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Braves suspend Dan Uggla for 1 game
The Associated Press
Dan Uggla
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CHICAGO -- Dan Uggla's future in Atlanta was in question Sunday after the Braves suspended the struggling second baseman for their final game before the All-Star break.

 The team announced the suspension on its Twitter feed, with no further explanation. Manager Fredi Gonzalez also declined to elaborate when asked about the punishment before the Braves' 10-7 victory at the Chicago Cubs.

 "I'm not going to say anything other than that it's an internal matter," he said. "That's the way I like to handle stuff, and the Atlanta Braves like to handle stuff. And that's it. You can ask me 400 different ways and my way is that we're going to handle it internally."

 The 34-year-old Uggla has played sparingly since rookie Tommy La Stella was promoted from Triple-A Gwinnett on May 28. The three-time All-Star is batting .162 with two homers and 10 RBIs in 48 games.

 The Braves acquired Uggla in a November 2010 trade with the Marlins, and then signed the three-time All-Star to a $62 million, five-year contract before his first game with Atlanta. He is slated to make $13 million next year in his final season under the deal.

 Uggla had a 33-game hitting streak and connected for 36 homers in his first season with the Braves, but most of his numbers have been trending down over the past couple of years. He hit just .179 with 22 homers and 171 strikeouts in 2013, when Atlanta won the NL East and lost to the Dodgers in the division series.

 Gonzalez said he expects Uggla to be with the team when it begins the second half at home against the Phillies on Friday. He also isn't worried about the effect of the suspension on his team.

 "I don't think so. I got a pretty good pulse of our clubhouse," he said. "If anybody wants to talk to me, my door is always open. And they know that."

 Atlanta also promoted infielder Phil Gosselin from Triple-A Gwinnett before its series finale against the Cubs. Gosselin hit .345 with five homers and 30 RBIs in 88 games with Gwinnett.

 "He's had a terrific first half of the Triple-A season," Gonzalez said.
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ALISA DOCTOROFF and John Ruskay 390.
(photo credit:Pnina Weiss)
NEW YORK (JTA) -- John Ruskay will be leaving his position as executive vice president and CEO of UJA-Federation of New York.The federation announced Ruskay's departure on Tuesday. His last day as head of the nation's largest federation will be on June 30, 2014.Ruskay joined the federation in 1993 and has been CEO since 1999. In Ruskay's time at the helm, UJA-Federation raised more than $2.7 billion and increased its endowment from $330 million to more than $860 million, according to the federation."I have been blessed to have a job that has enabled me to bring together three of my lifelong passions: my conviction that Judaism enhances life; my commitment to care for every being; and my belief in the value of community," Ruskay said in a letter announcing his departure.The search for Ruskay's successor will be handled by the federation's executive committee and guided by board chairwoman Alisa Doctoroff, the federation said.Ruskay came to the federation from the Conservative movement's Jewish Theological Seminary of America, where he was vice chancellor. In the early 1980s, Ruskay was educational director of the 92nd Street Y on Manhattan's Upper East Side.He is a graduate of the University of Pittsburgh and earned a doctorate in political science from Columbia University.
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Tel: (818)788-2199
Grades: K - 6
Valley Beth Shalom Harold M.
Schulweis Day School, a K-6 Solomon Schechter elementary school, offers a superior education and enriching foundation for life's journey.
Students thrive in an environment that focuses on academic excellence, strong Jewish values, a dynamic community, and personal growth.
Students reach their learning potential guided by talented teachers through individual learning approaches and small group instruction.
Established in 1978, VBS Day School has more than 30 years of experience.
Affiliated with the Solomon Schecter Day School Association, VBS has a rich history and a unique community fostered by the involvement of parents, VBS rabbis and cantors, and a thriving synagogue that engages the entire family in Jewish life.
Upon commencement, VBS Day School students have attained much more than a high quality education.
They have discovered an academic, emotional, and spiritual basis for life's journey as it continues beyond secondary school and into adulthood showing that they can make a difference in the world.
School Overview
|School Membership(s)School Assoc.
|Other school association(s)
Western States Association of Schools and Colleges (WASC)
California Association of Independent Schools (CAIS)
|Religious Affiliation
|Grades Offered
|Grades Kindergarten - 6
Student Body
|Total Students
|Student Body Type
Academics and Faculty
|Total Classroom Teachers
|30 teachers
|Average Class Size
|19 students
Finances and Admission
|Admission Deadline
|Jan. 29 / rolling
|Yearly Tuition Cost
|Tuition Notes
|1,000 new student fee 100 parent org dues 100 supplemental fee synagogue membership (approximately $2,500)
|% on Financial Aid
|Average Financial Aid Grant
|Admissions Director
|Cindy Goodman
|Total Sports Offered
|6 sports
|Basketball, Dance, Flag Football, Football, Soccer, VolleyballBasketball, Dance,
Flag Football, Football,
Soccer, Volleyball,
|Total ExtracurricularsTotal Extra-curric.
|6 extracurriculars
|art, cooking, drama, karate, mathemagic, sports art, cooking, drama, karate, mathemagic, sports,
School Notes:
Our mission is to empower each child to reach his/her potential as a confident, skilled, and passionate learner with a strong Jewish identity. Exceptional, forward-thinking academic general and Judaic studies programs emphasize inquiry, critical thinking, and creativity while instilling Jewish ethics, values, spirituality, a personal connection to Israel, and a strong sense of social responsibility. Embraced by a nurturing and dynamic community, our students build a foundation that fosters academic achievement, celebrates the joy of Jewish life, and cultivates a desire to make a difference in the world.
Profile last updated: 02/02/2015
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who is owned by Team Valor International, is trained by Rick Mettee and
was ridden Alan Garcia. The ownership partnership includes Olympic
swimming legend Michael Phelps, a Baltimore native, his longtime coach
Bob Bowman and former VISA USA chief executive Carl Pascarella.
Cerro won by a nose, with Dynamic Strike finishing second. The winner covered the 1-1/8th distance in 1:51.81 and paid $3.20. Dreaming of Jazz was a distant third, 12-3/4 lengths behind the first two.
knew on paper this was a closer race than what the odds said," Mettee
said. "We knew it was going to be a tough race and he got the head bob. I
think those first two are pretty solid horses."
ran very well," said Forest Boyce, who was aboard Dynamic Strike. "He
runs better when he is in striking distance. I had to move early because
the other horse was getting his own way early on. I am very proud of
the effort and he is just going to get better and better."
is now three-for-eight lifetime and improved his career earnings to
$109,125. After breaking his maiden in Italy last summer, the son of Mr.
Greeley raced at Gulfstream Park and Keeneland earlier this year under
the tutelage of Graham Motion and posted a sixth place finish behind
Kentucky Derby winner Orb in the Fountain of Youth (G2) and a fourth
place finish in the Lexington Stakes (G3).
was the first official win as a trainer since 2001 for Mettee, who like
Phelps is a Towson High School graduate. Mettee, who spent many years
running Godolphin's U.S. division for the Dubai royal family, began his new job at the Fair Hill Training Center on May 1."It is nice to get a off to a great start. Stakes wins are hard to come by,"
added Mettee, who now has a win and two seconds from three starters
this year. "Things are going well. Fair Hill is a wonderful place to
train. We have a few nice horses and are going to try to spot them in
the right races. I have fond memories of Pimlico. My grandmother lived
in Hampden and I used to take the bus here on Saturday's, which is how I
got into racing."
Canonero was the last of 25 stakes races carded at Pimlico during the
spring meet, which ends a week from today. Three days remain in the
stand with live racing also conducted tomorrow and Friday afternoons.
Marbre Rose collared the front-running Endless Lig...
Are You Kidding Me, confidently ridden by Alan Gar...
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Every year race fans debate the running styles of...
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1895 $2 1/2Click the image to load the highest resolution version.
NGC 1895 PR 66 Cameo. A singularly impressive proof gold piece that shows heavily contrasted fields and devices with a light hazy patina surrounding the outer devices. This piece is tied for the finest known example of the date. One estimate places the number of survivors between 45 and 55 pieces out of a mintage of 119 proofs. The 1895 proof quarter eagle is 8 to 10 times rarer than the more famous proof Morgan of the year. (NGC ID# 7KFT, PCGS# 7921)
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Wednesday, January 18, 2012
Cougar Town Returns On Valentine's Day On ABC; Sheen's New Sitcom Anger Management Premieres In June On FX
Yesterday we hinted that the Cougar Town season premiere date would be revealed and it was. We broke the news on Twitter that the series will return for its third season on Tuesday, Feb. 14 - Valentine's Day - at 8:30pm. The comedy will air Tuesdays at 8:30pm. It has a 15 episode order (down from the original 22 it was given last May) since it is launching in mid-season. The series will air repeat free from Feb. 14 to May 15. On the third season premiere episode "Ain't Love Strange," Jules (Courteney Cox) is miffed when Grayson (Josh Hopkins), who has an ulterior motive, calls her "predictable," while Ellie (Christa Miller) frets that little Stan is turning into a "devil child," or even worse, could grow up to be like Laurie (Busy Phillips) and Travis (Dan Byrd) likes his new off campus housing, until Bobby (Brian Van Holt) tries to convince him to take dog Travis in.
Cougar Town is essentially replacing Work It, which was pulled after just two episodes. Repeats of Last Man Standing are airing for the rest of January in this timeslot. It is unclear right now what is airing at 8:30pm on Feb. 7, but Cougar Town will launch the week after on Feb. 14. Show some love and watch Cougar Town on Valentine's Day! Penny can!
FX announced Sunday at the TCA Winter 2012 Press Tour that Charlie Sheen's sitcom adaptation of the Adam Sandler-Jack Nicholson big screen comedy Anger Management will premiere in June 2012. Previously it was announced just as "Summer 2012." He'll fill the Nicholson role of an anger management counselor. The series of course will mark Sheen's return to television following his firing from the CBS sitcom Two and a Half Men last year following his erratic behavior. Sheen was on hand at the TCA winter press tour on Sunday.
FX also airs reruns of Two and a Half Men, so the new sitcom is a perfect fit for them. Ten episodes will air for sure of this new comedy and if ti does well, it will get a bulk order of about 90 episodes. There is plenty still to come on Anger Management, such as an actual premiere date and timeslot. So you'll want to stay with us, but we just had to mention that it was being introduced at the TCA winter press tour.
New on DVD/Blu-ray (August)
08/04 - The Comeback - The Complete Series
08/04 - I Love Lucy - Ultimate Season 2 (Blu-ray)
08/04 - Sgt. Bilko (The Phil Silvers Show) - Season Three
08/11 - The Jeffersons - Season Eight
08/11 - Maude - The Complete Second Season
08/11 - 2 Broke Girls - The Complete Fourth Season
08/11 - The Jeff Foxworthy Show - The COmplete Series (Mill Creek)
08/18 - Mike & Molly - The Complete Fifth Season
08/18 - Welcome Back, Kotter - The Final (Fourth) Season
08/25 - King of the Hill - The Complete 11th Season
08/25 - The Mindy Project - Season Three
More TV DVD Releases / DVD Reviews Archive / SitcomsOnline Digest
Sitcoms Airing Tonight
Saturday, August 29
Sitcom Stars on Talk Shows (Week of August 31) (All times ET unless noted)
Monday, August 31
- Victoria Justice (Victorious/Zoey 101) - Watch Victoria on The Tonight Show Starring Jimmy Fallon at 11:34pm on NBC.
- Roseanne Barr (Roseanne) - Roseanne stops by Jimmy Kimmel Live! at 11:35pm on ABC.
- Demi Lovato (Sonny with a Chance) - Demi is a panelist and musical guest on Jimmy Kimmel Live! at 11:35pm on ABC.
- Melora Hardin (Transparent/Wedding Band/The Office) - Melora is a guest on a repeat of The Late Late Show with James Corden at 12:37am on CBS.
- Amy Landecker (Transparent) - Amy will be on a repeat of The Late Late Show with James Corden at 12:37am on CBS.
- Abby Elliott (Odd Mom Out) - Abby appears on a repeat of Watch What Happens: Live at 11pm on Bravo.
- Tim Conway (McHale's Navy/Rango) - Tim is a guest on a repeat of The Queen Latifah Show, so check your local listings.
- Cedric the Entertainer (The Soul Man/The Steve Harvey Show) and Niecy Nash (The Soul Man/Getting On/Reno 911!) - Cedric and Niecy are guests on a repeat of The Talk on CBS at 2pm ET/1pm CT-PT.
- Jeremy Sisto (Suburgatory) and David Walton (About a Boy/Bent/Perfect Couples) - Jeremy and David talk about their new film Break Point on NBC's Today in the 9am hour, on the AOL Build Show, on SI Now and on New York Live on WNBC in New York at 12:30pm ET.


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Sergio Aguero believes the entire Manchester City team deserve the plaudits for Sunday's 4-1 demolition of Manchester United.
The Argentina international netted a brace to lead Manuel Pellegrini's men to a comfortable victory at the Etihad Stadium, despite Wayne Rooney grabbing a late consolation courtesy of a free-kick.
But Aguero has refused to accept sole credit for the win, insisting his team-mates deserve plenty of praise for their approach to the game.
"The most important thing is that the goals gave us the win," he told the club's official website.
"I'm very happy that we won three important points, especially against United. We were really motivated to win, and that lead us to victory.
"The motivation helped us play without any anxiety. The confidence and the attitude that the team had was very good, and in the second half, despite winning 2-0, we kept playing like that.
"All the team were brilliant, the defence as well. We're all one team. There are no individual heroes."
Aguero has scored 38 goals in 69 Premier League appearances since joining City from Atletico Madrid in 2011.
S. Agüero 16'
(assist by A. Kolarov)
1 - 0
2 - 0
3 - 0
S. Nasri 50'
(assist by Jesús Navas)
4 - 0
4 - 1
87' W. Rooney
|J. Hart
|V. Kompany
|P. Zabaleta
|A. Kolarov
|M. Nastasić
|S. Nasri
|Y. Touré
|Jesús Navas
|S. Agüero
|16' 47'
|Coach: M. Pellegrini
|De Gea
|R. Ferdinand
|N. Vidić
|P. Evra
|C. Smalling
|M. Carrick
|A. Valencia
|A. Young
|M. Fellaini
|W. Rooney
|30' 87'
|D. Welbeck
|Coach: D. Moyes
for Jesús Navas 71'
for Negredo 75'
for S. Agüero 86'
for A. Young 51'
|Ruddy hoping to impress Hodgson
|Wolfsburg proved there is life after De Bruyne - Hecking
|Van Gaal unsure if Romero will replace De Gea long-term
|Dzeko wants Totti partnership at Roma
|No excuses for City - Pellegrini
|San Jose Earthquakes 1 LA Galaxy 0: Salinas´ header levels Cali Clasico tally
|Koeman plays down expectations
|Stuttgart´s Langerak suffers surgery setback
|Rodgers hails Milner´s leadership, mentality
|Conte hints at Giovinco recall, doesn´t rule out Balotelli
|Martinez slams Chelsea over Stones pursuit
|Leverkusen are title contenders - Guardiola
|Babel in sexism controversy
|Pellegrini prepared to wait for Otamendi
|Sevilla v Atletico Madrid: Llorente hoping to repay faith
|Veloso back for Portugal
|Kranevitter joins Atletico on five-year deal
|Maiga leaves West Ham for Al Nassr
|Blackburn Rovers 0 Bolton Wanderers 0: Lancashire derby ends in stalemate
|Coutinho, Rafinha called into Brazil squad
|Guingamp 2 Marseille 0: Privat and Benezet inflict more misery on visitors
|Wolfsburg 3 Schalke 0: Hosts canter to victory without De Bruyne
|Villarreal 3 Espanyol 1: Soldado inspires turnaround
|Carpi v Inter: Mancini demands full focus
|De Bruyne set to complete City move, reveals Allofs
|Roma v Juventus: Champions seek to bounce back
|Motta pens new PSG deal
|Settled Bale in the hunt for more titles at Real
|Blind hands Robben Netherlands armband
|Rodriguez joins Everton from River Plate Montevideo
|Bolivia appoint Baldivieso
|Southampton v Norwich City: Neil holds south-coast club up as inspiration
|Monaco v Paris Saint-Germain: Rabiot wants champions to send a message
|Barca face tough group - Luis Enrique
|Swansea City v Manchester United: Van Gaal celebrates 50th game in charge
|Herrera pushing for United start, says Van Gaal
|Borussia Dortmund v Hertha Berlin: Tuchel puts perfect record on the line
|Michu still not part of my plans if he stays – Monk
|Hughes not expecting late transfer deals at Stoke
|FIFA or bust in Platini´s presidency bid
|Cuadrado struggles to explain Chelsea snub
|Atletico seal Borre deal
|Schalke loan Hojbjerg from Bayern
|Sissoko in contention to face Arsenal
|Advocaat confident of more signings, but De Guzman not among them
|Berahino ´not just a lump of meat´ - Pulis
|Ajax set to face Champions League quality - Van der Sar
|Pellegrini quiet on intense De Bruyne speculation
|Van Persie and Nani offer cause for Celtic excitement - Hawthorn
|Lopes seals Monaco switch
|Mourinho silent on Stones saga
|Milan snap up Kucka
|Can earns first Germany call-up
|Dortmund get kind draw, Sousa takes Fiorentina back to Basel
|Costa and Mata return for Spain qualifiers, De Gea gets the nod
|Rodriguez omission not personal - Benitez
|Allofs frustrated by Premier League´s financial muscle
|Sherwood hopeful over Traore fitness
|Leverkusen sign Kampl from Dortmund
|Toivonen joins Sunderland on loan from Rennes
|Markovic has Liverpool future, says Rodgers
|Martinez insists Stones in perfect environment at Everton
|Tottenham wrap up Son deal
|Schmeichel wants Real target De Gea to re-sign with United
|Cech is one of the best - Cudicini
|Rodwell hoping for more goals
|Thauvin needs time to settle at Newcastle – Haidara
|Kennedy takes blame for Celtic´s loss, stands by zonal marking
|CONCACAF Champions League Review: Comunicaciones, Motagua off the mark
|Rooney´s contribution undervalued - Schmeichel
|Jedinak ruled out as Socceroos make changes
|Sampdoria not a ´discount store´ - president Ferrero
|Montolivo: No issue with Mihajlovic
|Gilardino signs for Palermo
|Chelsea target ´China´s Sergio Ramos´
|Striker search like looking for love - Pochettino
|Hecking ´sick´ of De Bruyne talk
|Deschamps calls up Martial, leaves out Sakho
|´The only thing they can is long balls´ - Midtjylland´s skipper slams Southampton
|UEFA Europa League Review: Reus leads Dortmund rout, AZ complete late comeback
|Messi should win Ballon d´Or - Bartomeu
|Koeman rues refereeing decisions after Europa League defeat
|Tottenham deal for Son not complete, say Leverkusen
|Tuchel thrilled with aggressive Dortmund display
|Midtjylland 1 Southampton 0 (2-1 agg): Premier League side crash out
|Borussia Dortmund 7 Odd 2 (11-5 agg): Reus hat-trick highlights hammering
|Cudicini tips Mourinho to avoid Porto upset
|Anything is possible with Neymar´s future - Belletti
|Burnley bring in Barton
|Bayern Munich v Bayer Leverkusen: Vidal putting friendships on hold
|De Bruyne edges closer to City move after further Wolfsburg talks
|Real Madrid v Real Betis: Benzema back as Real look to hit the goal trail
|Barcelona v Malaga: Rosales hopes for another upset
|West Brom hit out at Tottenham´s Berahino pursuit
|Stoke City v West Brom: Pulis set for Britannia return
|Tottenham v Everton: Pochettino´s men eye first win
|Everton reject Stones´ transfer request
|Messi named UEFA Player of the Year
|Pocehttino quiet on Berahino bids
|Real Madrid to meet PSG in Champions League, Barca drawn with Leverkusen
|Bournemouth v Leicester City: Howe eager to entertain
|Ranieri coy on Gray link
|Newcastle United v Arsenal: Wenger hopes for sharper shooting
|PSG snap up Kurzawa from Monaco
|Aston Villa v Sunderland: Sinclair aims to replicate cup form
|Grabban a silly boy - Neil
|Chelsea v Crystal Palace: Pardew braced to face stronger champions
|Manchester City v Watford: Flores heads to Etihad with confidence
|Marseille loan Real Madrid youngster Lucas Silva
|Howe surprised by Harte´s retirement
|Liverpool v West Ham: History counts for nothing, says Bilic
|Bolasie set for Palace comeback
|De Bruyne to City not a done deal - Allofs
|Sevilla complete Llorente swoop
|Wenger supports video technology
|Milan v Empoli: Zapata sets sights on ´must-win´ fixture
|Watford boss Flores ´not happy´ with transfer situation
|Balotelli: I am no longer a kid
|Bilic has no issue with Valencia
|Arsenal ´not close´ to any late deals
|Balotelli finalises return to Milan on loan
|West Ham confirm Nolan departure
|Thiago signs new Bayern deal
|Schmidt saddened as Son nears exit
|CONCACAF Champions League Review: Sounders lose in Honduras
|Van Gaal considered early Herrera substitution
|MLS Review: Fire stun Red Bulls
|Carroll nears West Ham return
|Rodriguez hoping for England recall
|Leverkusen can challenge best - Schmidt
|Ozil defends United recruit Schweinsteiger
|Sporting ´better over two legs´ - Jesus
|Stoilov revels in historic Astana triumph
|Pioli: Lazio not ready for Champions League
|UEFA Champions League Review: Rooney nets treble and Astana make history
|Everton to reject Stones´ transfer request - Martinez


text: More from SI SI Media Podcast: Garbage Time host Katie Nolan SI Media Podcast: Garbage Time host Katie Nolan Watch: Dafne Schippers now third fastest 200m sprinter Watch: Dafne Schippers now third fastest 200m sprinter By Christopher Chavez Usain Bolt considers retiring after Rio 2016 Usain Bolt considers retiring after Rio 2016 Documentary series marks anniversary of Katrina Documentary series marks anniversary of Katrina Watch Usain Bolt defend his 200-meter world title Watch Usain Bolt defend his 200-meter world title By Christopher Chavez High school coach fired over rap video about drugs High school coach fired over rap video about drugs Watch: Three men run sub-44 seconds for 400-meters Watch: Three men run sub-44 seconds for 400-meters By Christopher Chavez Kenyan runners suspended after failed drug tests Kenyan runners suspended after failed drug tests Future of N.J. sports betting after denied appeal? Future of N.J. sports betting after denied appeal? By Michael McCann New Jersey's sports betting law denied on appeal New Jersey's sports betting law denied on appeal World record holder Genzebe Dibaba wins 1500m gold World record holder Genzebe Dibaba wins 1500m gold By Christopher Chavez Brain on Sports Podcast: Why athletes talk trash Brain on Sports Podcast: Why athletes talk trash By SI.com Staff Sports have helped New Orleans heal after Katrina Sports have helped New Orleans heal after Katrina By Tim Layden Watch: Emily Infeld stuns for 10,000-meter bronze Watch: Emily Infeld stuns for 10,000-meter bronze By Christopher Chavez Aisha Praught makes strides in Jamaican debut Aisha Praught makes strides in Jamaican debut By Christopher Chavez Watch: Usain Bolt beats Justin Gatlin for gold Watch: Usain Bolt beats Justin Gatlin for gold By Christopher Chavez Farah repeats as 10,000-meter world champion Farah repeats as 10,000-meter world champion By Christopher Chavez IAAF World Championships: Teen wins marathon IAAF World Championships: Teen wins marathon By Christopher Chavez WWE Rollins talks trash, Glen Davis on Rihanna WWE Rollins talks trash, Glen Davis on Rihanna Podcast with coordinating producer Fred Gaudelli Podcast with coordinating producer Fred Gaudelli 2015 IAAF World Championship: Startlists & results 2015 IAAF World Championship: Startlists & results 2015 IAAF World Championships: TV schedule 2015 IAAF World Championships: TV schedule Bolt vs. Gatlin: 100 meters for the soul of track? 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Nick Symmonds left off USATF roster for World Champions... Close Tweet0 Share0 Comment0 Share0 Share0 Stumble It0 Print0 More More Sports Zimmermann leaps to top of wide-open NL Cy Young field by Cliff Corcoran Twitter Email Posted: Thu Aug. 2, 2012 Though we'll never know for sure, the trade deadline may have altered the National League Cy Young race by sending Ryan Dempster, the major league ERA+ leader, and Zack Greinke to the other league. Dempster hadn't factored in my rankings due to his two disabled list stints, and Greinke had a 3.44 ERA for the Brewers, but it's not out of the question that either could have entered the race with a strong final two months.With those two out of the picture and mid-season leaders R.A. Dickey and Matt Cain cooling off of late, the NL Cy Young race is lacking a truly dominant performance. Fortunately, the American League race more than makes up for it with a tightly bunched sextet of outstanding seasons, one of which I had to eliminate given that I only have five spots to work with here (sorry, David Price).NOTE: All stats are through Wednesday, August 1. League leaders are in bold, major league leaders in bold italics. The number in parentheses after each player's name reflects his rank on the previous list.1. Jordan Zimmermann, RHP, Nationals (N/A)Season Stats: 8-6, 2.28 ERA, 1.07 WHIP, 6.4 K/9, 4.00 K/BB, 6.4 IP/GS, 175 ERA+Last Four Starts: 3-0, 0.75 ERA, 0.79 WHIP, 8.3 K/9, 11.00 K/BB, 6.0 IP/GSWhile teammates like Stephen Strasburg and Gio Gonzalez have been regular in this space, Zimmermann has been lurking just outside my top five for most of the season. He leaps to the top of the class this week on the strength of a red-hot run in which he hasn't allowed more than one earned run in any of his last seven starts and has allowed just five runs total over that span to go 5-0 with a 1.02 ERA since the end of June. Zimmermann has completed at least six innings in every one of his starts this season, leads the major leagues with 19 quality starts (in 21 turns), and both of his non-quality starts saw him allow just four runs in six innings.On only one other occasion did he allow as many as four runs in a game, and in that game one run was unearned. All three of those four-run starts came in May, and he has allowed as many as three runs just twice in his 11 starts since the calendar flipped to June (5-1, 1.80 ERA).Impressive as all of that is, Zimmermann also hasn't pitched more than seven innings in any of his starts this season as the Nationals are still being careful with his arm. Zimmermann is 26, three years removed from Tommy John surgery, and his 161 1/3 innings last year were a career high. With Stephen Strasburg still scheduled to be shut down once he reaches his innings limit this year, the Nationals need to keep Zimmermann available through the playoffs without putting him at risk.As a result, he has reached 100 pitches just seven times in 21 starts, has come out before 100 pitches in each of his last seven starts and has come out before reaching 90 pitches six times this year, including in two of his last four turns. That's partially a testament to Zimmermann's efficiency; he has walked just 1.6 men per nine innings this year, but despite all that coddling, he has experienced some shoulder inflammation recently and is getting an extra day of rest this week as a result.2. Johnny Cueto, RHP, Reds (2)Season Stats: 13-5, 2.39 ERA, 1.21 WHIP, 6.8 K/9, 3.12 K/BB, 6.6 IP/GS, 2 CG, 175 ERA+Last Four Starts: 4-0, 2.55 ERA, 1.54 WHIP, 7.3 K/9, 2.22 K/BB, 6.2 IP/GSIn two starts against the Rockies this season, including one on July 28, Cueto has allowed 10 runs (nine earned) in 10 2/3 innings. In 19 starts against the rest of the major leagues (not inlcuding his Thursday afternoon start against the Padres in Cincinnati), he has only once allowed more than three runs in a start and posted an aggregate ERA of 1.96. Fortunately for him, the Reds don't play Colorado again for the rest of the year.3. Ryan Vogelsong, RHP, Giants (5)Season Stats: 8-5, 2.22 ERA, 1.13 WHIP, 6.6 K/9, 2.21 K/BB, 6.8 IP/GS, 158 ERA+Last Four Starts: 1-2, 2.08 ERA, 1.19 WHIP, 8.0 K/9, 2.56 K/BB, 6.5 IP/GSVogelsong actually trumps Zimmermann as the most consistent starter in the major leagues this year. He has one fewer quality start than Zimmermann (18 to 19), but due to a season-opening injury, has made two fewer starts on the season and thus leads the majors in quality start percentage (95 percent). The exception came back on April 26 and saw him allow just four runs in six innings. Since then he has turned in 16 straight quality starts, going seven innings in 13 of them, and allowing as many as three runs in just three of them for a 1.88 ERA over that stretch. However, he has not completed eight innings in a single start this season and, unlike Zimmermann, that can't be blamed on coddling from management.R.A. Dickey, RHP, Mets (1)Season Stats:14-2, 2.83 ERA, 1.03 WHIP, 9.0 K/9, 4.45 K/BB, 6.9 IP/GS, 3 CG, 2 SHO, 134 ERA+Last Four Starts*: 2-1, 4.78 ERA, 1.48 WHIP, 8.2 K/9, 3.43 K/BB, 6.3 IP/GSSince his back-to-back one-hitters in mid-June, Dickey has posted a 4.56 ERA in seven starts and one relief appearance (*that relief appearance is included in his Last Four Starts line above). Just two of those seven starts have been quality. That seems like an overcorrection. In his first two seasons with the Mets, Dickey posted a 3.08 ERA, so it seems as likely that he'll rebound from this rough stretch as it was that he'd cool off from his historic hot streak in June. In the meantime, it's that incredible run of six mid-season starts that is keeping him on this list.Matt Cain, RHP, Giants (3)Season Stats: 10-4, 2.82 ERA, 1.00 WHIP, 8.3 K/9, 4.50 K/BB, 7.0 IP/GS, 2 SHO, 125 ERA+-Last Four Starts: 1-1, 3.76 ERA, 1.22 WHIP, 5.8 K/9, 2.83 K/BB, 6.6 IP/GSCain has posted a 4.01 ERA in eight starts since his perfect game, and only half of those outings have been quality. One reason for the change has been the longball. Despite being an extreme fly ball pitcher, in his first 13 starts this season (in which he went 8-2 with a 2.18 ERA), Cain allowed just seven home runs at a rate of 0.66 per nine innings. Since then, he has allowed nine more taters in eight turns at a rate of 1.57 per nine innings. In those last eight outings, Cain has also experienced a small correction in his luck on balls in play and seen his walk and strikeout rates return to something closer to his career averages.So much for this being a breakout year for Cain. Outside of his strikeout-to-walk ratio, his overall numbers are starting to look a lot like they have over the last couple of years. That's not a bad thing, but it's not a Cy Young thing, either.Off the list: James McDonald (4)1. Justin Verlander, RHP, Tigers (1)Season Stats: 11-7, 2.63 ERA, 0.97 WHIP, 8.5 K/9, 3.80 K/BB, 7.3 IP/GS, 6 CG, 1 SHO, 159 ERA+Last Four Starts: 2-2, 2.89 ERA, 1.11 WHIP, 7.7 K/9, 2.40 K/BB, 7.0 IP/GS, 1 CG*Those who don't look past triple crown stats will shocked that I don't have AL wins and ERA leader Jered Weaver first on this list. Of course, wins are a team-bases statistic, heavily dependent on run and bullpen support, something even the typically traditionalist awards voters have come to recognize in recent years. Verlander has received just 3.6 runs per 27 outs of support from the Tigers lineup, thrice failing to pick up a win in a game in which he threw eight innings and allowed two or fewer runs, enough to make up the difference between his win total and that of Weaver, who in stark contrast to last year, has received 6.8 runs of support per 27 outs.As for ERA, if you adjust it for the player's ballparks and present it as a percentage of the league average, you get their ERA+, a Baseball-Reference stat that I've added to the Season Stats lines this week. Looking at ERA+, Verlander has been 96 percent as effective as Weaver in 32 percent more innings. Throw in Verlander's nearly identical WHIP and superior strike zone peripherals and he's the clear choice for me, though this is shaping up to be a very compelling race.*Verlander's last complete game lasted just five innings in a rain-shortened loss to the Red Sox. He threw 107 pitches in those five innings and, by game score, it was actually his third-worst start of the year.2. Chris Sale, LHP, White Sox (2)Season Stats: 12-3, 2.61 ERA, 1.02 WHIP, 8.3 K/9, 3.68 K/BB, 6.8 IP/GS, 1 CG, 165 ERA+Last Three Starts: 2-1, 4.64 ERA, 1.36 WHIP, 6.8 K/9, 2.67 K/BB, 7.1 IP/GSBy the time Sale makes his next start, scheduled for Tuesday, he will have had three stretches of 10 days this season during which he didn't make a start. The first came in early May, when the White Sox briefly moved him into the bullpen due to concerns over some elbow pain he was experiencing. The second was around the All-Star break, when the Sox gave him a full 11 days of rest (the reason only his last three starts are tallied above). The third is right now as the team is giving him 10 days of rest between starts due to what they're describing as a dead-arm period.Despite all those gaps, he has thrown two more innings than Weaver, who missed more than three weeks due to a back injury, and after adjusting for his launching pad of a home ballpark with ERA+, Sale has been every bit as effective as Weaver in those innings with, like Verlander, superior strike zone peripherals.Second place on this list is a virtual coin-flip between Sale and Weaver at this point. If you throw out wins and losses, as I do, and consider that their adjusted ERAs are effectively identical (Weaver has a tiny right-of-the-decimal advantage, which is why he leads the league in ERA+ and Sale doesn't), the difference between the two comes down to Weaver's superior WHIP against Sale's superior strike zone peripherals. With the former being more defense-dependent, I'm going with Sale for the second spot.Incidentally, Sale, the 13th overall pick in the 2010 draft, has now thrown 218 1/3 major league innings, roughly a full-season's worth, and has these career numbers: 16-6, 225 K, 2.60 ERA, 1.06 WHIP, 9.3 K/9, 3.31 K/BB. Yes, 95 1/3 of those innings came in relief, but that's still impressive.3. Jered Weaver, RHP, Angels (3)Season Stats:14-1, 2.29 ERA, 0.95 WHIP, 6.8 K/9, 3.41 K/BB, 6.4 IP/GS, 2 CG, 1 SHO, 165 ERA+Last Four Starts: 4-0, 3.55 ERA, 1.14 WHIP, 6.8 K/9, 3.80 K/BB, 6.3 IP/GSHere, finally, is Weaver and all of his bold-text stats. His late-May back injury is the primary reason he's "way" down here in third place (I use those sarcastic quotes because this race is so close). However, his dwindling strikeout rate (down from 9.3 in 2010, a roughly career-average 7.6 last year, and just 5.9 since his return from the disabled list) is both underwhelming and, in the bigger picture, something of a red flag. The other alarming thing about Weaver's season is his home/road split. Check this out:Home: 9 GS, 8-0, 0.92 ERA, 0.65 WHIP, 7.7 K/9, 6.25 K/BB, 0.5 HR/9, 7.3 IP/GS*Road: 10 GS, 6-1, 3.55 ERA, 1.23 WHIP, 6.0 K/9, 2.21 K/BB, 1.0 HR/9, 6.3 IP/GS*Weaver hurt his back before recording an out in a home start against the Yankees on May 28. I've left that start out of the denominator in his IP/GS figure here.On the road this season, Weaver hasn't been much better than league average. At home, he has been nearly unhittable. The only home start in which he didn't pick up a win was his injury-shortened start mentioned above, and one of the other eight was an actual no-hitter.Weaver is no stranger to extreme home/road splits. Over the course of his career, his ERA at Angel Stadium has been 1.34 runs lower than his road mark, which was one reason that his decision to sign an extension with the Angels last year made so much sense. However that gap has nearly doubled this year, and while his opponent's batting average on balls in play on the road is close to his career mark (.277 this year to .279 career), his home BABIP is an absurdly low .178 (compared to .268 career).4. Jake Peavy, RHP, White Sox (4)Season Stats: 9-7, 3.04 ERA, 1.05 WHIP, 8.1 K/9, 4.32 K/BB, 7.0 IP/GS, 4 CG, 1 SHO, 142 ERA+Last Four Starts: 2-2, 3.86 ERA, 1.29 WHIP, 8.4 K/9, 5.20 K/BB, 7.0 IP/GSPeavy never really went away, but he has to be a candidate for the comeback player of the year award in the American League. Now 31, Peavy hasn't had a fully healthy season since he won the National League Cy Young in 2007 at the age of 26. In 2008, swelling in his elbow cost him a month. In 2009, he tore a muscle in his ankle and missed three months, a period during which the Padres traded him to Chicago. In 2010, he suffered a catastrophic, season-ending injury in early July when his latissimus dorsi actually detached from his pitching shoulder. He didn't return until May of the next year, then missed 16 days in June with a groin strain.This year, however, Peavy has not only been healthy, but has ranked among the league leaders in innings pitched. He has already made more starts and thrown more innings than in any season since 2008, and he is on pace to reach 30 starts and 200 frames for the first time since '07 and to throw a career-high 231 innings. That alone is remarkable given his injury woes, particularly that lat injury, but that he has also largely rediscovered his effectiveness is especially impressive. Peavy isn't striking out more than a man per inning the way he was during his Padres peak, but he has reduced his walks to, thus far, equal his career-best strikeout-to-walk ratio, and that 142 ERA+ would stand as the second-best mark of his career, behind only his 158 mark from his Cy Young season.5. Felix Hernandez, RHP, Mariners (N/A)Season Stats: 9-5, 2.79 ERA, 1.15 WHIP, 8.9 K/9, 3.73 K/BB, 7.0 IP/GS, 2 SHO, 135 ERA+Last Four Starts: 3-0, 1.44 ERA, 0.83 WHIP, 7.2 K/9, 4.17 K/BB, 7.8 IP/GS, 1 SHOHernandez had an ugly stretch of six starts from May into June in which he went 1-4 with a 6.37 ERA with just one quality start. That left him with a 4-5 record and a 3.70 ERA on the season in mid June. Prior to that he was 3-1 with a 1.89 ERA in seven starts, and since then, he has gone 5-0 with a 1.60 ERA in nine starts, two of them shutouts, and three of them (including both shutouts) seeing him strikeout 10 or more men against one or no walks. Hernandez allowed seven home runs over that lousy six-start stretch at a rate of 1.8 per nine innings. In his other 16 starts this season he has allowed just three home runs.Hernandez skipped a start at the tail end of his rough stretch due to some back pain, but that seemed to be an isolated injury, not something related to his struggles. He was clearly off his game during that stretch, but he was also monstrously unlucky, with his opponents hitting .415 on balls in play. Since then, his BABIP has been a more conventional .287, which means the dominant King Felix is the real one, but you already knew that.Off the list: C.J. Wilson (5) Promoted Stories Comments


text:
|Publication number
|Publication type
|Application number
|Publication date
|Dec 18, 1979
|Filing date
|Nov 9, 1977
|Priority date
|Nov 9, 1977
|Publication number
|Elroy M. Gladrow, Kenneth S. Wheelock
|Original Assignee
|Exxon Research & Engineering Co.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (5), Referenced by (27), Classifications (15)
|External Links: USPTO, USPTO Assignment, Espacenet
1. Field of the Invention
The present invention relates to a cracking catalyst comprising a perovskite and uses thereof in hydrocarbon cracking processes.
2. Description of the Prior Art
Catalytic cracking processes in which a hydrocarbonaceous oil is converted to lower boiling hydrocarbon products in the presence of cracking catalysts are well known.
Hydrocarbon conversion catalysts comprising a zeolite dispersed in a siliceous matrix are known, see, for example, U.S. Pat. No. 3,140,249 and U.S. Pat. No. 3,352,796. Hydrocarbon conversion catalysts comprising a physical mixture of silica and a crystalline aluminosilicate zeolite in a siliceous matrix are also known, see, for example, U.S. Pat. No. 3,558,476.
U.S. Pat. No. 3,780,126 discloses the use of manganese compounds of the perovskite structure as catalysts for the oxidative dehydrogenation of hydrocarbons.
U.S. Pat. No. 3,450,789 discloses the use of a lanthanum chromium ferrite perovskite catalyst for the oxidative dehydrogenation of hydrocarbons.
U.S. Pat. No. 3,595,809 discloses a lanthanum ferrite perovskite catalyst as hydrocarbon conversion catalyst, e.g. butene-2 to butadiene. The catalyst can be employed with a carrier.
It has now been found that improved hydrocarbon cracking results can be obtained with a cracking catalyst comprising a perovskite component.
In accordance with the invention there is provided a catalyst comprising (1) a crystalline aluminosilicate zeolite, (2) an inorganic oxide gel, and (3) an effective amount of a perovskite having at least one transition metal cation.
Furthermore, in accordance with the invention there is provided a process for the conversion of a hydrocarbonaceous oil to lower boiling hydrocarbon products which comprises: contacting said oil at catalytic cracking conditions with a catalyst comprising (1) a crystalline aluminosilicate zeolite, (2) an inorganic oxide gel, and (3) a perovskite having at least one transition metal cation. The term "transition metal" is used herein to designate elements of the Periodic Table of Elements having atomic numbers ranging from 21 through 30, from 39 through 48, from 57 through 80, and from 89 through 92.
The catalyst composition of the present invention will comprise generally a crystalline aluminosilicate zeolite, an inorganic oxide gel, a perovskite having at least one transition metal cation, and, optionally, a catalytically inert porous material.
The crystalline aluminosilicate zeolite component of the present invention may be chosen from any of the known zeolites. Examples of these zeolites include the zeolites designated by the Linde Division of Union Carbide Corporation by the letters X, Y, A, L (these zeolites are described in U.S. Pat. Nos. 2,882,244; 3,130,007; 3,882,243 and Belgian Pat. No. 575,117, respectively) as well as the naturally occurring crystalline zeolites such as faujasite, chabazite, erionite, mordenite, offretite, gmelinite, analcite, etc.
In general, the chemical formula of anhydrous crystalline aluminosilicate zeolite expressed in terms of moles may be generally represented as follows:
0.9� 0.2M2 /n O:Al2 O3 :ZSiO2
wherein M is selected from the group consisting of hydrogen, monovalent, divalent and trivalent metal cations and mixtures thereof, n is the valence of the cation and Z is a number from about 1.5 to about 12, said value being dependent upon the particular type of zeolite. The zeolites as produced or found in nature normally contain an alkali metal such as sodium, and/or potassium and/or an alkaline earth metal such as calcium and magnesium. The zeolites differ from each other in structure, composition and particularly in the ratio of silica to alumina contained in the crystal lattice structure. For use in hydrocarbon conversion processes, the higher silica to alumina ratio among isostructural zeolites are preferred because of their higher stability at elevated temperature, particularly in the presence of steam. Therefore, whereas the zeolite component of the present invention may be any of the above stated zeolites, the zeolites having silica to alumina ratios above 3 will be preferred. This includes natural and synthetic faujasite and mordenite. Typical among these zeolites is the synthetic faujasite variety wherein Z in the above formula is about 2.3 to 7, preferably 3 to 6, more preferably 4.5 to 5.5. A high silica to alumina ratio zeolite is zeolite Y. Type X zeolite wherein Z in the above formula is less than 3, e.g. 2.5, may also be used to advantage although the most preferred zeolite components for use in the catalyst of the present invention wll be those having a silica to alumina ratio greater than 3. The crystalline zeolites have uniform pore openings ranging in diameter from about 3 to about 15 Angstroms. The preferred pore size catalyst for use as zeolite component in the present invention will be zeolites having uniform pore size diameters ranging from about 6 to about 15 Angstroms. For use as hydrocarbon conversion catalyst component, it is usually necessary to reduce the alkali metal content of the crystalline aluminosilicate zeolite to a content of less than 10 weight percent, preferably less than 6 weight percent, more preferably from about 1 to about 5 weight percent since the alkali metal components are normally undesirable catalytic components for the desired hydrocarbon conversion reactions. The alkali metal content reduction may be accomplished, as is well known in the art, by exchange with one or more of the cations selected from Group IB through Group VIII metals of the Periodic Table of Elements (the Periodic Table referred to herein is given in the Handbook of Chemistry and Physics, published by Chemical Rubber Publishing Co., Cleveland, Ohio, 45th edition 1964), as well as hydrogen cation or hydrogen precursor (i.e. NH4 +) capable of conversion to hydrogen cation. The preferred cations are those selected from the group consisting of rare earth metals, calcium, magnesium and hydrogen or mixtures thereof. Desirably, the zeolite comprises from about 3 to about 20, preferably from about 5 to about 16 weight percent of the total catalyst.
Inorganic oxide gels suitable as components of the catalysts of the present invention are amorphous catalytic inorganic oxides such as silica, silica-alumina, silica-zirconia, silica-magnesia, alumina-boria, alumina-titania and the like and mixtures thereof. Preferably, the inorganic oxide gel is a silica-containing gel in which silica is present in major amounts (e.g. more than 50 weight percent), more preferably the inorganic oxide gel is an amorphous silica-alumina component such as a conventional silica-alumina cracking catalyst, several types and compositions of which are commercially available. These materials are generally prepared as a co-gel of silica and alumina or as alumina precipitated on a preformed and preaged silica hydrogel. In general, silica is present as the major component in the catalytic solids present in such gels, being present in amounts ranging between about 55 and 100 weight percent, preferably the silica will be present in amounts ranging from about 70 to about 90 weight percent. Particularly preferred are two cogels, one comprising about 75 weight percent silica and 25 weight percent alumina and the other comprising about 87 weight percent silica and 13 weight percent alumina. The inorganic oxide gel component will suitably be present in the catalyst of the present invention in an amount ranging from about 45 to about 95 weight percent, preferably from about 60 to about 90 weight percent, based on the total catalyst.
The term "perovskite" is intended herein to designate metal oxides having the ideal and non-ideal perovskite-type crystalline structure. The ideal perovskite crystalline structure is defined by the empirical formula ABO3 in which A and B are cations of two different metals and in which the A cation is coordinated to 12 oxygen atoms while the B cation occupies octahedral sites and is coordinated to 6 oxygen atoms. The ideal perovskite structure is cubic; however, few compounds have this ideal structure. The term "perovskite" structure draws its name from the mineral perovskite (CaTiO3) which was first thought to have a cubic structure that has now been determined to be orthorhombic. For example, the compound LaMnO3 has the ideal structure while some complex oxides such as La0.7 Sr0.3 MnO3, which exhibit a variety of other structures, are still classed as perovskite-type structures. A more complex description of the perovskite-type structure is found in Structural Inorganic Chemistry, A. F. Wells, Third Edition, Oxford, The Clarendon Press, 1962, pages 494-499. In general, the algebraic sum of the ionic charges of the two or more metals (cations) of the perovskite equals plus 6. Suitable perovskites as component of the catalyst of the present invention include perovskites having at least one transition metal cation, preferably perovskites having at least two transition metal cations. Preferred transition metal cations of the perovskites include lanthanum, cobalt, cerium, hafnium, chromium, zirconium and mixtures thereof. A preferred perovskite is LaCoO3. Desirably, the perovskite is added to the catalyst composition in an amount ranging from about 0.5 to about 10 weight percent, based on the total catalyst, preferably from about 1.5 to about 4 weight percent of the total catalyst. If desired, the perovskite may be dispersed in the inorganic oxide gel by conventional means, that is, by preforming the perovskite in a finely divided form, e.g., particle size of less than about 1 micron, slurrying it in an aqueous medium, and then blending with the inorganic oxide hydrogel before drying the mixture.
Optionally, a catalytically inert porous material may be present in the finished catalyst. The inert porous component may be chosen from a wide variety of solid porous catalytically inert materials. By the term "catalytically inert" is intended herein that the porous material has substantially no catalytic activity or less catalytic activity than the inorganic gel component of the catalyst. Preferably, the inert component will be an adsorptive bulk material. The term "bulk" with reference to the adsorptive inert component is intended herein to designate a material which has been preformed and placed in a physical form such that its surface area and pore structure are stabilized so that when it is added to an impure inorganic gel containing considerable amounts of residual soluble salts, the salts will not alter the surface and pore characteristics measurably nor will they promote chemical attack on the preformed porous inert material which could then undergo change. For example, the addition of "bulk" alumina will mean a material which has been formed by suitable chemical reaction, the slurry aged, filtered, dried, washed free of residual salts and then heated to reduce its content of volatile material to less than 15 weight percent. The resulting inert porous adsorbent is suitable for use as an optional component of the catalyst of the present invention. Suitable inert porous material for use in the catalyst of the present invention include alumina, titania, silica, zirconia, magnesia and mixtures thereof. Preferably, the porous inert material is a bulk alumina. Any type of alumina is suitable provided that it be porous and substantially inert. The porous inert material, when used as a component of the catalyst of the present invention, is suitably present in the finished catalyst in an amount ranging from about 15 to about 40 weight percent, preferably from about 20 to about 35 weight percent based on the total catalyst. Instead of adding the porous inert material as a separate component to the catalyst, a supported perovskite may be used wherein the porous inert material would be comprised in the support of the perovskite. Suitable supported perovskites for use in the catalyst of the present invention to provide the perovskite component as well as the inert porous component are described in U.S. Pat. application No. 676,511, filed Apr. 13, 1976, now U.S. Pat. No. 4,055,513, the teachings of which are hereby incorporated by reference.
The catalyst of the present invention may be prepared by any one of several methods. The preferred method of preparing a catalyst of the present invention is to make an inorganic oxide hydrogel and separate aqueous slurries of the zeolite, if desired, the inert porous material, and the perovskite. The slurries are blended into the hydrogel and the mixture is homogenized. The resulting homogeneous mixture is spray-dried and washed free of extraneous soluble salts using, for example, a dilute ammonium sulfate solution and water. After filtering, the resulting catalyst is calcined to reduce the volatile content to less than 12 weight percent. The amounts of each slurry used to blend with the inorganic oxide hydrogel can be varied to produce the desired final composition of the catalyst.
The catalyst of the present invention is particularly suited as a catalytic cracking catalyst for the conversion of hydrocarbonaceous feeds to lower boiling hydrocarbon products. Catalytic cracking with a catalyst of the present invention can be conducted in any conventional catalytic cracking manner. Suitable catalytic cracking conditions include a temperature from about 700 to about 1200� F., preferably from about 850 to about 1025� F. and a pressure ranging from about subatmospheric to several hundreds of atmospheres, preferably from about 0 to 150 psig, more preferably from about 0 to 50 psig.
The catalyst of the present invention can be used to convert any of the conventional hydrocarbon feeds used in catalytic cracking, that is, to crack heavy naphtha; gas oils, that is, a mixture of hydrocarbons boiling at atmospheric pressure from about 430� F. to about 1100� F., typically from about 600� to 1050� F., and residual oils including heavy crudes and residua having a high content of metal contaminants, e.g. atmospheric petroleum residua or vacuum residua. The catalytic cracking process of the present invention may be carried out in a fixed bed, a moving bed, and an ebullient bed, slurry, transferline or fluidized bed operation.
The following examples are presented to illustrate the invention.
A perovskite having the empirical formula of LaCoO3 was made as follows:
In a vessel, dissolve 176.6 grams La(NO3)3.6H2 O and 119.4 grams Co(NO3)2.6H2 O in sufficient H2 O to make 1 liter of solution.
In a second vessel, dissolve 200 grams (NH4)2 CO3 in water. Add 200cc concentrated NH4 OH (28% wt. NH3) and bring to 2 liters total volume with water.
With stirring, add the mixed lanthanum/cobalt solution to the ammoniacal carbonate solution. A bright purple flocculent precipitate was formed. The mixture was gently heated and evaporated to dryness in the presence of air over a period of several days during which time the cobalt was oxidized to the +3 state (by oxygen in the air) and the precipitated mass turned black. The dried material was then placed in a vacuum oven at 338� F. for 3 hours, and then calcined in air for 16 hours at 1730� F. X-ray analysis showed the characteristic perovskite crystal structure (about 97-99% purity) for LaCoO3 with a small amount of excess La2 O3.
The calcined material was ball milled for 16 hours and the milled product used in making cracking catalysts as described in subsequent examples.
A catalyst of the invention was made by blending a small amount of the LaCoO3 from Example 1 with calcined rare earth exchanged faujasite (type Y) and impure silica/alumina hydrogel, drying the composite and washing the dried material with (NH4)2 SO4 and water to remove residual soluble salts. The catalyst comprises 1% LaCoO3 /11% calcined rare earth exchanged faujasite (type Y)/88% silica-alumina and is designated herein "A". The calcined rare earth faujasite is made by exchanging about 67 to 95% of the sodium ions of the faujasite using a solution of mixed rare earth cations, predominantly lanthanum, cerium, praseodymium and neodymium, filtering, drying and calcining the exchanged faujasite for at least 0.5 hours at a temperature ranging from about 800� to about 1400� F. in air or with steam added. The resulting rare earth exchanged faujasite comprised 23.4 weight percent rare earth metal constituents as oxide.
A catalyst of the invention was made by blending a larger amount of LaCoO3 from Example 1 with the same calcined rare earth exchanged faujasite (type Y) as given in Example 1 and impure silica/alumina hydrogel, drying, and washing to remove extraneous soluble salts. The catalyst comprises 5% LaCoO3 /11% calcined rare earth exchanged faujasite (type Y)/84% silica-alumina and is designated "B".
A comparative catalyst was made by blending the same calcined rare earth exchanged faujasite (type Y) and impure silica/alumina hydrogel, drying and washing to remove extraneous soluble salts. The comparative catalyst comprises 11% calcined rare earth exchanged faujasite (type Y)/89% silica-alumina and is designated "C".
Catalysts "A", "B" and "C" were each calcined 16 hours at 1000� F. and then steamed at 1400� F. for 16 hours and 0 psig. The catalysts were tested in a batch fluid bed unit feeding a 500�-700� F. boiling range virgin gas oil at 950� F. over a 2 minute cycle period. Summarized data in Table I below compare the catalysts at a common conversion level of 75 wt. %.
TABLE I______________________________________CatalystAt 75% Conv.: "A" "B" "C"______________________________________W/Hr./W 13.0 12.6 12.4Carbon, % 2.2 2.4 2.2C5 /430, Wt.% 56.0 55.6 56.7C3 H6, Wt.% 4.0 4.1 3.8H2, SCF/B 55 91 24______________________________________
The data show that catalysts "A" and "B", which are catalysts in accordance with the invention, are at least as active as the reference catalyst "C". In addition, yields of coke and C5 /430� F. naphtha are about the same among all three catalysts. However, yields of C3 H6 (and presumably other light olefins) and H2 for catalysts "A" and "B" are slightly higher, indicating a small dehydrogenation property of catalysts "A" and "B" due to the added LaCoO3. These are indications that the naphtha would likely be more aromatic and have a higher octane number rating than that naphtha obtained from "C".
A catalyst, in accordance with the present invention, was made by admixing a minor amount of LaCoO3 from Example 1 with the same calcined rare earth exchanged faujasite (type Y) as given in Example 1, bulk hydrous alumina and impure silica-alumina hydrogel, spray drying the mixture and washing the product free of soluble impurities. The catalyst had a composition of 2% LaCoO3 /11% calcined rare earth exchanged faujasite (type Y)/28% bulk Al2 O3 /59% silica-alumina and is designated "D".
A comparative catalyst was made exactly like catalyst "D" except no LaCoO3 was added. This catalyst has a composition of 11% calcined rare earth exchanged faujasite (type Y)/29% Al2 O3 /60% silica-alumina and is designated "E".
Catalysts "D" and "E" were each calcined 16 hours at 1000� F. and then steamed 16 hours at 1400� F. and 0 psig. They were tested for cracking performance as described in Example 5 above. Data are summarized in Table II below at a common 75% conversion level.
TABLE II______________________________________CatalystAt 75% Conv.: "D" "E"______________________________________W/Hr./W 13.1 11.3Carbon, % 0.9 2.3C5 /430� F., Wt. % 55.2 54.6C3 H6, Wt. % 4.9 4.2H2, SCF/B 75 48______________________________________
The data show the high activity and superior product distribution for the catalyst "D", which is a catalyst in accordance with the invention, as compared to comparative catalyst "E". Note again that light olefin yield was improved and there was an increase in H2 yield which indicates the naphtha to have an improved octane number over that with comparative catalyst "E" which did not contain the perovskite.
Another comparative catalyst is a widely used commercial cracking catalyst. It is believed to contain about 16% rare earth exchanged faujasite (type Y) in a matrix of kaolin and silica-alumina gel. It is designated "F" in the next example. It contains about 3.6 weight percent rare earth metal constituents as oxide in the total catalyst.
Catalysts "D" and "F" were each steamed 16 hours at 1400� F. and 0 psig and then used as catalyst in a continuous transferline type cracking operation feeding a heavy gas oil (27.5� API gravity). The results are summarized in Table III below and the catalysts compared at the same 75 Vol. % conversion.
TABLE III______________________________________Catalyst "D" "F"______________________________________Relative Activity 1.32 1.00CO2 /CO Ratio in Regen. ∞ 0.96Flue GasCarbon, % 5.2 3.0Hydrogen, Wt. % 0.14 0.04C5 /430� F., Vol. % 62.1 64.2API Gravity 59.7 62.6RON-Clear 91.1 89.3______________________________________
The data show the high activity of the catalyst "D" of the present invention. The data show a marked increase in the octane rating of the naphtha of 1.8 research octane numbers (91.1 vs. 89.3). Also the lower API gravity of the naphtha suggests that the octane improvement may result from a higher aromatic content in the naphtha relative to reference catalyst "F". There is a higher coke and a higher H2 yield with catalyst "D"; these can be suitably used in a modern refinery using high temperature regeneration. Likewise, the higher H2 content in the light ends can be efficiently utilized. Surprisingly, it is noted that the catalyst of the invention, "D", effectively promotes the oxidation of CO to CO2 in the regenerator, thus achieving greater heat generation and recovery.
Catalysts "D" and "F" were each steamed 16 hours at 1400� F. and 0 psig and then used as the catalyst in a continuous transferline type cracking operation feeding a heavy gas oil (27.5� API gravity). The operation was conducted at 925� F. in the reactor. In Table IV, the catalysts are compared at a common space velocity of 15 W/Hr./V and a common 70 vol. % conversion.
TABLE IV______________________________________Catalyst "D" "F"______________________________________Relative Activity 1.24 1.00CO2 /CO Ratio in Regen. Flue Gas ∞ ∞Carbon, % 2.7 2.7Hydrogen, Wt. % 0.24 0.03C5 /430� F., Vol % 64.2 60.1API Gravity 57.3 56.9RON-Clear 90.5 89.7______________________________________
The data show that the catalyst "D", which is a catalyst in accordance with the present invention, is markedly superior to the standard commercial reference catalyst "F". The activity of "D" is higher; the regenerability of "D" is superior because it produces the maximum amount of heat from the coke on the spent catalyst and in so doing reduces pollutants in the regenerator flue gas that is vented to the atmosphere; more importantly, the yield of C5 /430� F. naphtha and the clear octane number of the naphtha are improved; there is no difference in carbon yields with catalyst "D" and "F". There is a noticeable increase in hydrogen yields for "D" over "F" and it is believed that this is a property of the catalyst of the present invention which leads to a higher octane number naphtha by selective dehydrogenation which does not affect naphtha yield.
Experiments were performed with perovskite promoted cracking catalysts having the following general formula: 11 weight percent calcined rare earth exchanged Y-type faujasite, 29 weight percent bulk alumina; 58 weight percent silica-alumina gel (75 weight percent silica and 25 weight percent alumina, based on the gel); and 2 weight percent of a perovskite. These catalysts were compared against a standard catalyst wherein the composition had been changed by increasing the amount of the above defined silica-alumina gel to 60 weight percent of the catalyst, that is, having the same amount of faujasite and bulk alumina and eliminating the perovskite component. Furthermore, all the perovskite-containing catalysts comprised at least one transition metal, except catalyst P, which comprised SrSnO3 as the perovskite. Tests were made in small batch units at 900� F. using as feed a 500� to 800� F. boiling range virgin gas oil cut from a West Texas Devonian crude. The results of these experiments are summarized in Table V.
TABLE V______________________________________Cata- Gas (H2) Carbonlyst Perovskite Producing Producing PercentNo. Promoter Factor Factor Conversion______________________________________G LaCoO3 4.03 0.89 82.1H La0.9 Ce0.1 CoO3 3.66 1.07 81.2I LaCO0.9 Cr0.1 O3 3.04 0.90 80.4J LaCrO3 3.10 0.94 79.7K CaHfO3 2.90 0.83 80.1L SrHfO3 2.10 1.19 72.1M BaHfO3 2.12 0.86 79.4N SrZrO3 1.94 0.78 80.3O BaZrO3 2.72 0.79 80.2P SrSnO3 1.74 0.86 77.7Q None (ref. std.) 1.80 0.93 81.6______________________________________
Referring to the above given table and interpreting the gas producing factor as an index of hydrogen production and, therefore, an increased olefin and aromatics content in the liquid product and hence a liquid product with a higher octane number, it can be seen that the incorporation of a perovskite having at least one transition metal improved product octane as indicated by slightly higher gas (hydrogen) producing factor. Incorporation of a perovskite comprising two transition metals gave a catalyst of comparable activity as the reference standard catalyst (catalyst Q) and improved octane numbers. Catalyst "P" comprised 2 weight percent SrSnO3, which has a perovskite structure but which contains no transition metal as hereinbefore defined, and hence is not a catalyst in accordance with the present invention.
|Cited Patent
|Filing date
|Publication date
|Jul 13, 1954
|Sep 30, 1958
|Socony Mobil Oil Co Inc
|Catalytic conversion of hydrocarbons with separate regeneration of the several components
|May 21, 1968
|Jun 17, 1969
|Goodrich Gulf Chem Inc
|Dehydrogenation process
|Jun 27, 1969
|Jul 27, 1971
|Gulf Research Development Co
|Lanthanum chromium ferrite catalyst
|Apr 24, 1974
|May 18, 1976
|W. R. Grace & Co.
|Stable, catalytically active and coke selective zeolite
|Apr 13, 1976
|Oct 25, 1977
|Exxon Research & Engineering Co.
|Perovskite catalysts and process for their preparation
|Citing Patent
|Filing date
|Publication date
|Feb 24, 1982
|Oct 25, 1983
|Exxon Research And Engineering Co.
|Fluid coking with the addition of perovskite-containing catalysts
|Feb 24, 1982
|Nov 1, 1983
|Exxon Research And Engineering Co.
|Process for reactivating perovskite catalysts and hydrocarbon treating processes utilizing the reactivated catalysts
|Feb 24, 1982
|Nov 29, 1983
|Exxon Research And Engineering Co.
|Process for increasing the activity of perovskite catalysts and hydrocarbon treating processes using the activated catalyst
|Aug 25, 1982
|May 1, 1984
|Exxon Research And Engineering Co.
|Process for regenerating perovskite catalysts and hydrocarbon treating processes utilizing the regenerated catalyst
|Sep 28, 1983
|May 29, 1984
|Gulf Research & Development Company
|Vanadium passivation in a hydrocarbon catalytic cracking process
|Jun 24, 1983
|Jun 5, 1984
|Exxon Research And Engineering Co.
|Process for increasing the activity of perovskite catalysts and hydrocarbon treating processes using the activated catalyst
|Mar 19, 1984
|May 28, 1985
|Gulf Research & Development Company
|Vanadium passivation in a hydrocarbon catalytic cracking process
|Dec 23, 1983
|Jun 11, 1985
|Exxon Research & Engineering Co.
|Hydrocarbon treating processes using perovskite-containing catalytic compositions
|Nov 7, 1986
|Jun 14, 1988
|Ashland Oil, Inc.
|Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion
|Jul 14, 1987
|Sep 13, 1988
|Katalistiks International, Inc.
|Hydrocarbon cracking process and catalyst for use in same
|Mar 7, 1986
|Dec 13, 1988
|Akzo N.V.
|Barium titanium oxide-containing fluidizable cracking catalyst composition
|Aug 27, 1987
|Mar 7, 1989
|Akzo N.V.
|Process for cracking metal-containing hydrocarbon feedstocks
|Feb 13, 1987
|Apr 25, 1989
|Exxon Research And Engineering Company
|Cracking catalysts containing strontium carbonate
|Jun 30, 1988
|May 1, 1990
|Mobil Oil Corp.
|Metal passivating catalyst composition for cracking hydrocarbons
|Mar 27, 1989
|Jul 31, 1990
|Exxon Research And Engineering Company
|Process using cracking calalyst containing strontium carbonate
|Mar 27, 1989
|Aug 14, 1990
|Unilever Patent Holdings B.V.
|Jun 5, 1990
|Jun 4, 1991
|Unilever Patent Holdings B.V.
|Jul 11, 2006
|Apr 20, 2010
|Exxonmobil Chemical Patents Inc.
|Catalytic conversion of oxygenates to olefins
|Aug 4, 1987
|Oct 29, 1991
|Total Engineering And Research Company
|Method for catalytically converting residual oils
|Aug 15, 1991
|Jul 18, 1995
|Akzo N.V.
|Process for cracking metal-containing hydrocarbon feedstocks
|May 10, 1994
|Mar 5, 1996
|Unilever Patent Holdings B.V.
|Aug 15, 1991
|Dec 17, 1996
|Akzo N.V.
|Barium titanium oxide-containing fluidizable cracking catalyst composition
|Dec 24, 1999
|Aug 21, 2002
|Carbon monoxide combustion supporting agent and its preparing method
|Sep 1, 1988
|Mar 7, 1990
|KATALISTIKS INTERNATIONAL, Inc.
|Hydrocarbon cracking process and catalyst for use in same
|Jun 27, 1991
|Jan 23, 1992
|Philip Pomonis
|Method of intercalation of perovskitic particles in the form of pillars into layered clays
|Jun 30, 2006
|Feb 22, 2007
|Exxonmobil Chem Patents Inc
|Catalytic conversion of oxygenates to olefins
|Dec 5, 2011
|Jun 28, 2012
|General Electric Company
|Method and reactor containing perovskite coating for cracking hydrocarbon and method for coating the reactor
|U.S. Classification
|502/65, 502/73, 502/525, 208/120.1, 208/120.25, 208/120.3, 208/120.01
|International Classification
|Cooperative Classification
|European Classification


text:
Posts with tag "liam hemsworth"
Miley Cyrus Caught Kissing a Boy in ParisPosted Dec 11th 2009 at 10:40 AM by PopEater Staff
- Filed under:
- Famous Couples -
- Movie News -
- Music News -
- Photos -
- TV News
Miley Cyrus puts on a little public display of affection in the most romantic city in the world -- Paris. Photographers snapped the tween superstar smooching a boy on the Champs-Elysee. To our eyes, it looks like her rumored boyfriend and 'Last Song' co-star Liam Hemsworth, but we're not so sure. Who do you think it is?...
Miley Cyrus Raps about Quitting TwitterPosted Oct 11th 2009 at 09:01 AM by PopEater Staff
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- Celebrity Twitter
Miley Cyrus is finally speaking out about her abrupt departure from Twitter... in rap form. The 16-year-old singer tells her fans, "I had to say goodbye, and this little rap is to tell my fans why." Watch below: ...
Miley Cyrus Quits TwitterPosted Oct 8th 2009 at 12:09 PM by Chris Jancelewicz
- Filed under:
- Celebrity Twitter
Remember when you were a teenager, and you would throw wild tantrums at the most inconsequential things? You'd pack your bags and threaten your mother/father that you were leaving home and you'd never return? Well, it seems like Miley Cyrus has pulled a teenage tantrum of her own - but instead of leaving her family behind, she's closed her Twitter account. What will we do without all the pictures...
Crikey! Aussie Teen Blames Miley Cyrus for Her BreakupPosted Sep 1st 2009 at 07:27 AM by PopEater Staff
- Filed under:
- Famous Couples -
- Movie News -
- Music News -
- Splitsville -
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- Celebrity Scandal
Miley Cyrus has denied she's dating her 'Last Song' co-star Liam Hemsworth, but that hasn't stopped his ex-girlfriend from blaming the 'Hannah Montana' star for breaking them up. "He was my boyfriend and my best friend," Laura Griffin told Woman's Day, an Australian magazine. "There is no other reason why we would have broken up."...
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