversary, it won't be for two years but we would like to start planning and saving. We can't do anything too extravagant or too long. Where are your favorite places to go??
OT: Where would you go??
Posted 07/15/2014
Comments (7)
Posted 07/15/2014
We love mexico, but if it was a short trio maybe a couple days in Vegas? Cheap and there's tons of different things you could do
Posted 07/15/2014
Niagara falls we love it there but it depends on if taking the kids or not as far as where to go
Posted 07/15/2014
Vegas or a Cruise.
M&M (4/15/11) = KeeKee (4/24/14)
^Micah Aria^ born 11/3/2012 @ 22 Weeks- PreE/ HELLP
M&M (4/15/11) = KeeKee (4/24/14)
Missing our little Angel...
^Micah Aria^ born 11/3/2012 @ 22 Weeks- PreE/ HELLP
Posted 07/15/2014
Would need more information. Budget, what type of vacation are you looking for? (beach, cruise, all-inclusive, culture/history, etc?), how long of a vacation?
Posted 07/15/2014
I don't know where you live but I moved to California Bay Area a couple years ago and there's a ton of stuff to see and do here. You can rent a car and get around easily to a lot of beautiful, interesting places. Otherwise, we took the kids to Playa del Carmen and Tulum for a week last year, which was a lot of fun.
Posted 07/15/2014
Personally for me I'd want to go to either San diego and do things there. Or Mt. Ruidoso in New Mexico
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