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Posts Tagged 'Society of Operating Cameramen'
The Society of Camera Operators is excited to announce the recipients of the 2012 Lifetime Achievement Awards to be presented on Sunday, February 19, 2012 at the ATAS Goldenson Theater in North Hollywood, CA.
The recipient of the Lifetime Achievement as Camera Operator is Paul Babin, SOC. Beginning his credited work as a camera operator in 1987 Babin has operated on motion picture projects from blockbuster box office hits to hit television shows. Babin is known for Terminator 2: Judgement Day, Magnolia and The Soloist.
The recipient of the Lifetime Achievement as Camera Technician is Zoran Veselic. Beginning in 1979 Veselic has been the A Camera Technician of many major blockbuster feature films. Veselic is known for Moneyball, The Muppets, Men in Black, Spider-Man and Up in the Air.
The recipient of the Lifetime Achievement as Mobile Camera Platform Operator is Dolly Grip Harry Rez. Starting with credited work in 1973 Rez has a resume filled with feature films and television programs that have been major successes. Rez is known for Doogie Howser, M.D., Providence and Nashville.
The recipient of the Lifetime Achievement as Motion Picture Stills Photographer is Andrew E. Cooper, SMPSP. Starting with credited work in 1984 Cooper has built a portfolio of some of the industry's most iconic images. Cooper is known for The Departed, Braveheart and Kill Bill Vol. 1.
The SOC will be presenting a Lifetime Achievement Award for Distinguished Service to the Motion Picture Industry to Sol Negrin, ASC. Negrin has been a long time leader of the IATSE Local 600, a film school professor, Director of Photography and great supporter of the work of the SOC. He is known for his work on Kojak, The Patty Duke Show and Coming to America.
Additionally the Awards presentation will provide the results of the two Camera Operator of the Year contests, one for Feature Film, one for Television. Nominations are being accepted now.
In the very near future the SOC will be announcing the recipient of the Historical Shot, Board of Governors and President's Lifetime Achievement awards.
The SOC supports the Vision Center of Children's Hospital Los Angeles through fund raising efforts within the Lifetime Achievement Awards event. If you are interested in being a part of this effort, contact our event planner Judy Levy at Levy, Pazanti and Associates for details. Event ticketing, sponsorships, and the opportunity to place a congratulatory message to the recipients in the Awards Program Tribute Book are available as well. LPA can be reached at 310/201-5932 or email@example.com.
For more information, please visit: www.soc.org
The Society of Camera Operators (SOC) invites innovators, businesses, and inventors to submit products and technology that have made a distinct contribution to the art and craft of the camera operator. The awards will be presented by the SOC at the 2012 Society of Camera Operators Lifetime Achievement Awards, on Sunday, February 19th, 2012 at the Leonard Goldenson Theater, Academy of Television Arts and Sciences Campus in North Hollywood, CA. Submissions will be evaluated and decided upon by members of the SOC Technical Standards committee.
Past recipients have helped camera operators shoot in every environment, from under the ocean to the surface of the moon. Past awardees include: Arriflex Corporation, Buzz Aldrin and NASA, Cartoni USA, Chapman Studio Equipment, Cinema Products, Inc. and Garrett Brown, SOC, Doggiecam, Fuji Photo Optical Company, Inc., Geo Film Group, George H Worral, Sr., GPI/PRO Camera Support System, Hot Gears and Mehran Salamati, Hydroflex, JL Fisher, Inc., John M. Stephens, Louma Crane, Matthews Studio Equipment and Bob Nettmann, Nelson Tyler, OConnor, Panavision, Inc. and Albert Mayer, Sr., Preston Cinema Systems, Sachtler, Shotmaker Company, Slit Scan Motion Picture Photography Process, Sony Corporation, Technocrane, Ltd., Tiffen, Inc. and Steadicam Ultra2, Ultimate Arm Gyro Stabilized Camera Crane, Vinten, and Weaver/SteadmanThe Society of Camera Operators Lifetime Achievement Awards also serves as the SOC's primary fundraiser for the Vision Center at Children's Hospital Los Angeles, which the SOC has proudly supported since its charter in 1981, having to date donated over $160,000.
The SOC also invites companies and individuals to participate as sponsors of this important event. It is an ideal opportunity to celebrate our industry, innovators, and visionaries, while supporting a worthy cause. Corporate awards and event sponsorships are available with a variety of benefits including enhanced exposure and access to SOC members who make memorable shots using your company's products and services.
Applications are due no later than Midnight, December 9, 2011. To receive an application for consideration, please contact any of the following:
David Emmerichs, SOC
SOC Tech Standards Chair
David Frederick, SOC
SOC Awards Event Chair
Stan McLain, SOC
SOC Corporate Liaison
For more information, visit: www.soc.org


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Snooki reveals 'fierce' new leopard tattoo
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Nicole "Snooki" Polizzi is ringing in the new year with some new ink, commemorating her loved ones with a leopard tattoo.
RELATED: Reveal: Tattoos of 2012
The "Jersey Shore" star revealed her sixth tattoo on New Year's Eve, just hours before she and best friend Jenni "JWoww" Farley hosted MTV's "Club NYE" special.
Taking to her website, the 25-year-old posted a photo of her new tattoo on her upper left arm, which features a leopard with wings attached to its back. She wrote, "I got this last week when we shot our final Jersey Shore reunion. My fierce leopard tattoo. I wanted to get this because to me it represents being a strong independent woman, and obviously I love leopards/leopard print! The crown represents being a queen and being fabulous, and the wings represent everyone who has passed in my family."
RELATED: More ink for Rihanna
She continued, "Anytime I can incorporate my loved ones who have passed, I do it! This tattoo also will always remind me of getting it while being in LA shooting our FINAL reunion of Jersey Shore."
Polizzi and her "Shore" co-stars wrapped up the sixth and final season of the hit MTV show on Dec. 20, but her spin-off show with Farley, "Snooki and JWoww," begins its second season on Jan. 8.
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Carpetbaggers and the New Social South
The social aspect was also a major change in the South. It would take quite a bit of adjustment for both the blacks and the whites. It was also an aspect that carpetbaggers could take advantage of as well as give a large amount of aid.
Carpetbaggers and the South's Economy
The change in the economic status of the entire country played a major part in the treatment of the new freed slaves and the role of the carpetbagger. It began with the change in the status of the slaves combined with the effects of war on the land.
The Intent of the Carpetbagger
The world had changed for the South. Overall life as it had been was over. A new world awaited Southerners whether they liked it or not with the main areas being politics, economics, and social aspects. Carpetbaggers arriving showed how dramatically life in the south was going to change.
Origins of the Carpetbagger
It originated during the Reconstruction period of American history. After the civil war, the term was created to describe a "person from the northern United States who went to the South after the American Civil War to make money." From there it developed a negative connotation.
The Proposal of the Anaconda Plan
The first Union general to implement the 'Anaconda Plan' was Winfield Scott. He was one of many working with President Abraham Lincoln attempting to come up with an idea to end the war quickly and with little bloodshed. He believed the plan was the right way to go.
Grant's Shadowed Presidency
General Ulysses S. Grant is one of the most renown of the Civil War leaders. His success has been studied and marveled since the war began. It was no surprise when the war was over that he would be placed in the White House. What did surprise everyone was the rollercoaster ride he brought with him.
Union Options Into the South
The very size of the Confederate states allowed many avenues for the Union army to penetrate and defeat the seceding states.
Samples of Confederate Losses
1862 proved to be crucial for the Confederacy in decision making and loses on the battlefield. In losing Nashville, New Orleans, and Memphis, the South lost strategic points in their military planning. Each one would prove to hurt the Confederacy long-term.
Decisions Made by Davis That Led to Failure
Hind-sight is twenty-twenty. After the fact, one can easily point out where Jefferson Davis made his mistakes and how the Confederacy lost the war. Starting in the West, Davis found himself regretting many of his decisions that would became fateful for the newly created nation.
Brandy Station as a Turning Point
Brandy Station would become a turning point solely due to pride. Sometimes it takes a defeat to get the fires roaring and the ambition to push harder to achieve more. That was the case here.
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The Hershey girls improved their season record to 12-1 Tuesday, defeating rival Sutherland 53-46 with a strong third quarter.
Hershey got off to the best start, staking out an 11-4 lead after one quarter. But Sutherland came back in the second quarter to within two points at halftime.
In the third quarter, Hershey outscored Sutherland 14-9.
The teams played evenly in the final stanza.
Tayler Baker scored 16 points to lead Hershey's offense.
Allison Stewart had 15 points for Sutherland on perfect 5 of 5 shooting from three point range. Kaley Stokey chipped in 10 for Sutherland, including two three pointers. Sam Staggs had trouble getting on track, hitting only 1 of 8 from two point range.
The Sailors did not shoot well inside but hit a blistering 63 percent from three-point land.
Sutherland's record is now 7-4.
Score by quarters
Sutherland: 4-18-9-15 - 46
Hershey: 11-13-14-15 - 53
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Upstate News
Darryl Geddes 315 464-4828
Health Science Center Physician to Chat Live On-Line June 14 at Americas Doctor.com
Sharon Brangman, M.D., associate professor of geriatrics and division chief of geriatrics at the State University of New York Health Science Center and University Hospital, will chat live on-line Monday, June 14 from 8 to 9 p.m.on Americas Doctor.com.
Dr. Brangman, who is included in the most recent edition of "The Best Doctors in America" (Woodward/White, Aiken, S.C), will discuss "Caring for the Elderly." To chat with Dr. Brangman go to www.americasdoctor.com.
University Hospital is the first hospital in New York to "go live" on Americas Doctor.com, which operates a consumer-based healthcare web site on the Internet and on America OnLine. Consumers can talk one-on-one with a physician, participate in chat groups with specialty physicians, seek information on medical topics as well as locate providers by specialty in their geographic area at no cost.
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- Sharon Brangman on leading through challenges: Be willing to leave your comfort zone
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Today's media-savvy youth respond well to a medium where the message is projected and amplified
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Customer feedback
|Contribute Your Feedback
|Click the button below or email email@example.com to contribute your experiences with this product. Although not necessary, it's interesting to have a first name, city, state and country (no email addresses will be used). Any information submitted becomes the property of Tennis Warehouse.
Please include any relevant information such as skill level and style of play.
Comments: I got this 6-pack bag to match my growing collection of Volkl racquets. Great purchase for that reason.
While the racquets are high quality and amazing all around, I would say their bags are not on the same level. This is not to say the
bags are bad, they're just a little better than ok. I've always had Wilson bags just because I was trying to show my love for Federer.
In comparison, this bag has some design issues. I'm not used to having the straps on the top of the bag, which makes opening it
up to grab a racquet a little more awkward. The glossy plastic/vinyl part of the bag is great in looks but not really effective in the
long run as you can see where it will crease and show wear and tear. Zippers are not as big as on the Wilsons. All the previous
issues I can certainly deal with but i have two main issues with this bag. The first is that it does not have a handle or loop at the
top of the thin part of the bag. I tend to pick up my bag from that area. I thought it was because I've always had a Mega sorta bag
but even the mega in this version doesn't have that loop. Secondly, the backpack straps are thin width-wise as well as padding-
wise. But the biggest issues with the straps is how they're sewn onto the bag itself. If you take a good look at the picture, the
straps are sewn on with a piece of fabric and then onto the bag. Perhaps it's because the straps are at the top, this is to give them
more room to move around. But you can clearly tell that it's an area that will have wear and tear. All in all, definitely a great
looking bag that will serve it's purpose enough.
Comments: This mega bag is awesome! I was using a backpack type bag, but with two racquets and a lot of gear, I
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compartment is very large as well, enough to hold all the miscellaneous items I carry. It also has a department for the shoes which
find very nice, as they can get very dirty after playing on clay.
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2 people found this helpful
"Great Place to Work!! "
- Comp & Benefits
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I have been working at Gentiva
Everyone works as a team & the manager cares about each of her employees. The PTO is great. Work hours are flexable and everyone is so nice.
Because the company is so large communication can sometimes be an issue. It's a challenge making sure everyone is on the same page.
Keep an open mind, and make sure you try to visit as many locations as you can. It is very important that employees can put a face with the name.
231 Other Employee Reviews for Gentiva (View Most Recent)Sort: Rating Date
"Great if patient-focused "
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I worked at GentivaPros
terrific educational opportunities; great programs to benefit Seniors; fair pay; trying to standardize across the country; some great clkinical managersCons
communication clarity and style needs to be positive rather than punitive; need to have more practical respect for clinicians in the fieldAdvice to ManagementAdvice
being a publicly traded company may be good for stock holders, not so much for the SeniorsRecommendsDisapproves of CEO
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great employees and great patient careCons
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relax and don't be so uptightRecommendsApproves of CEO


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October 26, 2010
Alberta Prime Time Live Interview
An Alberta Prime Time Live Interview with Ted Tederoff (Alberta Home Education Association President), Larry Booi (former teacher and past president of the Alberta Teachers' Association) and Marco Pacione (Vice Principal at the Centre for Learning at Home) was originally aired October 14, 2010. To watch the interview please go to:
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Comfort Hotel Lamarck ensures to complement its large selection of rooms with a high level of service. The hotel is easily accessible due to its proximity to Marcadet – Poissonniers. The proximity of this location to attractions including Montmartre and Moulin Rouge makes it a great choice. A visit to Basilique du Sacre-Coeur will leave a great impression. Le Parc de Bercy, always worth a visit, can be found close to the hotel.
Comfort Hotel Lamarck demonstrates a commitment to your comfort and convenience with services including a late check-out option and much more besides. Total room count is 66.
The rooms of Comfort Hotel Lamarck have air-conditioning. The standard room services here are enhanced by a wake-up service as well as a housekeeping service. A useful way to stay in touch, wireless high-speed Internet access (surcharge) is included in the rooms. The bathrooms of this hotel sensibly come with a complimentary toiletries set. The rooms are supplied with kitchen amenities, for example a microwave (upon request).
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Malaysian Indian Congress calls on Indian parties to unite.
Kuala Lumpur Kuala Lumpur (kwä`lə lm`pr), city (1990 est. pop. , Nov.9 (ANI): Former Malaysian Indian Congress This article may not be compliant with the content policies of Wikipedia. (MIC) deputy president S. Subramaniam has said while it has played the role of an umbrella body for Indians since its inception in 1946, it must take steps to maintain community unity with a new zest and determination.
"It (unity) is achievable, if we in the community are prepared to move ahead in unison, putting aside our differences and harnessing our similarities. After all, the basic and fundamental aim is to serve the community and Malaysians at large. It's sad to see the Indians in disarray now," The Star quoted him, as saying at the opening of the Malaysian Indian The Indian Malaysians are a group of Malaysians largely descended from those who migrated from southern India during the British colonization of Malaya. Prior to British colonization, Tamils had been conspicuous in the archipelago much earlier, especially since the period of the Youth Council headquarters yesterday.
Subramaniam was among the main guests at the event, along with former People's Progressive Party There are several parties named People's Progressive Party:
- People's Progressive Party (The Gambia)
- People's Progressive Party (Guyana)
- People's Progressive Party (Liberia)
- People's Progressive Party (Malaysia)
- People's Progress Party (Papua New Guinea)
Subramaniam further said: "As long as we are not united, our voices will not be heard and the community will not be recognized or respected."
Murugiah said being united was the only practical solution for the woes faced by the Indian community. Forming new parties, he added, would be counter productive to the community as none of them could wield the necessary political influence.
"For the sake of the community and unity, I am willing to work with anyone, including (PPP (Point-to-Point Protocol) The most popular method for transporting IP packets over a serial link between the user and the ISP. Developed in 1994 by the IETF and superseding the SLIP protocol, PPP establishes the session between the user's computer and the ISP using president) Datuk M. Kayveas. There is no point forming new parties when we are so divided and there is no understanding. I appeal that we don't form any more new parties but instead strengthen the existing ones," he added. (ANI)
Copyright 2009 Asian News International The Asian News International (ANI) agency provides multimedia news to China and 50 bureaus in India. It covers virtually all of South Asia since its foundation and presently claims, on its official website, to be the leading South Asia-wide news agency. (ANI) - All Rights Reserved.
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I have stayed here several times and i think it was even better than last time! The staffs attitude to their customers was really excellent and nothing was too much trouble, particularly for the bar staff and especially the girl serving there. My only other comment about the staff was that there was a Spanish lady at reception for both... More
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Posts tagged harold-ramis
Burnout Paradise salutes Harold Ramis with free 'Legendary Cars'
Hollywood legend Harold Ramis passed away this week and the few folks left at Criterion Games are going full stream by honoring him with a free car pack in Burnout Paradise. The "Legendary Cars" pack features homages of iconic whips from Knight Rider, The Dukes of Hazzard, Back to the Future...
Harold Ramis talks Ghostbusters and lengthy game scripts
MTV Multiplayer's Stephen Totilo used his MTV Movies contacts to get some info out of Ghostbusters writer and star Harold Ramis regarding the upcoming video game. Ramis said that he and Dan Ackroyd both contributed to the game's narrative, in addition to lending their voices to their old...
Wii ain't afraid of no ghosts
Over a year ago, a British magazine compiled what seemed like a joking list of great possible ideas for Wii games -- and one of those is about to become a reality. Not long after a rumor surfaced of a beloved 80s franchise getting remade in gaming form, Game Informer revealed their December cover...
Breaking News
Dying Light cancelled on Xbox 360, PS3
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Games we love and hate
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Super Joystiq Podcast 122: Far Cry 4, GTA V, Assassin's Creed Rogue, WWE 15
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Nathan Hartswick and More Set for VT's Town Hall Theater Comedy Night, 2/28
Town Hall Theater Cabaret presents an evening of comedy featuring Nathan Hartswick, Seven Days' "Best Vermont Stand-up Comedian" of 2012; actor and comedienne Natalie Miller; and Addison County's Jim Inglis.
Smart and funny for ages 18 to 88. Cash bar and light snacks. Byers Studio on the theater's lower level on Thursday, February 28 at 7:00 pm.
Tickets, $10, are available by calling 802-382-9222, at www.townhalltheater.org, or at the box office Monday-Saturday, noon - 5:00 pm.
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February 28, 2013
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- Time Warner Cable Brings Your Favorite 'Musicals' to On Demand


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- 22 Resorts
- Consistent Snow
- Diverse destinations
- Resorts open before those of many other states
- Home to Vail, Beaver Creek, Copper Mountain
Enter your start location for step by step directions:
A summer and winter tourist resort in northwestern Slovenia near the borders with Austria and Italy, Kranjska Gora touches Triglav National Park to the south. The Kranjska Gora ski lifts have the longest history in Slovenia. They are easily reached since they are located near international highways, and because of their altitude (the lower station is at 813 meters) they offer favourable weather and snow conditions. The slopes are suitable for all levels of skiing skills. Beginners and recreational skiers will enjoy the slopes and trails in Kranjska Gora, Gozd Martuljek, and while the Podkoren trail is more demanding.
Get email updates of snow reports, forecasts and conditions for Kranjska Gora.
Get OnTheSnow on the go
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Reddit: Better than coal...
« McDonald's Custy Kindness: Couple Receives Bag of Money Instead of Breakfast, Returns It | Main | Nutella For The Christmas Tree »
My... My... MY CHILDHOOD! WTF?! @_@
Posted by: Ilia | Sunday, December 08, 2013 at 09:05 AM
Funny, I always saw Santa as the Dom with Mrs. Claus as the Sub. I mean, he does like to punish the naughty after all.
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Find what you need at BlackCohosh.net. This is where you will find all of the Black Cohosh you can't find anywhere else, including Tampons and Maxi Pads. Get it here at BlackCohosh.net. All this in a simple to use shopping interface. Checkout securely online with the help of BlackCohosh.net. Have a great day!
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Jordye Bacon Elementary recently concluded the school year with a Jeopardy-style quiz bowl for K-2 and a three-strike elimination quiz bowl for grades 3-5. Winners of the K-2 were on team 3; Diamond Stiff, Michael Alexis and Jakorian Willis. Winners of the black history bowl were Tyma Bullard, first place, Kylee Proffitt second, and Kyshon Campbell, third.
LUDOWICI -- Long County High School will have its 2009 graduation at 8 p.m. Friday in at Veterans Stadium.
Haleigh Hawkins won the Liberty County School System's 2008-09 Spelling Bee winner. She is a seventh-grader at Lewis Frasier Middle School. Students who participated in the bee ranged from fourth through eighth grades and each elementary and middle school within the system was represented by its top spellers.
As a part of the GREAT (Gang Resistance Education and Training) program, each class must do a class project.
The top Accelerated Readers for the year at Lewis Frasier Middle School were treated to a recent ice cream social, complete with prizes. Fifty-one students who earned 200 or more points for the year also attended Wii parties and were eligible to win a Wii game system.
Liberty Elementary students who reached their individual Accelerated Reader goals for the fourth grading period of the just ended school year recently got a party thrown for them at the school.
Snelson-Golden Middle School is inviting parents and students who missed the Transition Night for students who will attend the school in 2009-10 to stop by to get packets to help rising fifth graders prepare for middle school.
The summer reading program at Live Oak Public Libraries, including the Liberty Branch in Hinesville and Midway-Riceboro Branch in Midway, kick off the summer reading program Monday.
LUDOWICI - Denise Montgomery was recently selected as the 2009 teacher of the year for Long County High School and, according to students, she deserves the award.
Exemplifying his generation's notorious infatuation with technology, Bradwell Institute salutatorian Young-Min Kim admitted to fellow graduates, friends and families that he consulted Google when researching his speech.
Bradwell Institute senior Robert Motley drove a brand-new Chevy Cobalt to his high school graduation yesterday - and it was flawless.
It certainly rained Saturday, but not on the Liberty County High School graduates' parade.
The Long County Alumni Association recently donated $2,000 worth of books to the Smiley Elementary School Media Center to help the school's reading program.
Anyone who walks through the Pentagon is bound to cross paths with highly skilled military or civilian employees who have disabilities - including the Defense Department's director of disability programs, who has been legally blind since age 16.
The Liberty County School System's high-school graduation rate has increased since last year, rising from 72.3 percent in 2013 to 75.8 percent in 2014. The graduation rate at Bradwell Institute held steady at 72.4 percent, while the graduation rate at Liberty County High School made a statistically significant gain of 8.7 percentage points, rising to 81.6 percent.
First grade: Savannah Dickey
Air Evac Lifeteam members recently spoke to Liberty County Pre-K students as part of the pre-K center's community-helpers study.


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WORLD NEWSMay 23, 2008
more »
KDE Rallies Bug HuntersMay 16, 2008
Sunday is the 4th KDE Bug Day with the focus on finding errors in Konqueror.more »
CeBIT 2008 Hanging out in Hannover, GermanyMay 01, 2008
At CeBIT 2008, the world's biggest computer fair, popular topics included Green IT, mini-PCs, and open source.more »
FOSDEM 2008 A report from FOSDEM 2008May 01, 2008
Now into its eighth year, the FOSDEM developer conference in Brussels, Belgium, demonstrates that it is very much alive and kicking, and even celebrating records.more »
SCALE 6x SCALE 6x: Women in Open Source ConferenceMay 01, 2008
In February, Linux and open source enthusiasts met in southern California for SCALE 6x. The conference kicked off with a day of "Friday Special Events," including a Women in Open Source conference.more »
Free Live Stream of Apachecon Europe KeynotesApr 07, 2008
Linux Magazine is broadcasting a live stream from ApacheCon Europe 2008, Amsterdam, the Netherlands (April 9 through 11). The keynotes from the developer conference are available free of charge.more »
USENIX Announces Open Access to Conference ProceedingsMar 31, 2008
USENIX conference proceedings now available free of charge to general public.more »
Brazil Says "NO" Again to OOXMLMar 26, 2008
In his blog, Avi Alkalay, an Open Standards, Open Source and Linux advisor at IBM Brazil, reports on the official Brazilian vote, which was decided by consensus of the entire technical team, and quite firmly says that OOXML does not deserve to be an international ISO standard.more »
Issue 170/2015
Buy this issue as a PDF
TOR Network Isn't So Anonymous
A new study says it is possible to unmask 81% of TOR users.
.NET Goes Open Source
Redmond joins the revolution by turning the .NET Core Runtime into a GitHub project.
Drupal Advisory Unleashes a Torrent of Attacks
Users only had 7 hours to update before the intrusions started.
HTML5 Gets Promoted to a Standard
It's official: The new web arrives
Linus Addresses Criticism for Harsh Language
Kernel king admits his tone has alienated volunteers, but says the demands of the process require directness.
New SSL Attack Lets a Malicious Listener Steal Session Cookies
New flaw in an old encryption scheme leaves the experts scrambling to disable SSL 3
Leading Open Source Coder Rants about Rants
Lennart Poettering wants to change the way Linux developers talk to each other.
HP Splits into Two Companies
Enterprise giant frees itself from ink and home PCs (and visa versa).
Mozilla Labs Shuts Down
Mozilla's product think tank sinks silently into history.
Internet Giants Launch Collaboration to Improve Open Source
TODO group will focus on open source tools in large-scale environments.


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Weekly Runs
Go The Distance
"Go the Distance" is weekly program which offers CRR members supported training runs for longer distances. The runs are held weekly on Saturday mornings at various locations in the Atlanta area. We support each Saturday run with maps and fluid stops for various mileages – typically up to 20 miles. The run locations rotate to different locations throughout the Atlanta area and cover all of the different terrains that Atlanta has to offer.
Go the Distance is for all levels of runners – you do not have to be a long distance runner to join in the Go the Distance program, but for members who might want to train for a half or full marathon, or simply like to run longer distances, Go the Distance will definitely give you the training distances you are looking for. This is a great way to meet new people and enjoy longer runs with others.
This Saturday's GTD Run
- November 22 at 7:30 AM
- West Stride
- 3517 Northside Pkwy, Atlanta, GA 30327 - Map it
- We'll have maps with distances from 6 - 20 miles and water and Powerade stops along the way.
- Nike will be out offering 20% off all Nike shoes and apparel - more details on Facebook
- For more information please email: GTD Contact


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A method of operating a multi-phase downflow reactor so as to induce a pulsing flow regime is disclosed. The pulse may be induced by increasing the gas rate while maintaining the liquid rate until a pressure drop sufficient to induce the pulse flow is achieved. The method is particularly useful in the sulfuric acid catalyzed alkylation of olefins in a reactor packed with a stainless steel/polypropylene mesh.
1. A method of producing alkylate in a sulfuric acid alkylation comprising feeding a hydrocarbon component consisting of an olefin, olefin precursor or mixture thereof and an isoalkane, in at least a partial gaseous state to a downflow reactor in the presence of liquid sulfuric acid fed at a constant rate and an internal static mixing system wherein the rate of feed of said olefin, olefin precursor or mixture is increased until a pressure drop sufficient to induce the pulse flow is achieved.
2. The process according to
3. The method according to
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This application claims the benefit of provisional application 60/313,987 filed Aug. 21, 2001, provisional application 60/323,227 filed Sep. 19, 2001, and provisional application 60/334,560 filed Nov. 30, 2001.
1. Field of the Invention
The present invention relates to multi-phase reactions where a hydraulic regime is utilized, which provides pulsations, to yield greater mixing and associated interfacial mass transfer and heat transfer. By obtaining a desired vapor and liquid mass flux in a down flow reactor process, fluid pulsations can be induced.
2. Related Information
The pulse flow regime has been studied in regard to trickle-bed reactors. Generally, trickle-bed reactor refers to a solid particulate pack bed down flow reactor operating in the trickle flow or gas continuous regime. A hydraulic map called a Baker plot is often used to indicate the mass fluxes required to obtain a given hydraulic regime (i.e., Trickle, pulse, bubble flow). Weekman, V. W., Jr., and J. E. Myers, �Fluid-Flow characteristics of concurrent gas-liquid flow in packed beds�, AlChE Journal, 10, 951 (1964), provides a map of the various hydraulic regimes found in packed beds. These pulses yield turbulent mixing within the reactor system and provide a higher level of mass and heat transfer, not typical of commercial reactors which tend to operate in the hydraulic region known as trickle flow.
Pulse flow in a mixed phase reactor is defined as a hydraulic region in which waves of liquid continuous slugs of material move down the reactor. In between each wave is a region of flow which is considered to be gas continuous. The pulses are discrete bands of material with higher overall density than that of the material both in front and behind the pulse or wave. By changing the overall liquid and vapor mass fluxes within this hydraulic region, the frequency at which the pulses flow down the reactor can be manipulated. Higher overall mass flux, yields higher frequency pulses, and lower mass flux yield lower frequency pulses. The mechanism for development of this type of flow is not due to oscillations provided by some type of mechanical device, rather it is a known two phase (vapor/liquid) hydraulic region which is a function of the relative vapor and liquid velocities.
Fukushima, S. and Kusaka, K., J. of Chem. Eng. Japan 10, p. 468 (1977) provided Equations 1 and 2, which demonstrate the increase in mass transfer as one moves into the pulse flow regime. The difference between the liquid to gas mass transfer coefficient for trickle flow and pulsing flow can be seen from the following two equations where equation (1) is for trickle flow and equation (2) is for pulsing flow:
kL is the mass transfer coefficient
ai is the specific interfacial surface area
Sp is the external surface of particle divided by the square of the particle diameter
Rel is the modified Reynolds number of the liquid (density removed)
ReG is the modified Reynolds number of the gas (density removed)
Sc is Schmidt number (ratio of the momentum diffusivity to the mass diffusivity
dp is the particle diameter,
D is the diameter of the reactor,
hext is the liquid hold up (ratio of the volume of liquid held up in the reactor over the total reactor volume), and
Dml is the molecular diffusivity of the gas
This is presented graphically in FIG. 1 where the ratio of pulse flow mass transfer coefficient to trickle bed mass transfer coefficient is shown to increase with the Reynolds number of the liquid or gas. The Reynolds number of either the liquid or gas is directly proportional to the flow rate, all other variables (diameter of reactor, density and viscosity of component) being constant.
Schuster et al U.S. Pat. No. 4,288,640 identifies a narrow region within the Baker plot where heat transfer benefit occurs as one increases the mass fluxes of the gas and liquid and approaches pulse flow. This region of operation is called transitional flow. Transitional flow represents a narrow region of mass fluxes between trickle flow and pulse flow. This region is essentially on the transition line of the flow map separating pulse flow from trickle flow, which lies at a point where a small change in liquid flow causes a relatively large change in differential pressure drop across the bed. Schuster et. al list a range of ΔP/L of twice the ΔP/L obtained during trickle bed operation and characterizes the pulse region as one where fluctuations in the pressure difference across the reactor occur and the pressure fluctuations as having the same frequency as the pulses. It is known, however, that the pulse regime extends far beyond the differential pressure drop change of twice trickle flow.
A plot of gas vs. liquid mass flux for pilot and commercial scale reactors was presented in �Trickle Bed Reactors�, Charles Satterfield, AlChE Journal, Vol. 21, No. 2, March 1975, pp. 209-228. The author observed that the operating region for the pilot scale reactors was in trickle regime; whereas, some commercial reactors operated in the pulse region. This suggests that during scale-up to commercial size some commercial reactors were inadvertently designed to operate in the pulse region, since at the time, running in pulse mode was considered to lead to undesirable hydraulic instability and breakup of catalyst particles in the packed bed.
With typical trickle bed reactors, like those used for hydrotreating using a solid catalyst, the main resistance towards the desired hydrogenation include: 1) mass transfer from the gas phase into the liquid phase, 2) mass transfer from the liquid phase onto and off of the catalyst surface, 3) diffusion into and out of the catalyst pore space, 4) adsorption of the reactants onto the catalyst surface, 5) chemical reaction, and 6) desorption of the products into the pore space.
Although reactor operation in the pulse flow region may provide interesting mass transfer benefits, two main concerns exist. The first addresses fixed bed catalyst life. Due to the high liquid and vapor rates, vibration of the fixed bed may occur causing physical catalyst degradation and abrasion over time. Secondly a problem in scale up from pilot plant units may be encountered. The small size of pilot plant reactors induces wall effects which occlude space for radial pulse dispersion and it is not known whether larger diameter reactors provide an equivalent flow pattern at the same liquid and vapor velocities. It is an advantage of this invention that a multi-phase co-current flow reactor system that operates efficiently in the pulse flow region is provided.
Briefly the present invention is the operation a multi-phase downflow reactor under conditions of liquid and vapor flow and the packing to induce a pulse flow regime. The process is preferably carried out in a vertically disposed reactor containing a contact structure having a void space of greater than 50 volume %. The packing system may be comprised of materials that are either inert or catalytically active in nature.
FIG. 1 is a comparison in graphical form of the mass transfer coefficients in pulse flow and trickle flow.
FIG. 2 is a plot of differential pressure versus the product of the Froude Number of the light liquid and the Reynolds Number of the vapor in a packed reactor.
FIG. 3 is a plot of the ratio of the pressure deviations caused by pulse flow to the overall pressure drop versus the overall pressure drop when a three phase (gas/liquid/liquid) system is used.
FIG. 4 is a schematic representation of the first aspect of the present apparatus in which the present alkylation process may be carried out.
Pulse flow is obtained at high gas and liquid flow rates. The pulses are characterized by large mass and heat transfer rates. Increased catalyst wetting and a continuous mixing between parallel flowing rivulets diminish flow maldistribution. In addition, the formation of local hot spots is reduced, leading to an intrinsically safer process and diminished catalyst deactivation. The pulses continuously mobilize the stagnant liquid holdup to the point where its stagnant nature disappears. Since stagnant holdup represents about 10 to 30 percent of the total liquid holdup in trickle flow operations, its more dynamic character during pulsing flow enhances reactor performance. Axial dispersion is considerably less compared to trickle flow, due to effective radial mixing between the different parallel flowing liquid streams and disappearance of stagnant liquid hold up. Especially undesired consecutive reactions are reduced to lower levels due to better overall plug flow behavior. A further advantage of pulsing flow is much higher radial conductivity. In some cases, depending on the pulse frequency, significant changes in both yield and selectivity occur.
The main benefit with pulse regime reactor operation is that of increased mass transfer and heat transfer due to the associated turbulence produced. When the catalyst physical characteristics are optimized and the reaction kinetics are not limiting, increasing mass transfer is a key to increasing the process performance.
Some example reactions that can be conducted in the multi-phase pulsed flow reactor include:
1.) Vapor/Liquid/Liquid systems in which the packing is inert and one of the liquid phases is the catalyst for the reaction. An example is olefin/paraffin alkylation using sulfuric acid or HF as catalyst.
2.) Vapor/Liquid systems in which the packing is an inert structure that functions as a container for solid particulate catalyst, as a support for catalytic materials deposited on the surface of the structure, or is comprised of materials that are not inert and have catalytic properties. An example is hydrodesulfurization of hydrocarbon feed stocks over a supported Co�Mo catalyst.
3.) Vapor/Liquid/Solid systems in which the packing is inert. Finely divided catalyst is the solid phase dispersed in the liquid phase. An example is synthesis of methanol from CO/H2. The liquid phase is an inert hydrocarbon oil containing finely divided methanol synthesis catalyst.
The pulse may be induced by increasing the gas rate while maintaining the liquid rate until a pressure drop sufficient to induce the pulse flow is achieved. Further the pulsing may be dampened while keeping the mixing characteristics by utilizing a second liquid of different viscosity. The dampening reduces the wear and tear on catalysts and also maintains more even flow rates.
The disperser comprises at least 50 volume % open space up to about 99 volume % open space. Dispersers are position within the reaction zone in the reactor. Thus, for example, the multi filament component and the structural element, e.g., knit wire, should comprise about 3 volume % to about 50 volume % of the total disperser, the remainder being open space. Such packings may be composed of metals, ceramics, plastics, and/or composite materials. Some of these materials include: Carbon steel, 304 SS, 304 L SS, 316 SS, 316 L SS, Alloy 20, Monel, Inconel, PVC, PTFE, Titanium, Nickel, Hastelloy, aluminum, other alloys, polypropylene, polyethylene, Kynar, and Teflon. A list of packings containing desirable void fractions include:
(1) Random or dumped distillation packings which are catalytically inert Dumped packings contain higher void fraction and maintain a relatively large surface area, such as, Berl Saddles (Ceramic), Raschig Rings (Ceramic), Raschig Rings (Steel), Pall rings (Metal), Pall rings (Plastic�polypropylene), Intalox� saddles, Hy-pak�, K-PAC�, Ballast-plus�, CMR�, Chempak�, Levapak�, Nutter Rings�, HcPp�, FLEXIMAX�, Hiflow�, Jaeger Tri-packs�, NOR PAC�, Intalox� Snowflake�, LANPAC�, and IMPAC�.
(2) Random or dumped distillation packings which are catalytically active. Random packings which contain at least one catalytically active ingredient. Such ingredients could include elements such as Ag, Rh, Pd, Ni, Cr, Cu, Zn, Pt, Tu, Ru, Co, Ti, Au, Mo, V, and Fe as well as impregnated components such a metal-chelate complexes, acids such as phosphoric acid, or bonded, inorganic, powdered materials with catalytic activity.
Other available dumped packings would include catalytic materials in the form of small wires which are bent and formed into various geometrical shapes such as cubes, cylinders, spheres.
(3) Structured packings which are catalytically inert. These packings are typically constructed of corrugated metal bent at various angles, wire mesh which is crimped, or grids which are horizontally stacked one on top of the other, such as GOODLOE�, MONTZ A�, and MONTZ B� and the device of U.S. Pat. No. 6,000,685 which is incorporated herein in its entirety, which discloses contact structures comprising a plurality of sheets of wire mesh formed into vee shaped corrugations having flats between the vees, said plurality of sheets being of substantially uniform size having the peaks oriented in the same direction and substantially in alignment, said sheets being separated by a plurality of rigid members oriented normally to and said resting upon said vees.
(4) Structured catalytic distillation packings which are intended to hold particulate catalysts, or structured distillation packings composed of a catalytically active material. Structures similar in form to the structured distillation packings or rolled bales which contain pockets can be used to contain particulate catalysts. These are commercially know as catalytic distillation packings, such as packing composed of flexible, semi-rigid open mesh tubular elements which contain particulate catalyst(s) (U.S. Pat. No. 5,431,890). Other suitable structures are disclosed in U.S. Pat. No. 5,730,843 which is incorporated herein in its entirety and which discloses structures that have a rigid frame made of two substantially vertical duplicate grids spaced apart and held rigid by a plurality of substantially horizontal rigid members and a plurality of substantially horizontal wire mesh tubes mounted to the grids to form a plurality of fluid pathways among the tubes, said tubes being empty or containing catalytic or non catalytic materials.
In particular the pulse flow is utilized in the sulfuric acid alkylation process wherein an olefin is reacted with an iso-alkane in the presence of sulfuric acid using an internal static mixing system comprising the combination of a vertical reactor having a reaction zone and the disperser disposed in said reaction zone, particularly for carrying out paraffin alkylation using an acid catalyst. A preferred disperser comprises mesh wire with a multi filament component or expanded metal intertwined with a multi filament component, said multi filament selected from inert polymers, catalytic polymers, catalytic metals or mixtures thereof. The wire mesh provides the structural integrity of the system as well as the open space required in reactors for the movement of vapors and liquids though the system. The disperser may be comprised of sheets, bundles or bales of the co-knit wire and the multi filament component. The system may also comprise the co-knit wire and multi filaments within a frame. The reaction zone may comprise the entire column or a portion thereof. The present dispersers achieve radial dispersion of the fluid or fluidized materials in the reactor.
(5) Demisters and Co-knit structures which are catalytically inert or active. Demisters and co-knit structures are typically used for liquid-liquid coalescers and coalescing of mists. They are known as �mist eliminators� or demisters and are composed of one or more materials which are knit together to form a mesh. The stitched mesh is then crimped, stretched, and folded or bundled to provide the desired amount of surface area per volume ratio.
Several demister and coalescer materials such as those constructed by Amistco Separation Products, Inc. of Alvin, Tex. are composed of single materials or co-knit metal wires and multi-filaments of polypropylene, Teflon, PVDF, or polyester. Information used to describe these filaments include: a) the filament count, and b) the denier of the filaments. Other acceptable demisters include perforated sheets and expanded metals, open flow cross channel structures which are co-woven.
Additionally, catalytic materials can be woven or interwoven into structures such as sulfonated vinyl rein (e.g. Amberlyst) and catalytic metals such as Ag, Rh, Pd, Ni, Cr, Cu, Zn, Pt, Tu, Ru, Co, Ti, Au, Mo, V, and Fe. There may be up to 100 or more multi filaments intertwined with the knitted wire or expanded metal. The catalytic metal filaments are generally of higher denier because of their greater density.
(6) Monoliths which are catalytically inert or active. Monoliths are structures containing multiple, independent, vertical channels and may be constructed of various materials such as plastic, ceramic, or metals. The channels are typically square; however, other geometries could be utilized. The segmented channels could be constructed, impregnated, or coated with active catalytic materials.
A preferred disperser comprises a conventional liquid-liquid coalescer of a type which is operative for coalescing vaporized liquids. These are commonly known as �mist eliminators� or �demisters�, however, in the present invention the element functions to disperse the fluid materials in the reactor for better contact. A suitable disperser comprises a mesh such as a co-knit wire and fiberglass mesh. For example, it has been found that a 90 needle tubular co-knit mesh of wire and multi filament fiberglass such as manufactured by ACS Industries LLC of Houston, Tex., can be effectively utilized, however, it will be understood that various other materials such as co-knit wire and multi filament Teflon (Dupont�), steel wool, polypropylene, PVDF, polyester or various other co-knit materials can also be effectively utilized in the apparatus. Various wire screen type packings may be employed where the screens are woven rather than knitted. Other acceptable dispersers include perforated sheets and expanded metals, open flow cross channel structures which are co-woven with fiberglass or other materials such as polymers co-knit with the wire mesh expanded or perforated sheets. Various wire screen type packings may be employed where the screens are woven rather than knitted. Thus, preferably the multi filament component and the structural element, e.g., knit wire, should comprise about 35 volume % to 80 volume % of the total disperser.
In a preferred embodiment the reactor is packed with a special disperser comprising a wire mesh packing material containing 0.011 SS306 turned wire and interwoven 800 denier polypropylene. One source of the material is Amistco Separation Products, Inc. of Alvin, Tex. The packing is useful for contacting alkylation reactants, i.e., olefins and alkanes, and the liquid sulfuric acid catalyst. Packing density for this material is approximately 7 lbs/ft.3 which provides a surface area of 444 ft.2 for five feet of the material in a four inch diameter glass column. Surface area relating to the walls only of the column is 5.23 ft2. The alkylation reactor is packed with a wire mesh packing material containing 0.011 SS306 turned wire and interwoven 800 denier polypropylene. A pressure drop of at least about 0.06 psi/ft of packing has been shown sufficient to produce pulse flow for this packing.
Other suitable dispersers are disclosed in U.S. Pat. No. 5,730,843 which is incorporated herein in its entirety and which discloses structures that have a rigid frame made of two substantially vertical duplicate grids spaced apart and held rigid by a plurality of substantially horizontal rigid members and a plurality of substantially horizontal wire mesh tubes mounted to the grids to form a plurality of fluid pathways among the tubes, said tubes being empty or containing catalytic or non catalytic materials and U.S. Pat. No. 6,000,685 which is incorporated herein in its entirety and which discloses contact structures comprising a plurality of sheets of wire mesh formed into vee shaped corrugations having flats between the vees, said plurality of sheets being of substantially uniform size having the peaks oriented in the same direction and substantially in alignment, said sheets being separated by a plurality of rigid members oriented normally to and said resting upon said vees.
The changes in holdup and pressure for the packing were determined for a three phase trickle bed reactor using a model system to simulate the sulfuric acid alkylation of butene with isobutane. Sulfolane was used to simulate the acid (heavy liquid, HL), normal hexane to simulate the liquid hydrocarbon (light liquid, LL) and nitrogen to simulate the gaseous hydrocarbon feed (gas, g). Measurements were made for 1) liquid holdup and 2) pressure drop across the packed column containing five feet of the packing as described. In the data below four main sets of conditions were measured including: 1) Boundary, 2) Base Case, 3) High LL Case, and 4) High HL Case. Herein HL stand for heavy.
FIG. 2 depicts graphically the effect of flow rates on the pressure drop. The pressure drop in pounds per square inch per foot of column is plotted as a function of the product of the Froude Number of the hexane, Fr(LL), and the Reynolds Number of the nitrogen, RE(g). The Froude Number is the superficial velocity of the fluid (in this case the hexane) divided by the square root of the product of the gravity constant times the diameter of the reactor. The error bars for given values are a result of the data being taken in the pulse flow regime. As shown, all of the points beyond a Fr(LL)Re(g)=5 are in the pulse regime. This equates to approximately a 0.06 psi/ft pressure drop provided by the packing which induces the pulse flow.
A unique feature of using a three phase (vapor/liquid/liquid) system is that mass fluxes can be adjusted whereby only one liquid phase is essentially operating in the pulse regime. With higher viscosity fluids (such as sulfolane or sulfuric acid) it was found that in order to obtain pulse flow at a fixed gas flux, the liquid mass flux would have to be increased when compared to a lower viscosity fluid (such as hexane or iso-butane). When the liquids of different viscosity are used it was found that there was a controlling fluid which forced pulsing (i.e. the lower viscosity fluid). Combination of a low viscosity fluid and a high viscosity fluid allows for operation where one liquid is essentially operating in pulse flow and the other in trickle. This type of operation is useful because it provides the good mixing associated with pulse flow but limits the pressure swings caused by the pulses due to dampening by the second viscous liquid phase. This is graphically depicted in FIG. 3 wherein the ratio of the pressure deviation to the overall pressure drop is plotted against the overall pressure drop.
The present pulse system is useful in a process for the alkylation of isoparaffin with olefin or olefin precursor comprising contacting a fluid system comprising acid catalyst, isoalkane and olefin in concurrent flow, preferably downflow into contact in a reaction zone with present system under conditions of temperature and pressure to react said isoparaffin and said olefin to produce an alkylate product. Preferably, the fluid system comprises a liquid and is maintained at about its boiling point in the reaction zone. The olefin precursor is an oligomer of one or more tertiary olefins such as the dimer, trimer, etc. of isobutene or a material which corresponds to said oligomer.
The reaction of oligomer of tertiary olefins with isoalkanes is on a molar basis with the constituent tertiary olefins of the oligomer rather than the oligomers. The alkylate product corresponds to the reaction of the tertiary olefin and isoalkanes.
For the purpose of illustration and not a limitation of the process, it is believed that instead of the expected reaction between the oligomer and the isoalkane, the oligomer is cracked into its olefin components which react with the isoalkane on a molar basis:
1) diisobutene+2 isobutane→2 isooctane (2,2,4-trimethyl pentane)
2) triisobutene+3 isobutane→3 isooctane (2,2,4-trimethyl pentane)
The conventional view had been that the product of 1) would be a C12 alkane and the product of 2) would be a C16 alkane whereas the product of reactions 1) and 2) is the same and is indistinguishable from a conventional cold acid alkylation product of the reaction:
3) 2 butene-2+2 isobutane→2 isooctane
4) 3 butene-2+3 isobutane→3 isooctane
The great advantage of the present invention is that although acid alkylations are extremely exothermic and require substantial refrigeration to maintain the reaction temperature in optimum range to prevent side reactions, the present reaction of the oligomers with the isoalkane to produce the alkylate in the same yields required less refrigeration making the process less expensive for the same yield of useful product.
One particular method of producing oligomer is that carried out in a catalytic distillation, for example, units formerly used to produce MTBE can readily be converted to producing oligomer merely by changing the feed to the reactor since the same catalyst serves both reactions.
Preferably, the oligomer comprises C8 to C16 olefins corresponding to oligomer prepared from C3 to C5 olefin. In a preferred embodiment the oligomer has 6 to 16 carbon atoms and corresponds to oligomers which are prepared from C4 to C5 olefins.
The widest use of the paraffin alkylation is for the preparation of a C8 gasoline component. The feed to this process is usually normal butene and tertiary butane contained in a �cold acid� reaction usually with sulfuric acid or HF. The normal butene (butene-2, for example) is a component of light naphtha along with normal butane, isobutane and tertiary butene. The separation of the normal butene from the isobutene can be effected by fractionation with difficulty because of their close boiling point. A preferred way to separate these olefin isomers or those of the C5 analogs is to react the more reactive tertiary olefin to form a heavier product which is easily separated from the normal olefins by fractionation.
Heretofore, the tertiary olefin was reacted with a lower alcohol, such as methanol or ethanol, to form ethers, such as methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME) which have been used as gasoline octane improvers but are being phased out because of health concerns.
The oligomerization of the tertiary olefin is also a preferred reaction when carried out on a naphtha stream with the separation of normal olefin being easily achieved by fractionation from the heavier (higher boiling) oligomers (mainly dimer and trimer). The oligomers may be used as gasoline components but there are limits to the amount of olefin material desirable or allowed in gasoline and it is frequently necessary to hydrogenate the oligomers for use in gasoline. The most desirable component for gasoline blending is C8, e.g., isoctane (2,2,4 trimethyl pentane).
The oligomer may be cracked back to the original tertiary olefins and used in cold acid reaction. However, the present invention has found that it is not necessary to crack the oligomer which may constitute the olefin feed to cold acid reaction with the alkane or may be co-fed with mono olefins. As noted above the result is the same product as the mono olefin alone with the additional benefit of a less exothermic overall reaction requiring less refrigeration and, hence, a lower energy cost for the alkylation.
The oligomerization process produces a heat of reaction that does not require the magnitude of heat removal as in the cold acid process. In fact, when the oligomerization is carried out in a catalytic distillation type reaction, the heat of reaction is removed as boilup, which in this type of reaction is the lower boiling mono olefins and alkanes which are being separated from the oligomer. Thus, even though there is heat produced in the oligomerization it is of no cost to the production of the gasoline since it is used in the fractionation, and the operating cost of the alkylation unit is reduced by the use of oligomer to replace some or all of the conventional short chain olefin.
In a preferred embodiment of the present alkylation process, a light naphtha stream comprising normal and tertiary olefins is contacted with an acid resin catalyst under oligomerization conditions to preferentially react a portion of the tertiary olefins with themselves to form oligomers, and feeding said oligomers to an alkylation zone with an isoalkane in the presence of an acid alkylation catalyst to produce an alkylation product comprising the alkylate of said tertiary olefin and said isoalkane.
The oligomerization may be carried out in a partial liquid phase in the presence of an acid cation resin catalyst either in straight pass type reaction or in a catalytic distillation reaction where there is both a vapor and liquid phase and a concurrent reaction/fractionation. Preferably, the feed is a C4-C5, C4 or C5 light naphtha cut. The tertiary olefins may include isobutene, and isoamylenes and are more reactive than the normal olefin isomers and are preferentially oligomerized. The primary oligomer products are dimers and trimers. The isoalkanes preferably comprise isobutane, isopentane or mixtures thereof.
When a straight pass reactor is used, such as that disclosed in U.S. Pat. Nos. 4,313,016; 4,540,839; 5,003,124; and 6,335,473, the entire effluent comprising the oligomer, normal olefins and isoalkanes may be fed to an acid alkylation reaction. The normal alkanes are inert under the conditions of the present alkylation. Under alkylation conditions the isoalkane reacts with the normal olefin to form alkylate product and with the individual constituent olefins of the oligomers to form the alkylate product. The implication of the result of the present process is that the oligomers are dissociated or in some manner make their constituent olefins available for reaction with isoalkanes. Thus, the reaction will produce:
1) isobutene oligomer+isobutane→isooctane;
2) isobutene oligomer+isopentane→branched C9 alkanes;
3) isoamylene oligomer+isobutane→branched C9 alkanes;
4) isoamylene oligomer+isopentane→branched C10 alkanes;
whereas it would have been expected that reaction 1) would produce at least or mostly C12 alkanes, reaction 2) would produce at least or mostly C13 alkanes, reaction 3) would produce at least or mostly C14 alkanes, and reaction 4) would produce at least or mostly C15 alkanes.
When a catalytic distillation reaction such as that disclosed in U.S. Pat. Nos. 4,242,530 or 4,375,576 is employed for the oligomerization, the oligomer is separated from the lower boiling normal olefins and alkanes in the reaction product by concurrent fractionation. The streams, normal olefins and alkanes (overheads) and oligomers (bottoms), may be united or individually fed to the alkylation or may be used individually with at least the oligomer being fed to the alkylation.
The present invention offers an improved contacting apparatus and process for producing and separating an alkylate product using sulfuric acid as catalyst. This same or similar device may also be used with other acids or acid mixtures.
The present process preferably employs a downflow reactor packed with contacting internals or packing material (which may be inert or catalytic) through which passes a concurrent multi phase mixture of sulfuric acid, hydrocarbon solvent and reactants at the boiling point of the system. The system comprises a hydrocarbon phase and an acid/hydrocarbon emulsion phase. A significant amount of sulfuric acid is held up on the packing. Reaction is believed to take place between the descending hydrocarbon phase and the sulfuric acid dispersed on the packing. Olefin continuously dissolves into the acid phase and alkylate product is continuously extracted into the hydrocarbon phase. Adjusting the pressure and hydrocarbon composition controls the boiling point temperature. The reactor is preferentially operated vapor continuous but may also be operated liquid continuous. The pressure is preferentially higher at the top of the reactor than at the bottom.
Adjusting the flow rates and the degree of vaporization controls the pressure drop across the reactor, e.g., total pressure drop across said reactor of between 0 and 4 psia. Multiple injection of olefin is preferred. The type of packing also influences the pressure drop due to the acid phase hold-up. The product mixture before fractionation is the preferred circulating solvent. The acid emulsion separates rapidly from the hydrocarbon liquid and is normally recycled with only a few minutes residence time in the bottom phase separator. Because the products are in essence rapidly extracted from the acid phase (emulsion), the reaction and/or emulsion promoters used in conventional sulfuric acid alkylation processes may be added without the usual concern for breaking the emulsion. The process may be described as hydrocarbon continuous as opposed to acid continuous.
The hydrocarbon feedstock undergoing alkylation by the method of the present invention is provided to the reaction zone in a continuous hydrocarbon phase containing effective amounts of olefinic and isoparaffinic starting materials which are sufficient for forming an alkylate product. The olefin:isoparaffin mole ratio in the total reactor feed should range from about 1:1.5 to about 1:30, and preferably from about 1:5 to about 1:15. Lower olefin:isoparaffin ratios may also be used.
The olefin component should preferably contain 2 to 16 carbon atoms and the isoparaffin component should preferably contain 4 to 12 carbon atoms. Representative examples of suitable isoparaffins include isobutane, isopentane, 3-methylhexane, 2-methylhexane, 2,3-dimethylbutane and 2,4-dimethylhexane. Representative examples of suitable olefins include butene-2, isobutylene, butene-1, propylene, pentenes, ethylene, hexene, octene, and heptene, merely to name a few and as described above may be oligomers of these olefins.
In the fluid process the system uses hydrofluoric or sulfuric acid catalysts under relatively low temperature conditions. For example, the sulfuric acid alkylation reaction is particularly sensitive to temperature with low temperatures being favored in order to minimize the side reaction of olefin polymerization. Petroleum refinery technology favors alkylation over polymerization because larger quantities of higher octane products can be produced per available light chain olefins. Acid strength in these liquid acid catalyzed alkylation processes is preferably maintained at 88 to 94% by weight using the continuous addition of fresh acid and the continuous withdrawal of spent acid. Other acids such as solid phosphoric acid may be used by supporting the catalysts within or on the packing material.
Preferably, the process of the present invention should incorporate relative amounts of acid and hydrocarbon fed to the top of the reactor in a volumetric ratio ranging from about 0.01:1 to about 2:1, and more preferably in a ratio ranging from about 0.05:1 to about 0.5:1. In the most preferred embodiment of the present invention, the ratio of acid to hydrocarbon should range from about 0.1:1 to about 0.3:1.
Additionally, the dispersion of the acid into the reaction zone should occur while maintaining the reactor vessel at a temperature ranging from about 0� F. to about 200� F., and more preferably from about 35� F. to about 130� F. Similarly, the pressure of the reactor vessel should be maintained at a level ranging from about 0.5 ATM to about 50 ATM, and more preferably from about 0.5 ATM to about 20 ATM. Most preferably, the reactor temperature should be maintained within a range from about 40� F. to about 110� F. and the reactor pressure should be maintained within a range from about 0.5 ATM to about 5 ATM.
In general, the particular operating conditions used in the process of the present invention will depend to some degree upon the specific alkylation reaction being performed. Process conditions such as temperature, pressure and space velocity as well as the molar ratio of the reactants will affect the characteristics of the resulting alkylate product and may be adjusted in accordance with parameters known to those skilled in the art.
An advantage of operating at the boiling point of the present reaction system is that there is some evaporation which aids in dissipating the heat of reaction and making the temperature of the incoming materials closer to that of the materials leaving the reactor as in an isothermal reaction.
Once the alkylation reaction has gone to completion, the reaction mixture is transferred to a suitable separation vessel where the hydrocarbon phase containing the alkylate product and any unreacted reactants is separated from the acid. Since the typical density for the hydrocarbon phase ranges from about 0.6 g/cc to about 0.8 g/cc and since densities for the acid generally fall within the ranges of about 0.9 g/cc to about 2.0 g/cc, the two phases are readily separable by conventional gravity settlers. Suitable gravitational separators include decanters. Hydrocyclones, which separate by density difference, are also suitable.
One alkylation embodiment is shown in the FIG. 4 which is a simplified schematic representation of the apparatus and flow of the process. Such items as valves, reboilers, pumps, etc., have been omitted.
The reactor 10 is shown containing a disperser mesh 40. The present dispersers achieve radial dispersion of the fluid or fluidized materials in the reactor. The feed to the reactor comprises an olefin fed via line 12 such as n-butene and an isoparaffin (e.g., isobutane) fed via line 14 through line 52. Preferably a portion of the olefin is fed along the reactor via lines 16 a, 16 b, and 16 c. A liquid acid catalyst such as H2SO4 is fed via line 56 and make-up acid may be supplied through line 38. The hydrocarbon reactants are fed to the reactor which is preferably a generally cylindrical column via line 58 and through appropriate dispersing means (not shown) into the disperser mesh 40, for example, a co-knit wire and fiberglass mesh.
The hydrocarbon reactants and non reactive hydrocarbons (e.g., normal butane) are intimately contacted with the acid catalyst as the alkylation proceeds. The reaction is exothermic. The pressure as well as the quantities of reactants are adjusted to keep the system components at the boiling point but partially in the liquid phase as the system components pass down flow through the reactor in mixed vapor\liquid phase and out through line 18 into decanter 30. In the decanter the system components are separated into an acid phase 46 containing the catalyst, a hydrocarbon phase 42 containing the alkylate, unreacted olefin and unreacted isoparaffin, and non reactive hydrocarbons and a vapor phase 44 which may contain some of each of the components and any lighter hydrocarbon components which are removed from the system via line 50 for further handling as appropriate.
Most of the acid phase is recycled via line 24 and 56 into the reactor. Make-up acid may be added via line 38 and build-up spent acid removed via line 48.
The hydrocarbon liquid phase is removed via line 22 with a portion recycled to the top of the reactor via line 28. The remainder of hydrocarbon phase is fed to distillation column 20 via line 26 where it is fractionated. Normal butane, if present in the feed, can be removed via line 36 and the alkylate product is removed via line 34. The overheads 32 are primarily unreacted isoalkane which is recycled via line 52 to the top of reactor 10.
Experimental Set Up for Alkylation of Isoparaffin+Olefin
For the following examples the laboratory reactor is 15 feet high by 1.5 inches diameter. It is packed with varying amounts and types of packing material. The H2SO4 inventory is about 1 liter depending on the holdup of the packing used. The surge reservoir is about 3 liters and passes all the acid plus liquid hydrocarbon out the bottom to circulate a two-phase mixture with a single pump. Feeds are introduced at the top of the reactor to flow down with the recycle mixture. Vapor is produced by heat of reaction plus ambient heat gains and helps force the liquids down through the packing creating great turbulence and mixing. Most of the vapors are condensed after the reactor outlet. Uncondensed vapor and liquid hydrocarbon product passes through an acid de-entrainer then through the backpressure regulator to the de-isobutanizer. Mass flow meters are used for feed flows and a Doppler meter measures the circulation rate. Liquid products from the de-isobutanizer are weighed. However, the vent flow rate is estimated as being the difference between the mass flow metered feed in and the weighed liquid products out. GC analyzes all hydrocarbon products, including the vent. Titration is used for spent acid assay.
In the following examples the experimental unit circulates hydrocarbon and acid down flow at the boiling point of the hydrocarbons present. Pressure and temperature readings are logged electronically. The reactor outlet temperature and pressure are used to calculate the amount of iC4 in the recycle hydrocarbon using an iC4/Alkylate flash calculation.
A backpressure regulator that passes both product liquid and vapor to the de-isobutanizer tower, maintains the pressure. A small amount of N2 may be used primarily to keep acid from backing up into the feed line. However, too much N2 will cause a decrease in product quality by diluting reactive isoparaffin in the vapor phase.
The circulation pump in the experimental setup circulates both the acid emulsion layer and the liquid hydrocarbon layer. Alternatively, these two phases may be pumped separately.
The acid inventory is maintained by momentarily diverting the entire recycle through a measuring tube using a three-way valve. The trapped material settles in seconds to form two layers. The volume percent acid layer and hydrocarbon layer is then used in conjunction with the Doppler meter reading to estimate the volumetric circulation rates of both phases.
The DP (pressure higher at the top or reactor inlet) is maintained between 0 and 3 psi by manipulating the circulation rates and the heat balance around the unit. Different packing usually requires different vapor and liquid flow rates to load to the same DP. Most of the time, the ambient heat gains and the heat of reaction provide adequate vapor (mostly iC4) loading.
Because of refrigeration constraints, about 1-3 lbs/hr of extra liquid iC4 may be introduced with the feed to provide some trim cooling. This excess iC4 is relatively small and does not significantly affect the iC4/Olefin ratio since the circulating hydrocarbon rates are typically on the order of 100-200 pounds per hour. It is the circulating hydrocarbon flow rate and composition that dominates the iC4 ratios to everything else.
Typical Operating Conditions for C4 Alkylation in the Examples
Expected vs. actual alkylation product MW's and moles iC4 uptake with various olefins (e.g. in theory 1 mole of C6 olefin should react with 1 mole of iC4 to form a C10 alkylate; MW=142) Results indicate depolymerization generating more and lower MW olefins that combine with additional iC4.
Patent Citations
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40% OFF! - On The Farm
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- Type: Combo Pack
- Designer: Paty Greif Digital Designer
- Software Category: Animals – Pets
- Download Size: 86.1 MB (approximate)
Design Elements
- Digital Papers: 22
- Page Elements: 63
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"On The Farm" Muuuuu!!!! Beeeee!!! Oinck!!!! All papers are in JPEG 3600x3600 - 300dpi. The elements are in PNG 300dpi PU/S4H Included: 66 Hand-drawn doodles elements 22 papers I hope you enjoy creating with this Kit! Xoxo Paty Greif
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comb-overLine breaks: comb-over
Definition of comb-over in English:
A strip of hair combed over a bald patch on a man's head in an attempt to conceal it.
Example sentences
- There are comb-overs, hair potions, and more drastic transplants.
- She stared at the back of the cabbie's head, at the lame comb-over attempt to hide a textbook case of male pattern baldness.
- Many men wear a comb-over to hide thinning or a receding hairline.
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Word of the day prepotent
Pronunciation: ˌprēˈpōtnt
greater than others in power or influence