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What's the beauty of being Villas-Boas? It's always someone else's fault
Andre Villas-Boas used to watch the game by crouching down on his haunches near the touchline. And then he stopped doing it. Isn't that strange? People were making fun of him, but even so. If he thought it was the way to get the greatest insight, why would he change?
Unless it was an affectation. A quirk, a gimmick to make him look brighter than he is. After all, there have been some fairly successful coaches through the last century or so, and not one of them chose to observe the action from the perspective of a dachshund. So maybe they were the smart ones.
Then, when Tottenham Hotspur goalkeeper Hugo Lloris suffered a head injury against Everton, Villas-Boas knew best again. He kept him on and then called all those who took issue with that decision – including some fairly serious medical professionals – ignorant.
Miserable: Andre Villas-Boas watched his Tottenham side as they were hammered 6-0 at Manchester City
A new stance: Villas-Boas would crouch to watch matches at Chelsea, but has a different approach now
Tough job: Villas-Boas must recover quickly if his Tottenham side are to reach the Champions League
Daniel Sturridge (below) says he has no regrets about playing for England against Germany, even though it cost him a starting place in the Merseyside derby.
Big mistake. One of the reasons many Liverpool fans never took to Michael Owen was the belief that he put his international career first.
They treat their football team like a republic up there. Any player who expresses a desire to represent England is suspected of disloyalty.
Meanwhile, Luis Suarez is free to return to Uruguay and slag off the club. Strange.
In the next game, against Newcastle United, Lloris was absent. Medical advice, apparently. So maybe those doctors weren't so dumb after all; or maybe Villas-Boas isn't quite as sharp as he thinks he is.
He certainly didn't look it when that sixth Manchester City goal went in on Sunday. He appeared stunned, much as he did when West Ham United scored three at White Hart Lane without a striker.
He said the players should be ashamed. That is the marvellous thing about being AVB — there is always someone around to carry the can.
So how are Chelsea's old guard going to take the fall for this one? It is surely only a matter of time before John Terry and Frank Lampard are fingered for the mess at Tottenham this season.
It was, after all, the senior players who undermined Villas-Boas at Chelsea. Not his pig-headed high line defence, utterly unsuited to the personnel at his disposal. Not his determination to change fast when evolution, not revolution, was needed. As ever, events and foes conspired to obstruct his genius.
Players, other managers, pesky head trauma experts, Villas-Boas is beleaguered by so many random factors. The game against Newcastle brought a once-in-a-lifetime display from goalkeeper Tim Krul; the defeat by West Ham saw a tactical masterclass from Sam Allardyce (although one cannot help noticing that his false striker system has landed two points from 15 since the win away at Tottenham on October 6).
Villas-Boas had every right to be critical after the defeat at Manchester City. It was a limp and inadequate display. But these are his players, his solution to the loss of Gareth Bale.
Tottenham had sold Elvis Presley and bought the Beatles was the claim. Except this lot look more like the fab four pastiche group the Rutles — if Nasty, Stig, Dirk and Barry had all decided to swap instruments five minutes before the gig.
Big loss: Gareth Bale (right) left for Real Madrid this summer and Spurs reacted by signing seven players and splashing out £107m. Like selling Elvis Presley (left) and buying The Beatles?
Fair trade: Tottenham's summer spree had been likened to swapping Elvis for The Beatles. Here, band members Paul McCartney, George Harrison, Ringo Starr and John Lennon pose for a group shot
Underwhelming: From left to right, Spurs' seven summer signings Paulinho, Christian Eriksen, Roberto Soldado, Nacer Chadli, Etienne Capoue, Vlad Chiriches and Erik Lamela line up ahead of this season
More from Martin Samuel - Sport for the Daily Mail...
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- No right time for Paul Scholes to lead Oldham Athletic in the modern game 12/10/17
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- Mark Sampson's sacking was an abuse scandal... and heads must roll at the FA 21/09/17
- One day we will tire of this circus... the draw between Gennady Golovkin and Canelo Alvarez is at best a farce and at worst a travesty 17/09/17
- There IS a way for kids to get a game in the Premier League, but not at an elite club... Aaron Mooy is a prime example 14/09/17
Yet if the team were poor against City, Villas-Boas made some equally flawed judgment calls from the bench. Jan Vertonghen, arguably the finest centre half at the club, struggled at left back.
Andros Townsend did not start, following a game and a 33-minute substitute appearance for England at Wembley, while Paulinho did despite flying to Miami to play 90 minutes for Brazil against Honduras before heading up to Toronto for another 84-minute stint against Chile.
Erik Lamela began in Townsend's position — he usually plays on the right — and was utterly insipid.
Tottenham spent £107million on players this summer and have gone backwards. The players were meant to have let him down at Chelsea, too. And then the same team went on to win the Champions League and FA Cup that season, after he left.
The popular myth is that the group started performing only after his departure — as if they could have been champions of Europe at any time, but just didn't fancy it previously.
More evidence-based is the theory that Roberto Di Matteo got them playing in a way that Villas-Boas could not and this, along with some heroic defending and good fortune, saved the day.
Roman Abramovich's notorious impatience then saved Villas-Boas because he was seen as the hapless victim of a crackpot club, sacked prematurely as a result of player power.
Yet what has changed? Villas-Boas remains impossibly stubborn — as he proved with his misguided outburst over Lloris — and his teams play his way, regardless of their needs.
Tottenham did not lose to Newcastle because Krul had the game of his life. That would only have produced a draw. Tottenham lost because Villas-Boas played a high line defence, as always, but with Brad Friedel in goal.
Under normal circumstances, Lloris plays almost as a sweeper, quickly off his line if the opposition get in behind the back four. Friedel, at 42, hasn't the same speed. So Tottenham should have sat a little deeper. They didn't, Loic Remy took advantage, and Friedel couldn't get out fast enough.
Krul then played magnificently, but goalkeepers will do that from time to time. It isn't misfortune.
At City on Sunday, Tottenham were behind after 14 seconds due to a poor clearance from Lloris, and no manager can do anything about that.
Yet, from there, it was clear that once again Villas-Boas was pleasing himself with his game plan. Michael Dawson isn't a high line defender, either, and Younes Kaboul might have wished for a little more security after 15 months without a league game.
Humiliation: Jesus Navas wheels away after netting his second against Spurs and Manchester City's sixth goal
Outfoxed: City, led by Sergio Aguero (centre), were much too strong for an abject Tottenham side
Powerless: Villas-Boas could only watch as Navas netted at the Etihad after just 14 seconds
Damning: The Etihad scoreboard tells the story as the match in Manchester draws to a close
Villas-Boas also prefers a lone striker, despite the fact that Tottenham have scored six goals from open play in 12 league matches this season. Their numbers are horrendous for a club with elite ambitions. Tottenham's goal difference is inferior to every team in the top 14 bar Hull City and they have scored as many goals as West Ham, who have played most of the season without a striker.
Going into Sunday's fixture with Manchester United, Tottenham will have scored nine in 12. They now cannot reach double figures before December. At this rate, Tottenham's goals aggregate for the season will be 28. Last May, the three teams relegated from the Premier League scored 30 goals, 43 and 60.
Impregnable: Tim Krul kept Tottenham at bay when Newcastle nicked a victory earlier this month
In the goals: Ravel Morrison and West Ham put Spurs to the sword at White Hart Lane
It's a knockout: Villas-Boas was belligerent with his opinions on Hugo Lloris' head injury
Tottenham are not about to get relegated, obviously. This may be a blip, quickly corrected. Defeat Manchester United in five days' time and recent struggles will be forgotten. Yet the flip side of that argument comes with the fear that one man made up for a heap of weakness last season — and he now plays at Real Madrid.
Take Bale away from Tottenham in 2012-13 and it is unlikely the team would have made Europe. He wasn't just influential, he was essential. His goals turned defeats into wins against Newcastle and West Ham, draws into wins against Manchester United, Southampton, Liverpool, West Bromwich Albion, Arsenal, Swansea City, Southampton again and Sunderland and defeats into draws against Norwich City and Wigan Athletic.
Purple patch: In his first season at White Hart Lane, Villas-Boas watched Bale exceed expectations
Not good enough: Erik Lamela (left) had no impact on Sunday and Roberto Soldado didn't muster a shot on goal
Clearly, had he not been selected, a team-mate would have played, and could have been important, too. Yet would his goals have compared?
Put it like this: Clint Dempsey's goals were worth seven points to Tottenham last season, Aaron Lennon's were worth six; Bale was good for 24. He hit Cristiano Ronaldo form, which is why Madrid wanted to make them a partnership.
So while it was a huge blow for Villas-Boas to lose the Welshman, it was a greater fillip to inherit him in his first season. It made the manager look very smart, very quick. Now he must survive on his wits alone.
His signings have been vast in number but not in impact. There was always a possibility it could go this way. Franco Baldini, the director of football, plundered the market in Europe and South America having seen what was about in England first-hand during his time with Fabio Capello, but he underestimated the unique demands of the Premier League.
The majority of imported players take time to adjust. Instant successes such as Luis Suarez and Sergio Aguero are rare. It is forgotten now, but even men like Didier Drogba and Michael Essien endured unconvincing first seasons; that is why Chelsea bought Michael Ballack and Andriy Shevchenko, who became redundant once Drogba found his feet second time out.
Tottenham may be flying in 12 months' time — but this first campaign with a hastily assembled squad was going to be a challenge. Behind the scenes the shifting of blame has already begun, with Villas-Boas distancing himself from some of the signings.
Boardroom: Villas-Boas began distancing himself from some of the signings that Franco Baldini (left) recruited
Unimpressed: Chairman Daniel Levy at the Etihad
The problem for the manager is that little has improved under his tenure. Are Tottenham higher up the table? No. Is the football more exciting? No. Are they nearer rivals Arsenal? No.
The high water mark of the Premier League era remains the years when the football played by Harry Redknapp's team was the most exciting in England and the club reached the last eight of the Champions League.
Villas-Boas said he hoped his players would bounce back via Thursday's Europa League tie against Tromso — but just saying the name of the tournament is in its own way an admission of failure, considering what went before. Tottenham were not meant to be back in the Europa League again.
One wonders, in his final season, what Redknapp might have achieved with even half the investment lavished on Villas-Boas, rather than a final January transfer window signing of Louis Saha as Tottenham's title challenge faded.
What we are seeing here is another case of Ex-Chelsea Manager Syndrome. These guys are often impossible to judge because their time at Stamford Bridge is so fleeting. Nobody could work out Avram Grant until he sleepwalked over the precipice at West Ham, and the evidence of Di Matteo's career only confuses.
Peaking: Gareth Bale and Tottenham reached the last eight of the Champions League under Harry Redknapp
Raising the bar: Redknapp took an exciting Spurs team into the Champions League
Villas-Boas looked a bright young manager at Porto and left Chelsea not even halfway through a project. This season we will discover how smart he really is.
It is very generous of Tottenham owner Joe Lewis to finance such a fascinating experiment. He must be delighted.
Crusade for women's sport is just hypocrisy
Helen Grant was asked five relatively straightforward questions about sport, and got each one wrong. In her defence, she is not the first Sports Minister to be exposed as a bluffer in this way — and she won't be the last.
Richard Caborn was equally ignorant about sport, yet is still hanging around committees six years after he stepped down from his ministerial role.
One of the gaps in Grant's knowledge, however, was enlightening: she couldn't name the Wimbledon women's champion.
VIDEO: Scroll down to watch Helen Grant's blunder
Straightforward: Helen Grant didn't answer one of five simple sports questions correctly
It was only last month that Grant called for a woman to be added to Greg Dyke's Football Association task force. She didn't specify which woman. She didn't identify an individual who would bring insight and innovation to the process. Any woman would do, it seemed. Maybe they could nab one who happens to be passing.
It now transpires that Grant is so attuned to the plight of women in sport that she cannot even place Marion Bartoli, a fairly memorable champion, considering Maria Miller, Secretary of State for Culture, Media and Sport — and effectively Grant's boss — as good as angled for John Inverdale to be sacked from the BBC's Wimbledon coverage for referring to her in a disparaging manner.
Grant didn't know who won the FA Cup either, but that is simple ignorance. Flunking on Bartoli sums up the hypocrisy around this issue.
Remember me? Marion Bartoli won Wimbledon at SW19 in the summer
Regrettable: John Inverdale referred to Bartoli in a disparaging manner after the tournament
To push for greater representation and publicity for female athletes is a very populist line — but it is plain Grant does not have the genuine interest to back up her views. Women's sport would be impossible to resist if only women supported it. Instead, the Sports Minister talks a grand game, while privately paying as little interest as any miserable sexist on a sofa. Her interest wanes beyond that first sound-bite, and her own career.
If there was a certain bet in life it was Mario Balotelli from the penalty spot. However madcap his antics, from 12 yards out he was coolness personified.
Going into this season he had never missed. Now he has, twice. His club, AC Milan, are 13th and falling. Funny thing, pressure. It comes for them all in the end: even those without a mind to crush.
Human after all: Mario Balotelli's previously unblemished penalty record has fallen by the wayside this season
Gotcha: Genoa's goalkeeper Mattia Perin celebrates after keeping Balotelli's spot-kick out
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Good Grief what has gotten into me lately? I've allowed some bad habits to sneak back in my life. Eating at night. :-( .
Monday i just gave in all together, Tuesday i did an awesome job, yesterday was great up until about 8pm....thats when all hell breaks loose.....
I was watching survivor with my kids and i wanted something sweet. So, instead of chewing gum like i would normally do, I got up with every intention of eating small snack. I start digging around in the cabinet and couldn't find anything. (Earlier that day i told my DD to throw out the leftover cake and since they didn't like the animal cookies i told her to give them to the dogs...and THANK GOODNESS or that would have been in my mouth at that moment!) Back to the story, so i was digging around and thought "oh, peanut butter!" (this is when it turns ugly) So instead of weighing the pb, i scoop out the high calorie dense gooey goodness in huge spoonfuls on a slice of whole wheat bread and literally shoved it into my mouth! WTH? Why did i do that? I measured everything yesterday (as i always do) and I don't measure this pb sandwich? Well the damage didn't end there...i also when back for another sandwich, this time a single fish fillet (gordons) with a small amount of tatar sauce on hamburger buns. I found a small amount of cocoa crispies left in the cabinet and munched on them while watching tv.
I will call it what it was; a binge. Smaller than usual though, binges in the old days were close to 3000 calories or more. Yesterdays was less than a third of that..
I can't help but wonder what made me cave in monday and yesterday? I pondered this while laying in bed this morning.
Im kinda stressed right now about finding a job. Frustrated because i've had to turn down jobs that didn't coincide with my families schedule. Im sure the excuses could go on forever...but thats just what they are; excuses. I came to the conclusion that i've simply allowed a nasty habit to over-power me! Those late night munchies are hard to break...but ive done it before and by george i will do it again! Thats the thing with me...my little inner light might go out for just a moment, but a torch comes back in its place! I don't give up on me. (I hope I didn't sound like a horses ass just now :o)
Oh and i got rid of that annoying daily reminder of how many calories i need to eat everyday. I already write down everything I eat and sometimes i don't exactly stick to a certain amount, as long as I keep it at a range between 1350-1800 I should be good! Just gotta keep those urges under control.
Yay, I finished my workout! I had ZERO motivation today for some reason. I did a 30 minute power walk then 30mins of Legs & Glutes (a heavy weight lifting DVD by Cathe) then the abb section on another of Cathe's workouts...KPC.


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First, there was a group date with 10 guys. They had a dodgeball tournament after being shown the ropes by a professional dodgeball team. Yes, I wrote that sentence, and yes it's true. There really are professional dodgeball players. Who knew??
At the cocktail party, Brad tells Des about his son and baby mama drama. I appreciate that this information waited until the third week and wasn't thrown on her immediately upon his arrival... Points for Brad for handling this information well. Brooks makes his triumphant return, and they make out. She's clearly digging him, even in his dodgeball get-up. Chris gets the rose after a very slightly-aired chat on the roof. Brooks shoots eye-daggers at him, but he doesn't notice as they walk to a private concert by Kate Earl (who???).
The one on one date goes to Kasey (ps-- when will people stop spelling their boy Casey names with a K??). But first, we have to deal with Brian. Brian apparently has a girlfriend, and she is PISSED (not to mention, a real winner...). They fight for a while, and I really don't believe either of their stories. Des sends him packing, and he's escorted out by some big dude.
Next up is Group Date #2! The five guys going on today's date are all excited about the Bentley or the limo that's going to take them to their destination only to walk out and find... a stagecoach and horses.
Sar!). James whines himself into getting the rose (she's such a sucker for a sad guy).
No cocktail party this evening, but a pool party instead! But before she can even walk in the door, Ben tries to grab her and get some time without any of the guys knowing. They make out in the driveway, and of course, everyone sees and just hates him even more.
I'm looking forward to next week's Mr. America competition! What did you guys think??


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Blasterball 3 unlock code working keys
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Chuzzle Deluxe Review. Play Games Online at WildTangent Games! Play 1,000's of Casual blasterball 3 unlock code Games, Enthusiast Games and Family Games! Try, Buy, or Rent! Neoseeker has over 81322 cheats and tips spread across more than 6000 titles. Try, Buy, or Rent! blasterball 3 unlock code New online games are added every day, so that any gamer will find a game to your taste! New online games are added every day, so that any gamer will find a game to your taste! Chuzzle Deluxe is a fun-filled match-three puzzle game that brings something for everyone. Play 1,000's of Casual Games, Enthusiast Games and Family Games! Play Games Online at WildTangent Games! The game is simple enough to learn and play, but. This Is My First Video So Sorry For Any Mistakes). blasterball 3 unlock code You may also be interested in our FAQs, Guides, and Walkthroughs Download Chuzzle today, or play this and 2400 other top games online for free at GameHouse Play online puzzle games for free on PlayAllFreeOnlineGames.com, the largest source of free Puzzle games, girl games. In any game, you can play online for free, without registration blasterball 3 unlock code Should I remove WildTangent Games App (HP Games) by WildTangent? In any game, you can play online for free, without registration. Play free games for Boys, Girls & Kids. WildTangent powers game services for several PC manufacturers including Hewlett-Packard branded …. Find WildTangent software downloads at CNET Download.com, the most comprehensive source for safe, trusted, and spyware-free downloads on the Web. Jul 14, 2013 · Please Change Quality, As it May Be Blurry Please Rate, Comment, Subscribe (P.S. blasterball 3 unlock code


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ugosh University
ugosh University
Piasecki M.,ugosh University |
Myronchuk G.,Lesya Ukrainka Eastern European National University |
Lakshminarayana G.,Los Alamos National Laboratory |
Reshak A.H.,University of South Bohemia |
And 4 more authors.
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy | Year: 2012
Complex spectral studies of near-band gap and photoconductive spectra for novel Ag 2In 2SiS 6 and Ag 2In 2GeS 6 single crystals are presented. The spectral dependences of photoconductivity clearly show an existence of spectral maxima within the 450 nm-540 nm and 780 nm-920 nm. The fundamental absorption edge is analyzed by Urbach rule. The origin of the spectral photoconductivity spectral maxima is discussed. Temperature dependences of the spectra were done. The obtained spectral features allow to propose the titled crystals as photosensors. An analysis of the absorption and photoconductivity spectra is given within a framework of oversimplified spectroscopic model of complex chalcogenide crystals. © 2012 Elsevier B.V. All rights reserved.
Parasyuk O.V.,Lesya Ukrainka Eastern European National University |
Myronchuk G.L.,Lesya Ukrainka Eastern European National University |
Fedorchuk A.O.,Lesya Ukrainka Eastern European National University |
El-Naggar A.M.,Ain Shams University |
And 5 more authors.
Crystals | Year: 2016
We have discovered a substantial enhancement of the piezoelectric coefficients (from 10 to 78 pm/V) in the chalcogenide Ag2Ga2SiS6 single crystals. The piezoelectric studies were done under the influence of a CO2 laser (wavelength 10.6 µm, time duration 200 ns, lasers with power densities varying up to 700 MW/cm2). Contrary to the earlier studies where the photoinduced piezoelectricity was done under the influence of the near IR lasers, the effect is higher by at least one order, which is a consequence of the phonon anharmonic contributions and photopolarizations. Such a discovery allows one to build infrared piezotronic devices, which may be used for the production of the IR laser tunable optoelectronic triggers and memories. This is additionally confirmed by the fact that analogous photoillumination by the near IR laser (Nd:YAG (1064 nm) and Er:glass laser (1540 nm)) gives the obtained values of the effective piezoelectricity at of least one order less. The effect is completely reversible with a relaxation time up to several milliseconds. In order to clarify the role of free carriers, additional studies of photoelectrical spectra were done. © 2016 by the authors; licensee MDPI, Basel, Switzerland.
Krishnakumar V.,Periyar University |
Nagalakshmi R.,National Institute of Technology Tiruchirappalli |
Manohar S.,Periyar University |
Piasecki M.,ugosh University |
And 2 more authors.
Physica B: Condensed Matter | Year: 2010
Good quality single crystals of a complex between urea and resorcinol (UR-C 6H 5O 2 -:(NH 2)CO(NH 3) +) in the ratio (1:1) have been grown by low temperature solution growth technique using acetone and a mixture of acetone and water (1:1). The solubility studies have been carried out in both the solvents at various temperatures. The X-ray diffraction studies show that the complex crystallized in orthorhombic space group P2 12 12 1. The linear electro optical, piezooptical and second harmonic generation measurements were performed. The results obtained in these studies were discussed in detail. The optical transparency window observed in the visible and near IR regions recommends the crystal for nonlinear optical applications. Dependence of the effective second order optical susceptibility on time of simultaneously applied dc-electric field and UV-treatment were performed and discussed. © 2009 Elsevier B.V. All rights reserved.
Douayar A.,Mohammed V University |
Belayachi A.,Mohammed V University |
Abd-Lefdil M.,Mohammed V University |
Nouneh K.,Innovation and Research Foundation |
And 5 more authors.
Journal of Alloys and Compounds | Year: 2013
The photoinduced linear electrooptical effect was measured using the bicolor laser light between the fundamental 10 ns Nd:YAG laser beam and its green doubled frequency. The optimal ratio of intensities between these two beams was equal to 5:1. As a probing beam, it was used cw 12 mW He-Ne laser beam and Senarmont method was used for detection of the birefringence with accuracy of 10-6. The studies were done on zinc oxide nanocrystalline films doped by Tm3+ ions. Maximal linear EO changes were obtained at minimal Tm3+ content equal to about 0.1% in weight units. With the further increase of the photoinducing beam the observed EO effect enhancement is not so evident and for the 0.5% of Tm3+ the effect disappears at all times during the illumination. The obtained results show that a principal role of localization of the rare earths in the observed effects may be a consequence of formation of the charge density non-centrosymmetry which is crucially dependent on the Tm3+ content in ZnO films. © 2012 Elsevier B.V. All rights reserved.


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Starts June 26th - August 31st
ages 7- 16 Monday thru Thursday 9:00 - 3:00 p.m.
$188 per week, light lunch served
8:00 a.m. Early morning drop off for additional $10 per day
Fabric and Supplies included in the fee.
There are no refunds.
Required: Sketchbook, Pencil, Snacks
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Traffic Ultimatum By George Brown – plus some free Stuff!
www.trafficultimatumreport.com – Traffic Ultimatum – Created by George Brown Google Sniper fame, the biggest traffic generation system that has ever hit the world! Watch as super affiliate, Gary Gregory, breaks it and gives free course backlinking and traffic generation techniques, plus a super-secret strategy that you do not want to miss! To know more, click on the link below! – Http Video Rating: 3/5


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This workbook by Leonie Dawson is changing my life – section after section and page after page. If you haven't ever heard of Leonie Dawson, you are missing out, my friend. She's a woman who really walks her talk. She's managed to create a half million dollar-a-year company by working a few hours a day, spending loads of time playing with her family + making art + living a really full life.
All posts for the month January, 2015
Leonie Dawson's 2015 Create Your Shining Year Life + Biz Workbook Review
Posted by Elizabeth on January 30, 2015
Recipe ~ Seasoned Pretzels
I absolutely LOVE pig out days at work. Everyone always brings in something yummy and our last get together was no different. I completely ran out of time to make something so I won't be partaking, but I did sneak some of these amazing pretzels that my co-worker made. She was gracious enough to share her recipe with me 🙂 I would have made my roll-ups if I would have had more time!
Posted by Elizabeth on January 29, 2015
Poll ~ Post or Not to Post
As we get closer and closer to the day we leave for Panama, I'm struggling with if and when I should update my blog while we are gone. The more I think about it, I would like to update it daily, but I'm not sure how realistic that is. It would really help me keep my thoughts in order as we will be seeing and doing so much. It might be a nice way to end the day…up on the pool deck with a glass of wine sharing my day with you 🙂 That way the posts won't get too long and I'll be able to document the day better. If I wait until I get back, I will probably have to write multiple days' worth of posts and might forget half of what we did by then! Well, probably not because I'm going to be photographing like a mad woman!!!
Posted by Elizabeth on January 28, 2015
Treats for Your Pups
Our black lab, Aayla, is a huge part of our life. She's 6 years old and 100+ pounds of love 🙂 We don't have any children, so she fills a big part of that void. She's spoiled rotten, I mean loved, and has more toys and beds than any dog really needs. I've always wanted to make treats for her from scratch, so the other weekend I decided to try two recipes I had found.
Posted by Elizabeth on January 26, 2015
2014 Photo Shoots – A Look Back
As we get started with a new year, I like to reflect back on my photo shoots from the last year to see how I've grown from year to year. I have some clients that have been coming to me for years and I also have brand new clients. Every January I get excited to see what new clients I'll get that year and look forward to working with my current clients.
Posted by Elizabeth on January 21, 2015
Recipe ~ Roasted Brussels Sprouts with Garlic Aioli
Can I just say that Pinterest might just make a cook out of me after all?! I've been finding so many recipes I want to try. When I came across this recipe from Cakes Cottage for roasted Brussels sprouts ,I knew this was something I needed to make right away. Lucky for me we already had fresh Brussels sprouts on hand!
Posted by Elizabeth on January 19, 2015
Adam & Sam ~ Engagement
I have been photographing my stepbrother and his now fiancé for many years. We always enjoy just walking around my dad's land and shooting on the fly. I was honored to be able to do their engagement session this past fall. Here are some favorites from their session. Better late than never!!
Posted by Elizabeth on January 14, 2015
Recipe ~ Chicken Soup
'Tis the season for colds which means it's also homemade chicken soup season 🙂 My husband makes the BEST chicken soup EVER! I always say it's because it's made with love, but I'll let you in on a little secret; he HATES making it lol. He says it's made out of spite . . . not spice. Since I'm battling my first cold of the new year, I figure this would be the perfect time for me to make it for myself.
Posted by Elizabeth on January 9, 2015
Soaring Eagles
On my way to work the other morning, a beautiful eagle flew over the road. There is something so magical about eagles. They are so powerful, yet their beauty is mesmerizing. Last year around this time we had a family of eagles that were nesting near my work. I may or may not have RUN to the doors each time I saw them take flight. Even thought I could hardly feel my fingers once I was back inside, it was worth every second. I took a look back at all the images I captured and wanted to share some of my favorites with you. These were taken over a few different days.
I'm hoping I'll get another chance to photograph some again this year. I hope it warms up a bit first, though! With temperatures sitting at -2 and wind chills at -20, I'm not in a hurry to repeat last years painful shoot. Yes, if they come around I WILL run out in the middle of whatever I'm doing to get another chance at a beautiful photo 🙂
Hope you enjoyed a different side to my photography. I look forward to sharing more of my nature inspired photos with you 🙂
Until next time.
Much love,
Posted by Elizabeth on January 7, 2015
December Thrift Store Finds
It's that time again to share my thrift store finds for the month.
Posted by Elizabeth on January 7, 2015


text:
|Publication number
|Publication type
|Application number
|Publication date
|Oct 9, 1990
|Filing date
|Feb 15, 1990
|Priority date
|Jun 23, 1988
|Fee status
|Also published as
|Publication number
|Catherine S. H. Chen, Margaret M. S. Wu
|Original Assignee
|Mobil Oil Corporation
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (10), Referenced by (35), Classifications (21), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a continuation in part of U.S. Pat. application Ser. No. 07/210,436, filed June 23, 1988, incorporated herein by reference.
This invention relates to a process for the production of hydrocarbon lubricants having high viscosity index (VI) from near linear alpha olefins derived from inexpensive lower alkenes by employing the intermediate production of near linear internal olefin oligomers. More particularly, the invention relates to the discovery that a complex mixture of higher alpha olefins produced by metathesis of slightly branched internal higher olefins can be oligomerized to provide lubricants that possess superior properties relating to pour point and viscosity index.
In the processes known in the art for catalytic conversion of olefins to heavier hydrocarbons by catalytic oligomerization using a medium pore shape selective acid crystalline zeolite, such as ZSM-5 type catalyst, process conditions can be varied to favor the formation of hydrocarbons of varying molecular weight. At moderate temperature and relatively high pressure, the conversion conditions favor C10 + aliphatic product. Lower olefinic feedstocks containing C2 -C8 alkenes may be converted; however, the distillate mode conditions do not convert a major fraction of ethylene. A typical reactive feedstock consists essentially of C3 -C6 mono-olefins, with varying amounts of nonreactive paraffins and the like being acceptable components.
U. S. Pat. Nos. 4,520,221, 4,568,786 and 4,658,079 to C. S. H. Chen et al., incorporated herein by reference in their entirety, disclose further advances in zeolite catalyzed olefin oligomerization. These patents disclose processes for the oligomerization of light, or lower, olefins using zeolite catalyst such as ZSM-5. The oligomers so produced are near linear in structure and contain internal olefin unsaturation. These unique olefinic oligomers are produced by surface deactivation of the ZSM-5 type catalyst by pretreatment with a surface-neutralizing base. The processes of Chen et al. provide a particularly useful means to prepare higher olefinic hydrocarbons from inexpensive lower olefins, particularly propylene.
Efforts to improve upon the performance of natural mineral oil based lubricants by the synthesis of oligomeric hydrocarbon fluids have led to the relatively recent market introduction of a number of superior polyalpha-olefin synthetic lubricants, primarily based on the oligomerization of alpha-olefins or 1-alkenes. Well known structure/property relationships have pointed the way to 1-alkenes as a fruitful field of investigation for the synthesis of oligomers with the structure thought to be needed to confer improved lubricant properties thereon. Building on that resource, oligomers of 1-alkenes from C6 to C20 have been prepared with commercially useful synthetic lubricants from 1-decene oligomerization yielding a distinctly superior lubricant product via either cationic or coordination catalyzed polymerization. Of notable importance is the inventions described in U.S. Pat. Nos. 4,827,064 and 4,827,073 to M. Wu, incorporated herein by reference, where superior hydrocarbon lubricants are prepared having low methyl to methylene branch ratio by oligomerization of alpha olefins using reduced valence state Group VIB metal oxide catalyst on porous support.
As a feedstock to prepare lubricants by cationic, coordination or Ziegler catalysis the olefinic oligomers provided by the aforementioned Chen process are illsuited for two reasons. First, they comprise predominately internal olefins where alpha olefins are required. Secondly, the olefinic oligomers are slightly branched. The prior art for the preparation of synthetic lubricants teaches the oligomerization of linear alpha olefins to produce lube oligomers where little or no branching is preferred. However, it is known that olefin metathesis carried out between lower alpha olefins such as ethylene and higher internal olefins produces higher alpha olefins. Olefin metathesis is described in Olefin Metathesis by K.J.Ivin, published by Academic Press, wherein Chapter 5 describes olefin metathesis with ethene. The olefin metathesis reaction applied to the olefinic oligomers of Chen et al. could provide a route to alpha olefins suitable for the production of synthetic lubricants.
It is an object of the present invention to provide a process for the production of high VI synthetic lubricants from slightly branched higher internal olefins.
It is another object of the present invention to provide a process for the production of slightly branched and linear alpha olefins suitable for the preparation of lubricant range oligomers.
A further object of the present invention is to provide a process for the oligomerization of slightly and linear alpha olefins using reduced valence state Group VIB metal oxide catalyst on porous support.
The discovery has been made that the near linear higher olefinic hydrocarbons produced by the oligomerization of lower olefins using surface deactivated zeolite catalyst can be converted to a mixture comprising slightly branched and linear higher alpha olefins. These alpha olefins are oligomerized to lubricant grade hydrocarbons in contact with cationic, Ziegler or coordination catalyst. Oligomerization of the aforementioned alpha olefins using reduced valence state Group VIB metal oxide catalyst on porous support provides a hydrocarbon lubricant with a viscosity index of greater than 130°.
More particularly, a process has been discovered for the production of hydrocarbon lubricant fluids having high viscosity index which comprises contacting a mixture of slightly branched and linear higher alpha olefins under oligomerization conditions with a reduced valence state Group VIB metal catalyst on porous support and separating the higher alpha olefins oligomerization reaction product to provide a lubricant having a viscosity index greater than 130 and a pour point less than -15° C. The higher alpha olefins oligomerization feedstock comprises the olefin metathesis reaction product of slightly branched higher olefinic hydrocarbons with lower olefinic hydrocarbons in contact with metathesis catalyst. The slightly branched higher olefinic hydrocarbons employed as feedstock in the metathesis reaction comprise the oligomerization product of lower alkene oligomerized in contact with surface deactivated, acidic, medium pore, shape selective metallosilicate catalyst under oligomerization conditions.
The invention also includes an integrated process for the production of liquid hydrocarbon fluid which comprises the following steps:
(a) contacting a feedstock comprising lower olefin such as propylene with surface deactivated, acidic, medium pore, shape selective metallosilicate catalyst, typically ZSM-5 or ZSM-23 under oligomerization conditions to provide a product comprising a mixture of slightly branched higher olefins;
(b) reacting this mixture with ethylene in contact with olefin metathesis catalyst, preferably rhenium oxide on aluminum oxide support with tetramethyl tin as co-catalyst, under metathesis conditions and separating a metathesis product comprising slightly branched and linear higher alpha olefins;
(c) oligomerizing the metathesis product in contact with a CO reduced chromium oxide metal catalyst on porous silica support to provide said lubricant having a viscosity above about 2 cS at 100° C. and VI above about 130°.
The Figure presents a block flow diagram of a particular embodiment of the present invention.
The invention comprises the steps of lower olefin oligomerization to near linear higher olefins; metathesis of these olefins to alpha olefins; and oligomerization of the alpha olefins to hydrocarbon lubricant fluids.
The olefin oligomers used as starting material in the present invention are prepared from C3 -C5 olefins according to the methods presented by Chen et al. in the aforementioned patents cited and N. Page and L. Young in U.S. Pat. No. 4,855,527 and incorporated herein by reference. Shape-selective oligomerization, as it applies to conversion of C3 -C5 olefins over ZSM-5, is known to produce higher olefins up to C30 and higher. Reaction conditions favoring higher molecular weight products are low temperature (200-260° C.), elevated pressure (about 2000 kPa or greater) and long contact times (less than 1 WHSV). The reaction under these conditions proceeds through the acid catalyzed steps of oligomerization, isomerization-cracking to a mixture of intermediate carbon number olefins, and interpolymerization to give a continuous boiling product containing all carbon numbers. The channel system of ZSM-5 type catalysts impose shape selective constraints on the configuration of large molecules, accounting for the differences with other catalysts.
The shape-selective oligomerization/polymerization catalysts preferred for use herein to prepare the olefin oligomers used as starting material in the invention include the crystalline aluminosilicate zeolites having a silica to alumina molar ratio of at least 12, a constraint index of about 1 to 12 and acid cracking activity of about 50-300. Representative of the ZSM-5 type zeolites are ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38. ZSM-5 is disclosed and claimed in U.S. Pat No. 3,702,886 and U.S. Pat. No. Re. 29,948; ZSM-11 is disclosed and claimed in U.S. Pat. No. 3,709,979. Also, see U.S. Pat. Nos. 3,832,449 for ZSM-12; 4,076,842 for ZSM-23; 4,016,245 for ZSM-35 and 4,046,839 for ZSM-38. The disclosures of these patents are incorporated herein by reference. A suitable shape selective medium pore catalyst for fixed bed is a small crystal H-ZSM-5 zeolite (silica:alumina ratio =70:1) with alumina binder in the form of cylindrical extrudates of about 1-5mm. Unless otherwise stated in this description, the catalyst shall consist essentially of ZSM-5, which has a crystallite size of about 0.02 to 0.05 micron, or ZSM-23. Other pentasil catalysts which may be used in one or more reactor stages include a variety of medium pore siliceous material disclosed in U.S. Pat. Nos. 4,414,423 and 4,417,088, incorporated herein by reference.
The acid catalysts are deactivated by pretreatment with a surface-neutralizing base, as disclosed by Chen et al. and Page et al. in the aforementioned patents incorporated by reference. Surface deactivation is carried out using bulky or sterically hindered bases, typically those comprising trialkyl substituted pyridines. These hindered bases have very limited access to the internal pore structure of the catalyst, leaving the pores active sites for near linear oligomerization. However, active surface sites which are not constrained, as pores are, to low branching oligomerization are neutralized.
Considering propylene oligomerization for purposes of illustration, the olefinic oligomerization-polymerization products include C10 + substantially linear aliphatic hydrocarbons. The ZSM-5 catalytic path for propylene feed provides a long chain with approximately one to two lower alkyl (e.g., methyl) substituent per 12 carbon atoms in the straight chain.
When propylene or butene are oligomerized according to processes described herein, a unique mixture of liquid hydrocarbon products are formed. More particularly, this mixture of hydrocarbons may comprise at least 95% by weight of mono-olefin oligomers of the empirical formula:
(Cn H2n)m
where n is 3 or 4 and m is an integer from 1 to approximately 10, the mono-olefin oligomers comprising at least 20 percent by weight of olefins having at least 12 carbon atoms. Those olefins having at least 12 carbon atoms have an average of from 0.80 to 2.50 methyl side groups per carbon chain. The olefin side groups are predominantly methyl.
It will be understood that methyl side groups are methyl groups which occupy positions other than the terminal positions of the first and last (i.e., alpha and omega) carbon atoms of the longest carbon chain. This longest carbon chain is also referred to herein as the carbon backbone chain of the olefin. The average number of methyl side groups for the C12 olefins may comprise any range within the range of 0.80 to 2.50
These oligomers may be separated into fractions by conventional distillation separation. When propylene is oligomerized, olefin fractions containing the following number of carbon atoms can be obtained: 6, 9, 12, 15, 18 and 21. When butene is oligomerized, olefin fractions containing the following numbers of carbon atoms may be obtained: 8, 12, 16, 20, 24 and 28. It is also possible to oligomerize a mixture of propylene and butene and to obtain a mixture of oligomers having at least 6 carbon atoms.
Page and Young (allowed Application Ser. No. 105,438, filed Oct. 7, 1987) described these new olefins as multicomponent mixtures of propylene oligomers having relatively few branching methyl groups on the carbon backbone. As an example of branching, the dodecene fraction prepared from propylene and HZSM-23 [ZSM23-dodecenes] typically has 1.3 methyl branches. This can be reduced to 1.0 or less by varying reaction conditions.
The olefin oligomers produced from surface deactivated zeolite catalysis contain a mixture of types of olefin unsaturation with internal disubstituted and trisubstituted olefins dominating. Table 1 shows a comparison of two ZSM-23 collidine derived C11 + propylene oligomers prepared according to the method of Page and Young. The oligomers have been determined by gas chromatography to contain 1.2 and 1.8 methyl branches per 12 carbon atoms. Analysis by proton NMR shows the following distribution of olefin types:
TABLE 1______________________________________C11 + Olefins - Mole Ratio of Olefin TypesOligomer Alpha Disubst. Trisubst. Vinylidene______________________________________1.2 CH3 /12C 0.0 44.9 49.0 6.11.8 CH3 /12C 5.7 39.1 54.2 1.0______________________________________
The metathesis of the slightly branched olefinic hydrocarbons resulting from the olefin oligomerization operation is carried out to provide alpha olefins in a primary reaction which can be thought of as comprising the breaking of two unsaturated bonds between first and second carbon atoms and between third and forth carbon atoms, respectively, and the equilibrium formation of two new alpha olefinic bonds in different molecules as illustrated in the following formulas employing ethylene as the feed alphaolefin: ##STR1##
The equilibrium is displaced to the right in the presence of excess ethylene.
The reaction produces linear alpha olefins, branched alpha olefins and vinylidene olefins. The structure and molecular weight of the product olefins depend on the structure of the starting oligomers. For olefins of carbon number Cn which have undergone the metathesis with ethylene, the product olefins have an average molecular weight, on a molar basis, of Cn/2 +1. The average molecular weight may be raised as appropriate for subsequent oligomerization by removal of <C9 olefins by distillation.
As described in Table 1, trisubstituted olefins account for a major share of olefins in the slightly branched olefin oligomers. Where these trisubstituted olefins are isoolefinic, i.e., having the structure ##STR2## they account for a major share, as well, of the methyl branching in the olefin oligomer. Their reaction in metathesis with ethylene produces an alpha olefin and a vinylidenic olefin, as already shown. Further, it is known that vinylidene olefins are unreactive in reduced chromium oxide catalyzed and Ziegler catalyst catalyzed oligomerization. Accordingly, the olefin metathesis reaction of slightly branched olefin described here produces a mixture of olefins where only a portion, alpha olefins, are oligomerizable with Ziegler or chromium catalyst to higher lubricant grade hydrocarbon oligomers. A large portion of the methyl branching in the starting olefins is effectively removed from inclusion in higher oligomers produced by coordination catalyst by conversion to vinylidene structures through metathesis with ethylene.
In general any of the C2-8 alpha olefins can be reacted with the oligomerization product effluent in the metathesis operation herein. Some specific examples of such alphaolefins are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and the like with ethylene being preferred.
Any of the catalysts heretofore employed in olefin metathesis are suitably utilized in the metathesis conversion herein. Many of these catalyst have been reported in the prior art. Preferably, the catalyst is one of molybdenum, tungsten, or rhenium oxide deposited on a support of silica, alumina, silica-alumina or aluminum phosphate. An additional metal oxide, e.g., a rare earth metal oxide, can also be present as is known. Prior to its use, the catalyst is activated by calcination carried out in a conventional manner. A particularly suitable catalyst is molybdenum oxide supported on a mixture of amorphous precipitated silica and colloidal silica. A preferred catalyst is rhenium oxide on alumina. Co-catalysts, including tetraalkyl tin, are useful. A particularly preferred catalyst is rhenium oxide on gamma-alumina plus tetramethyl tin co-catalyst.
Suitable conditions for the metathesis reaction include a pressure of from about 50-35000 KPa, a temperature of from about 0° C. to about 500° C., and space velocities of from about 1 to about 300 WHSV based on the nature of the metathesis catalyst. Although the activity of the catalyst is suitable within the broad ranges mentioned above, increased activity is generally found when the pressure is from about 700 to about 3500 KPa, the temperature range is from about 20°-100° C., and the WHSV is from about 0.5 to about 1000. The process can be carried out either in the presence or absence of a diluent. Diluents comprising paraffinic and cycloparaffinic hydrocarbons can be employed. Suitable diluents are, for example, propane, cyclohexanes, methylcyclohexane, normal pentane, normal hexane, isotane, dodecane, and the like, or mixtures thereof, including primarily those paraffins and cycloparaffins having up to 12 carbon atoms per molecule. The diluent should be nonreactive under the conditions of the reaction. The reaction can also be carried out in a single unit or a battery of units employing the same or a different catalyst.
The amount of alpha-olefin employed in the metathesis conversion can vary widely and will depend in part on the degree of unsaturation in the higher olefin feed which can be readily quantified employing known techniques, e.g., bromine number. Generally, the alpha-olefin, particularly, will be present in stoichiometric excess of the amount theoretically required but can be substantially less than this. The amount of alpha olefin should be an amount sufficient to suppress the self-metathesis reaction which can occur between two molecules of the near linear olefin feedstock. When ethylene is used as the alpha olefin that amount is typically about a two to five molar excess. If desired, excess alpha-olefin can be separated from the metathesis product effluent and recycled to this stage.
It has been discovered that in the metathesis reaction between the near linear higher olefins and ethylene trisubstituted olefins are less active than disubstituted olefins. The conversion of disubstituted olefins proceeds effectively at ambient temperature (23° C.) in the presence of a cocatalyst Sn(CH3)4, or at 75-100° C. in the absence of a cocatalyst Sn(CH3)4. Trisubstituted olefins, i.e., those containing isoolefin groups, are converted in the absence of a cocatalyst Sn(CH3)4 even at elevated temperature (75° C.). Optionally, this relationship can be readily utilized to reduce the extent of trisubstituted olefin metathesis to produce vinylidene olefins in favor of predominantly disubstituted olefin metathesis with ethylene to produce alpha olefins.
The following non-limiting Examples are provided to illustrate the olefin metathesis reaction employed in the present invention.
Near linear olefins were prepared from propylene or isobutene or refinery mixtures of propylene, butenes, propane and butanes, using 2,6-di-tert-butylpyridine modified HZSM-5B as the shape selective catalyst according to the procedures described in U.S. Pat. No. 4,520,221.
A 340° C.+ fraction is separated from the product mixture produced from propylene at 200° C. using 2,6-di-tert-butylpyridine modified HZSM-5B as the catalyst. This fraction contains on the average 26 carbons. NMR results lead to calculated ranges of 1.12 to 1.43 methyl branches per average molecule, 0.1 to 0.13 ethyl groups, and 0.18 to 0.23 propyl groups.
Near linear olefins with 1 to 2 methyl branches per 10 carbon atoms were prepared from propylene or refinery mixtures of propylene, butenes, propane and butane, using 2,4,6-collidine modified HSM-23 as the shape selective catalyst according to procedures described by Page and Young in the reference previously cited.
An oligomer mixture prepared from propylene according to Example I is removed of the C9 - fraction. The C9 - fraction is recycled with propylene to make high oligomers according to Example I or II. Two hundred grams of the C8 + oligomer feed are deoxygenated and charged into a 450 cc Parr reactor under nitrogen. A Re2 O7 /Al2 O3 catalyst with 22% Re2 O7 loading is prepared and activated by heating at 550° C. in a stream of air for 3 hours, followed by heating in nitrogen for one hour. A calculated amount of ReOx catalyst and Sn(CH3)4 cocatalyst is added into the reactor under nitrogen. The ratio of catalyst to cocatalyst is Re:Sn=1. The reactor is closed, flushed with ethylene and charged with 7000 KPa of ethylene. Different molar ratios of the olefin feed and activated Re2 O7 with Sn(CH3)4 are used in each Example. The number of moles of the olefin feed is determined by bromine titration. The reaction takes place at room temperature, and after five hours the maximum extent of cometathesis is reached. Due to the presence of excess ethylene, self metathesis is nearly completely suppressed.
______________________________________ Olefin/ReOx -Sn(CH3)4Expl. Mole Ratio Temp., °C. Conversion______________________________________III 50 Rm. temp. 65%IV 10 Rm. temp. 85%______________________________________
A total oligomer mixture prepared according to Example I is co-metathesized with ethylene as described in Example III-IV, except the catalyst used here is WCl6 which is purified by sublimation before it is added to the reactor. The reaction takes place at 70° C. and a maximum conversion is reached in five hours. Again, self metathesis of the olefins is nearly completely suppressed due to the presence of excess ethylene.
______________________________________Example Olefin/catalyst Mole Ratio Temp.,°C. Conversion______________________________________V 50 70 57%VI 10 70 80%______________________________________
25 grams of Re2 O7 /Al2 O3 containing 22% Re2 O7 are packed into a fixed bed reactor. The catalyst is activated in the reactor, and the reactor is flushed with ethylene and pressurized with ethylene at 7000 KPa. An oligomer mixture prepared from propylene according to Example II is distilled of the C6.sup.═ fraction and charged into an ISCO pump. The oligomers are pumped into the reactor passing through an online bomb containing deoxygenating agent. The reactor is maintained at 100° C. and 7000 KPa ethylene pressure by cofeeding ethylene, and the oligomers are pumped through the reactor (downflow) at 0.5 WHSV. The product contains 70-80% co-metathesized products as shown by GC.
The composition of the metathesized product varies according to the composition of the higher olefin starting material and reaction conditions, as illustrated in the following Examples VIII and XI.
Olefin metathesis was carried out under the following conditions and the product was analyzed by gas chromatography to provide the results shown in Table 2.
Catalyst: ReOx /gamma-Al2 O3, 3.0 gm
Oligomers: C11 + Olefins, (1.3 CH3/12C), 75 gms
Ethylene Pressure: 3500 Kpa at room temperature
TABLE 2______________________________________Olefin PercentCom- time (hrs)/Temp °C.ponent 0 46.1/23 94.3/24 142.3/24 244.0/26 264.0/22______________________________________= or 0 4.1 3.6 5.6 6.4 8.4<C6C7 -C8 0 7.0 7.7 10.1 10.9 10.8C9 1.0 5.0 5.5 6.9 7.0 6.9C10 -C11 0.6 8.3 9.2 11.0 10.8 10.8C12 40.3 31.5 29.4 29.8 26.9 26.8C13 -C14 2.2 5.3 6.7 6.4 6.4 6.4C15 37.8 25.9 23.7 19.5 19.8 19.3C16 -C17 0.9 1.5 1.7 1.6 1.8 1.5C18 13.6 8.2 9.4 6.8 7.7 7.0>C18 3.6 3.2 3.1 2.3 2.3 2.1______________________________________
Olefin metathesis was carried out under the following conditions and the product was analyzed by gas chromatography to provide the results shown in Table 3.
Catalyst: ReOx /gamma-Al2 O3, 3.0 gm
Oligomers: C11 + Olefins, (1.3 CH3/12C), 75 gms
Ethylene Pressure: 5600 Kpa at room temperature
Olefin metathesis was carried out under the following conditions and the product was analyzed by gas chromatography to provide the results shown in Table 4.
Catalyst: ReOx /gamma-Al2 O3, 4.0 gm
Oligomers: C11 + Olefins, (1.4 CH3/12C), 75 gms
Cocatalyst: 1.4 gms Sn(CH3)4 in 50 ml hexane : 10 ml
Ethylene Pressure: 5600 Kpa at room temperature
TABLE 3__________________________________________________________________________ Percent time (hrs)/Temp °C.Olefin Component 0 0.25/41-103 16.0/102 23.0/102 39.2/102 4 6.7/102 63.3/102__________________________________________________________________________= or <C6 0 0.5 3.5 4.7 5.1 5.2 6.0C7 -C8 0 0.5 7.0 10.4 11.6 10.9 11.6C9 1.0 1.2 5.4 7.5 8.2 7.7 8.4C10 -C11 0.6 1.5 8.1 11.9 12.6 12.2 12.9C12 40.3 39.7 30.3 25.8 24.1 23.6 24.1C13 -C14 2.2 2.1 5.7 7.9 7.8 8.4 8.2C15 37.8 37.1 25.3 19.0 17.3 17.8 17.1C16 -C17 0.9 0.9 2.3 2.8 3.2 3.5 2.9C18 13.6 13.3 9.5 6.6 6.9 7.2 5.9>C18 3.6 3.2 2.9 3.4 3.2 3.5 2.9__________________________________________________________________________
TABLE 4__________________________________________________________________________ Percent time (hrs)/Temp °C.Olefin Component 0 2.08/26 6.02/25 16.9/24 24.0/21 33.0/24 41.7/25__________________________________________________________________________= or <C6 0 2.7 7.1 7.7 9.4 9.6 9.0C7 -C8 0 3.7 13.1 17.4 19.8 19.7 19.6C9 0 2.9 7.5 9.6 10.6 10.6 10.5C10 -C11 1.7 4.0 12.3 16.1 17.0 16.9 16.5C12 43.9 40.2 27.5 22.3 20.0 20.2 19.9C13 -C14 1.1 2.5 5.8 7.6 7.5 7.8 7.7C15 35.2 29.3 16.9 12.3 10.3 9.0 10.2C16 -C17 0.2 0.4 1.1 1.2 1.2 1.3 1.4C18 13.7 11.1 6.8 4.8 2.9 3.6 4.0>C18 4.2 3.3 1.7 1.3 1.4 1.5 1.3__________________________________________________________________________
Olefin metathesis was carried out under the following conditions and the product was analyzed by gas chromatography to provide the results shown in Table 5.
Catalyst: ReOx /gamma-Al2 O3, 1.0 gm
Oligomers: C11 + Olefins, (1.8 CH3/12C), 50 gms
Co-catalyst: 1.4 gm Sn(CH3)4 in 100 ml hexane, 5 ml
Ethylene Pressure: 3500 Kpa at room temperature
TABLE 5______________________________________ Percent time (hrs)/Temp °C.Olefin Component 0 0.27/28-75 1.75/75 13.0/75 23.3/75______________________________________= or <C6 0 1.6 1.9 2.4 2.4C7 -C8 0 1.7 3.0 4.1 4.2C9 0.9 1.7 2.7 3.6 3.3C10 -C11 1.4 3.1 4.7 5.6 5.9C12 32.1 29.4 27.1 29.4 29.3C13 -C14 3.0 3.8 4.6 4.5 5.2C15 40.9 38.2 36.2 33.5 34.3C16 -C17 1.3 1.7 2.0 1.9 1.9C18 15.8 15.2 13.8 11.9 10.7>C18 4.2 3.5 3.4 2.8 2.8______________________________________
9.0 grams of Re2 O7 /Al2 O3 containing 22% Re2 O7 are placed in a fixed bed reactor. The catalyst is activated in the reactor. After cooling down to room temperature, 54 cc of a solution of Sn(CH3)4 in hexane (1.4% wt/v) was pumped into the reactor and allowed to stand with the catalys for 10 minutes. The reactor is then flushed with ethylene and pressurized with ethylene at 7000 KPa. The oligomers are pumped into the reactor passing through an online bomb containing deoxygenating agent. The reactor is maintained at room temperature and 7000 KPa ethylene pressure by cofeeding ethylene and the oligomers are pumped through the reactor (downflow) at 1.0 WHSV. The product contains 70-80% comeththesized products as shown by GC.
Examples XIII and XIV serve to illustrate the following significant features of the co-metathesis of propylene oligomers with ethylene: disubstituted olefin reactivity in cometathesis is greater than trisubstituted olefin reactivity; use of a cocatalyst affects reactivity of di and trisubstituted olefins; reaction temperature influences the reactivity of di and trisubstituted olefins.
Olefin metathesis was carried out under the following conditions and the product was analyzed by gas chromatography to provide the results shown in Table 6.
Catalyst: ReOx /gamma-Al2 O3, 3.0 gm
Oligomers: C11 + Olefins, (1.3 CH3/12C), 75 gms
Co-catalyst: 1.4 gm Sn(CH3)4 in 34 ml hexane: 5 ml
Ethylene Pressure: 5600 Kpa at room temperature
Temperature: Ambient
Table 6 includes the NMR analysis of the product showing the distribution of alpha olefins, disubstituted olefins, trisubstituted olefins and vinylidene olefins in the starting oligomers and the metathesized product on a mole percent basis. The Table also shows the percent of disubstituted and trisubstituted olefins in the starting oligomers which reacted in the metathesis reaction.
TABLE 6__________________________________________________________________________(Example XIII)__________________________________________________________________________ Percent time (hrs)/Temp °C.Olefin Component 0 1.35/34-24 18.6/21 42.7/23 117.7/20 141.3/20 169.1/21__________________________________________________________________________= or <C6 0 2.1 3.8 4.3 3.9 4.7 4.6C7 -C8 0 1.9 7.1 11.3 13.9 14.5 14.2C9 1.0 2.1 5.1 7.8 10.1 10.2 10.4C10 -C11 0.6 2.8 7.9 12.5 16.4 16.1 16.6C12 40.3 38.3 31.6 27.7 23.8 23.3 23.0C13 -C14 2.2 2.8 5.1 7.3 9.5 9.5 9.0C15 37.7 33.9 25.0 19.5 13.7 14.6 12.3C16 -C17 0.9 0.6 1.1 1.5 2.3 2.1 2.2C18 13.6 12.3 9.8 6.4 4.7 3.5 4.2>C18 3.6 3.2 2.4 1.7 1.7 1.5 1.7__________________________________________________________________________NMR data Mole % Olefin product__________________________________________________________________________alpha 0.31 7.4 23.1 31.6 45.6 -- 44.0disubstituted 38.5 33.9 21.9 14.4 6.6 -- 5.7trisubstituted 58.8 53.8 44.5 40.2 30.4 -- 32.6vinylidene 2.4 4.9 10.6 13.8 17.5 -- 17.7__________________________________________________________________________ % olefin reacted__________________________________________________________________________disubstituted -- 4.3 26.9 41.2 64.1 -- 63.3trisubstituted -- 1.4 13.0 17.8 30.5 -- 27.7__________________________________________________________________________ Final Total Increase, olefins: <C12 + (C13 to C14) +(C16 to C17) = 52.3%; Final Total Decrease, olefins: C12 + C15 + >C18 = -54.1%
TABLE 7__________________________________________________________________________(Example XIV)__________________________________________________________________________ Percent time (hrs)/ Temp °C.Olefen Component 0 0.25/27-75 1.25/75 7.67/75 17.6/75 47.3/75 71.3/75 115.1/75 138.6/75__________________________________________________________________________= or >C6 0 0.6 0.6 2.1 3.8 4.2 5.5 5.4 5.6C7 -C8 0 0.7 1.0 3.6 7.7 8.6 10.9 12.2 12.3C9 1.0 1.3 1.4 3.2 5.7 6.4 7.4 8.3 8.4C10 -C11 0.6 1.6 2.0 4.9 8.8 9.9 11.5 12.6 13.0C12 40.3 38.6 36.5 35.0 30.8 28.6 24.5 25.2 24.7C13 -C14 2.2 2.4 3.0 3.9 5.5 6.5 7.5 7.5 8.0C15 37.8 36.4 35.6 30.6 22.3 23.0 19.0 17.3 17.3C16 -C17 0.9 1.2 1.5 1.6 2.1 2.4 3.1 2.9 3.0C18 13.6 13.4 13.4 11.5 9.2 6.9 7.6 6.1 5.1>C18 3.6 3.8 4.9 3.6 4.1 3.5 3.0 2.5 2.6__________________________________________________________________________NMR data Mole % Olefin product__________________________________________________________________________alpha 0.31 -- 3.9 13.4 16.7 -- 29.3 -- 37.6disubstituted 38.5 -- 34.2 28.8 20.5 -- 12.9 -- 12.2trisubstituted 58.8 -- 57.7 52.8 57.4 -- 52.1 -- 44.9vinylidene 2.4 -- 4.2 5.1 5.4 -- 5.7 -- 5.3__________________________________________________________________________ % olefin reacted__________________________________________________________________________disubstituted -- -- 5.5 16.6 27.1 -- 48.1 -- 57.7trisubstituted -- -- 0.9 3.7 0.0 -- 0.0 -- 5.4__________________________________________________________________________ Final Total Increase, olefins: <C12 + (C13 to C14) + (C16 to C17) = 45.6%; Final Total Decrease, olefins: C12 + C15 + >C18 = -45.6%
Olefin metathesis was carried out under the following conditions and the product was analyzed by gas chromatography to provide the results shown in Table 7.
Catalyst: ReOx /gamma-Al2 O3, 3.0 gm
Oligomers: C11 + Olefins, (1.3 CH3/12C), 75 gms
Ethylene Pressure: 5600 Kpa at room temperature
Temperature: 75° C.
Table 7 also includes the NMR analysis of the product showing the distribution of alpha olefins, disubstituted olefins, trisubstituted olefins and vinylidene olefins in the starting oligomers and metathesized product on a mole percent basis. The Table also shows the percent of disubstituted and trisubstituted olefins in the starting oligomers which reacted in the metathesis reaction.
The primary purpose of performing co-metathesis reactions of near-linear propylene oligomers with ethylene is to produce alpha-olefins. The alpha-olefins so produced are complex mixtures containing two types of structures. One type is linear, but contains both even and odd number carbons, and a mixture of different molecular weights. The other is near-linear with one or two methyl branches, and also contain both even and odd number carbons, and a mixture of different molecular weights. Alpha-olefins are known to be polymerizable by chromium catalysis to produce high VI lubricants.
The olefins used to prepare lubes herein are from the co-methathesis reactions between propylene oligomers and ethylene. The lubes were prepared by using activated Cr (3%) on silica catalyst as described in the previously cited U.S. Patents to M. Wu. The starting olefins, experimental conditions employed, and the viscometric properties of the lubes produced according to this invention are described in Table 8 and 9.
TABLE 8______________________________________Composition ofCo-metathesized Olefins Used as Lube Feed in Example XV______________________________________A-DOlefin Example XV A-GComponents % A B C D E F G______________________________________≦C6 4.1 0 2.5 5.5 2.5 5.9 13.2C7 -C8 8.6 4.5 13.0 16.9 13.0 12.3 29.8C9 16.6 13.6 20.2 11.7 20.2 8.4 18.5C10 -C12 27.1 33.4 25.9 39.0 25.9 37.8 25.6C13 -C15 28.7 34.8 27.4 19.2 27.4 24.8 9.3C16 -C18 12.1 10.9 8.8 6.3 8.8 8.1 2.9>C18 2.9 2.8 2.2 1.7 2.2 2.9 0.7______________________________________Treatment of Lube FeedExpl.______________________________________XV A, 1.8 CH3 /12C, C11 = +, <C9 olefins partiallyremoved.XV B, 1.8 CH3 /12C, C11 = +, <C9 olefins mostlyremoved.XV C, 1.8 CH3 /12C, C11 = +, <C6 olefins mostlyremoved.XV D, 1.4 CH.sub. 3 /12C, C11 = +, nothing removed (totalproducts).XV E, Same as XV, CXV F, 1.3 CH3 /12C, C11 = +, no cocatalyst, nothingremovedXV G, 1.4 CH3 /12C, C8 = +, nothing removed, (totalproducts)______________________________________
The alpha-olefin oligomers are prepared by oligomerization reactions in which a major proportion of the double bonds of the alphaolefins are not isomerized. These reactions include alpha-olefin oligomerization by supported metal oxide catalysts, such as Cr compounds on silica or other supported IUPAC Periodic Table Group VIB compounds. The catalyst most preferred is a lower valence Group VIB metal oxide on an inert support. Preferred supports include silica, alumina, titania, silica alumina, magnesia and the like. The support material binds the metal oxide catalyst. Those porous substrates having a pore opening of at least 40 angstroms are preferred.
The support material usually has high surface area and large pore volumes with average pore size of 40 to about 350 angstroms. The high surface area are beneficial for supporting large amount of highly dispersive, active chromium metal centers and to give maximum efficiency of metal usage, resulting in very high activity catalyst. The support should have large average pore openings of at least 40 angstroms, with an average pore opening of >60 to 300 angstroms preferred. This large pore opening will not impose any diffusional restriction of the reactant and product to and away from the active catalytic metal centers, thus further optimizing the catalyst productivity. Also, for this catalyst to be used in fixed bed or slurry reactor and to be recycled and regenerated many times, a silica support with good physical strength is preferred to prevent catalyst particle attrition or disintegration during handling or reaction.
The supported metal oxide catalysts are preferably prepared by impregnating metal salts in water or organic solvents onto the support. Any suitable organic solvent known to the art may be used, for example, ethanol, methanol, or acetic acid. The solid catalyst precursor is then dried and calcined at 200 to 900° C. by air or other oxygen-containing gas. Thereafter the catalyst is reduced by any of several various and well known reducing agents such as, for example, CO, H2, NH3, H2 S, CS2, CH3 SCH3, CH3 SSCH3, metal alkyl containing compounds such as R3 Al, R3 B,R2 Mg, RLi, R2 Zn, where R is alkyl, alkoxy, aryl and the like. Preferred are CO or H2 or metal alkyl containing compounds. Alternatively, the Group VIB metal may be applied to the substrate in reduced form, such as CrII compounds. The resultant catalyst is very active for oligomerizing olefins at a temperature range from below room temperature to about 250° C. at a pressure of 0.1 atmosphere to 5000 psi. Contact time of both the olefin and the catalyst can vary from one second to 24 hours. The catalyst can be used in a batch type reactor or in a fixed bed, continuous-flow reactor.
In general the support material may be added to a solution of the metal compounds, e.g., acetates or nitrates, etc., and the mixture is then mixed and dried at room temperature. The dry solid gel is purged at successively higher temperatures to about 600° for a period of about 16 to 20 hours. Thereafter the catalyst is cooled down under an inert atmosphere to a temperature of about 250 to 450° C. and a stream of pure reducing agent is contacted therewith for a period when enough CO has passed through to reduce the catalyst as indicated by a distinct color change from bright orange to pale blue. Typically, the catalyst is treated with an amount of CO equivalent to a two-fold stoichiometric excess to reduce the catalyst to a lower valence CrII state. Finally the catalyst is cooled down to room temperature and is ready for use.
The product oligomers have a very wide range of viscosities with high viscosity indices suitable for high performance lubrication use. The product oligomers also have atactic molecular structure of mostly uniform head-to-tail connections with some head-to-head type connections in the structure. These low branch ratio oligomers have high viscosity indices at least about 15 to 20 units and typically 30-40 units higher than equivalent viscosity prior art oligomers, which regularly have higher branch ratios and correspondingly lower viscosity indices. These low branch oligomers maintain better or comparable pour points.
The branch ratios defined as the ratios of CH3 groups to CH2 groups in the lube oil are calculated from the weight fractions of methyl groups obtained by infrared methods, published in Analytical Chemistry. Vol. 25, No. 10, p. 1466 (1953). ##EQU1##
The alpha olefin oligomerization experiments Examples XV,A-G shown in Table 9 were carried out in a flask with a slight positive nitrogen pressure to keep the reaction atmosphere inert. The catalyst comprised CO reduced, 3% chromium on silica and the total reaction time was 16 hours. Preferably, all polymerizations are carried out in a closed reactor to obtain quantitative conversions. Lube product is isolated by filtering the catalyst and distilling under vacuum to remove light components with boiling point below 400° C.
The results obtained indicate that high quality lubes can be obtained from the alpha-olefins prepared from the co-methathesis of near-linear propylene oligomers and ethylene. They also indicate that high quality lubes can be obtained from a complex mixture of alpha-olefins. The lube products have higher VI than current PAO products of similar viscosity. One hydrogenated lube also has very low pour point. The unique structures of the starting alpha-olefins containing both linear and near-linear structures, with even and odd number carbons, and a broad distribution of molecular weights, are held to be most suitable for the production of high VI and low pour point lube product. The product can be hydrogenated by means well known in the art to eliminate olefin unsaturation and provide a stable, commercially useful lubricant.
TABLE 9______________________________________Olefin Oligomerization to Lubes Feed/ Polymeri- Cat. Wt ,zation Polymeriz- Kv, Cs LubeFeed ratio Temp., °C. 40° C. 100° C. VI pour point______________________________________XVA 10/1 125 466.15 46.96 158 -49° C.XVA' 15/1 102 126.19 19.49 176XVB 25/1 110 262.3 33.6 173XVC 25/1 110 269.79 33.1 167XVD 20/1 110 529.5 53.27 164XVE 25/1 110 487.5 52.3 171XVF 25/1 110 459.3 49.5 169XVG 25/1 110 438.5 41.5 145______________________________________
The lubricants produced from the near linear olefins prepared according to the process of this invention show remarkably high viscosity indices (VI) with low pour points at viscosities from 2cS (100° C.) and higher. They can be prepared in a wide range of viscosities typical of those achivable in the reduced chromium catalyzed reaction described in the cited patents of M. W. However, where the products described by M. Wu exhibit high VI by preparing oligomers having a branch index below 0.19, the branch indices of the lubricants prepared according to this invention are above 0.20.
The near linear alpha olefins oligomerized in this invention to provide high VI lubricant are characterized as having branching confined predominantly to the pendant alkyl group of the oligomer lubicant molecule. While it is known and taught in the cited Wu patents that branching in the backbone of the lubricant molecule adversely effects VI, it has been surprisingly discovered herein that lubricants with high VI can be prepared from slightly branched alpha olefins by reduced chromium catalysis if those branches are restricted predominantly to the pendant alkyl group of the oligomer molecule. While not wishing to be limited by theoretical considerations, it is believed that the CO reduced chromium oxide on silica catalyst described by Wu oligomerizes near linear alpha olefins with little isomerization and consequent branching occurring in the oligomer backbone. It is held that low backbone branching dominates the factors and intermolecular associations that provide high VI as an end result in the product, with branching in the pendant alkyl portions of the oligomer molecule found to have little effect on the degradation of VI.
Referring to the Figure, a block flow diagram is presented illustrating a particular embodiment of the present invention. In the Figure, a lower alkene 105, preferably propylene, is passed to alkene conversion or oligomerization zone 110 containing acidic zeolite catalyst particles. The zeolite is preferably ZSM-5 or ZSM-23 which has been pretreated with a bulky or sterically hindered amine to deactivate the surface of the catalyst. Oligomerization is carried out under the conditions previously described herein and further described in the aforementioned patents to C. S. H. Chen and the patent to Page et al. The reaction effluent 115 is passed to a separator 120, i.e., a distillation tower, wherein the slightly branched olefinic higher hydrocarbons are separated to provide a C9 - fraction 172 and a C8 + fraction 125. The C9 - fraction may be collected or passed as a recycle stream 175 to 110 for further oligomerization. The C9 + fraction is passed to the olefin metathesis reactor 130 in conjunction with an ethylene stream 135 comprising a stoichiometric excess of ethylene to suppress self-metathesis of higher olefinic hydrocarbons. In zone 130 the metathesis reaction is carried out, preferably at a temperature of about ambient (23° C.) and in contact with rhenium oxide catalyst and tetramethyl tin as co-catalyst. The mixture of olefins from the metathesis reaction 145 is passed to another separator 140 where it is fractionated to provide an unreacted ethylene stream 155 which can be recycled to zone 130; a stream 165 comprising olefinic hydrocarbons from C3 to C9 which can also be recycled 165 to the oligomerization zone 110; and a product stream 185 comprising a mixture of C9 + slightly branched and linear alpha olefins as well as some vinylidenic olefins. Obviously, in the present invention the cut taken in the separator 140 can be optionally adjusted to provide a stream 185 comprising C10 + or higher hydrocarbons.
The alpha olefin mixture, i.e., stream 185, is passed to an alpha olefins oligomerization zone 150 containing CO reduced chromium oxide catalyst on silica wherein the oligomerization is carried out under the condition described in the referenced patents to M. Wu. The product stream separated 200 comprises a slightly branched olefinic hydrocarbon lubricant with a high viscosity index and low pour point. Optionally, components of the reaction product below C20 or C30 (195) may be separated and recycled to zone 110 for further oligomerization.
The olefinic product 200 is typically hydrogenated by conventional means to provide a nearly saturated superior lubricant product.
While the instant invention has been described by specific examples and embodiments, there is no intent to limit the inventive concept except as set forth in the following claims.
|Cited Patent
|Filing date
|Publication date
|Oct 4, 1971
|May 13, 1975
|Phillips Petroleum Co
|Conversion of unsaturated compounds
|Feb 16, 1978
|Dec 25, 1979
|Phillips Petroleum Company
|Disproportionation/double-bond isomerization of olefins
|Aug 30, 1982
|Feb 14, 1984
|Phillips Petroleum Company
|Reduced polymer formation in disproportionation reaction by addition of CO to feed
|Oct 5, 1983
|Feb 12, 1985
|Phillips Petroleum Company
|Olefin metathesis and catalyst
|Sep 28, 1983
|Mar 12, 1985
|Phillips Petroleum Company
|Olefin metathesis and catalyst
|Jul 26, 1983
|May 14, 1985
|Phillips Petroleum Co.
|Olefin metathesis and catalyst
|May 4, 1984
|Sep 17, 1985
|Phillips Petroleum Company
|Olefin conversions and catalysts
|Feb 16, 1984
|Oct 15, 1985
|Phillips Petroleum Company
|Olefin conversion
|Jan 3, 1986
|May 12, 1987
|Mobil Oil Corporation
|Process for preparing alpha-olefins from light olefins
|Jun 23, 1988
|May 2, 1989
|Mobil Oil Corporation
|Process for manufacturing olefinic oligomers having lubricating properties
|Citing Patent
|Filing date
|Publication date
|Aug 22, 1990
|May 12, 1992
|Mobil Oil Corporation
|High viscosity index lubricant compositions
|Sep 23, 1991
|May 11, 1993
|Mobil Oil Corporation
|Process for the production of high cetane value clean fuels
|Sep 14, 1992
|Oct 3, 1995
|Badehi; Peirre
|Methods for producing packaged integrated circuit devices and packaged integrated circuit devices produced thereby
|May 26, 1995
|Dec 21, 1999
|Townsend; Phillip
|Catalytic distillation oligomerization of vinyl monomers to make polymerizable vinyl monomer oligomers uses thereof and methods for same
|Dec 22, 1999
|May 13, 2003
|Chevron Usa Inc
|Synthesis of narrow lube cuts from Fischer-Tropsch products
|Jan 11, 2001
|Feb 3, 2004
|Chevron U.S.A. Inc.
|Process for making a lube base stock from a lower molecular weight feedstock using at least two oligomerization zones
|Mar 23, 2000
|Mar 9, 2004
|Exxonmobil Research And Engineering Company
|Synthetic hydrocarbon fluids
|Jan 11, 2001
|Mar 16, 2004
|Chevron U.S.A. Inc.
|Process for making a lube base stock from a lower molecular weight feedstock
|Jan 11, 2001
|Jan 11, 2005
|Chevron U.S.A. Inc.
|Process for making a lube base stock from a lower molecular weight feedstock in a catalytic distillation unit
|Aug 10, 2001
|Jun 13, 2006
|Basf Aktiengesellschaft
|Method for producing alkyl aryl sulphonates
|Mar 10, 2006
|Mar 10, 2009
|Exxonmobil Chemical Patents Inc.
|Oligomerization of isobutene-containing feedstocks
|Jan 28, 2009
|Jun 15, 2010
|Exxonmobil Chemical Patents Inc.
|Oligomerization of isobutene-containing feedstocks
|Oct 1, 2009
|Aug 21, 2012
|Exxonmobil Research And Engineering Company
|HVI-PAO bi-modal lubricant compositions
|Oct 28, 2010
|Oct 30, 2012
|Exxonmobil Research And Engineering Company
|Base stock lubricant blends
|Aug 18, 2009
|Mar 12, 2013
|Exxonmobil Research And Engineering Company
|Low sulfur and low metal additive formulations for high performance industrial oils
|Oct 1, 2009
|Jul 2, 2013
|Exxonmobil Research And Engineering Company
|Chromium HVI-PAO bi-modal lubricant compositions
|Oct 27, 2010
|Aug 6, 2013
|Exxonmobil Research And Engineering Company
|High viscosity novel base stock lubricant viscosity blends
|Jun 4, 2007
|Sep 17, 2013
|Exxonmobil Research And Engineering Company
|High viscosity metallocene catalyst PAO novel base stock lubricant blends
|Jan 28, 2011
|Dec 3, 2013
|Exxonmobil Research And Engineering Company
|Method for improving the fuel efficiency of engine oil compositions for large low, medium and high speed engines by reducing the traction coefficient
|Jan 28, 2011
|Feb 4, 2014
|Exxonmobil Research And Engineering Company
|Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
|Sep 29, 2010
|May 6, 2014
|Exxonmobil Research And Engineering Company
|Alkylated naphtylene base stock lubricant formulations
|Jan 28, 2011
|May 20, 2014
|Exxonmobil Research And Engineering Company
|Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
|Jan 28, 2011
|Jun 10, 2014
|Exxonmobile Research And Engineering Company
|Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
|Jan 28, 2011
|Jun 24, 2014
|Exxonmobil Research And Engineering Company
|Method for improving the fuel efficiency of engine oil compositions for large low and medium speed engines by reducing the traction coefficient
|Jun 14, 2012
|Sep 16, 2014
|Exxonmobil Research And Engineering Company
|Gear oil compositions
|Mar 11, 2013
|Dec 30, 2014
|Exxonmobil Research And Engineering Company
|Gear oil compositions
|Jan 11, 2001
|Jul 5, 2001
|Krug Russell R.
|Process for making a lube base stockfrom a lower molecular weight feedstockin a catalystic distillation unit
|Aug 10, 2001
|Jan 15, 2004
|Heiko Maas
|Method for producing alkyl aryl sulphonates
|May 5, 2005
|Sep 15, 2005
|De Boer Eric J.M.
|Process for the preparation of oligomers
|Mar 22, 2006
|Jul 27, 2006
|Basf Aktiengesellschaft
|Process for the preparation of alkylarylsulfonates
|Mar 10, 2006
|Sep 13, 2007
|Brown Stephen H
|Oligomerization of isobutene-containing feedstocks
|Jan 28, 2009
|May 28, 2009
|Stephen Harold Brown
|Oligomerization of Isobutene-Containing Feedstocks
|Oct 1, 2009
|Apr 29, 2010
|Lee Gordon H
|Chromium HVI-PAO bi-modal lubricant compositions
|Jan 28, 2011
|Aug 11, 2011
|Exxonmobil Research And Engineering Company
|Method for improving the fuel efficiency of engine oil compositions for large low and medium speed gas engines by reducing the traction coefficient
|Sep 21, 1992
|Apr 1, 1993
|Mobil Oil Corporation
|Process for the production of high cetane value clean fuels
|U.S. Classification
|585/329, 585/533, 585/326, 585/502, 585/314, 585/504, 585/17, 585/315
|International Classification
|Cooperative Classification
|European Classification
|Feb 15, 1990
Owner name: MOBIL OIL CORPORATION, A CORP OF NY
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:CHEN, CATHERINE S. H.;WU, MARGARET M-S.;REEL/FRAME:005242/0127
Effective date: 19900129
|Nov 15, 1993
|Fee payment
Year of fee payment: 4
|May 5, 1998
|Maintenance fee reminder mailed
|Oct 11, 1998
|Lapse for failure to pay maintenance fees
|Dec 22, 1998
|Expired due to failure to pay maintenance fee
Effective date: 19981009


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Cajun Catfish Courtbouillon
2 medium onions -- chopped
3 stalks celery -- chopped
1 large bunch fresh parsley -- wash/drain/chop
1 large green pepper -- chopped
2 cloves garlic -- minced
5 pounds catfish fillets
salt and pepper -- to taste
red pepper -- to taste
3 tablespoons vegetable oil
2 tablespoons all-purpose flour -- divided
1 1/2 cups tomato sauce -- divided
1/4 cup water
2 lemon slices
1 large bay leaf
1/4 teaspoon thyme leaves
Combine vegetables; divide in half, and set aside.
Cut catfish into large pieces; generously sprinkle each piece with salt, pepper, and crushed red pepper. Set aside.
Put oil in a large cast iron pot; top with half of fish pieces. Place have of vegetable mixtures over fish; top with 1 tablespoon flour, then 3/4 cup tomato sauce. Repeat layers with remaining fish pieces, vegetables, flour and tomato sauce. Add remaining ingredients.
Cover and cook over low heat for one hour or until fish flakes easily when tested with a fork. Shake pot frequently to keep fish from sticking to the bottom (stirring will break up the fish). Add additional seasonings before serving, if desired.
Yield: 6 servings.
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HOUSTON --McNeil High School shooting guard Armoni Brooks became the newest member of the University of Houston Men's Basketball program with his signing of a National Letter of Intent on Wednesday afternoon, Head Coach Kelvin Sampson announced.
Brooks, who stands 6-foot-4 and weighs 180 pounds, was recently ranked as the No. 11 player in the state of Texas by TexasHoops.comRivals.
A native of Round Rock, Texas, Brooks chose Houston over Kansas State, Creighton, Tulsa and Nebraska.
As a junior during the 2014-15 season, he averaged 16.0 points and 6.0 rebounds per game for Head Coach Darrell Hagemann and buried a jumper with only five seconds left to lift the Mavericks to a 38-37 win in the Class 6A Regional Quarterfinal.
"Armoni has an elite skill set that translates well to our level. He is a tremendous 3-point shooter and is continuing to develop his game in other areas," Sampson said. "As talented a player as Armoni is, we are excited about the character he brings into our program. He comes from a good family and is a good student and will represent our University well as we move forward."
Leading the Mavericks to 26 wins and the Regional semifinals, Brooks – whose first name is pronounced Ar-MAH-Nee – was recognized as the District 13-6A Newcomer of the Year. He was an All-Region II First-Team honoree by the Texas Association of Basketball Coaches and was an All-District 13-6A First-Team selection.
In addition to his high school career, Brooks played for AAUs' THP Elite for Head Coach Tim Farley.
The Cougars take their first step in the 2015-16 season when they play host Montana Tech at 7 p.m., Friday, in the exhibition opener inside Hofheinz Pavilion. That game will be free admission for all fans with no court seating available.
Friday's exhibition will have special significance for Sampson, who began his head coaching career with the Orediggers in 1981. The Orediggers' home court at Montana Tech's HPER Complex is named in his honor.
Houston begins the regular season when it meets Prairie View A&M at 7 p.m., Wednesday, Nov. 18, inside Hofheinz Pavilion in the first of five consecutive regular-season home games to open the year.
Fans have a variety of ticket options to accommodate any budget. Season tickets, group tickets, single-game tickets and a 3-Point Pack are on sale now. To purchase tickets or for complete information, fans can visit uhcougars.com/tickets and follow the appropriate links or click here.
Fans also can call 713-GO-COOGS (462-6647) or visit the Athletics Ticket Office from 10 a.m., to 5:30 p.m., Monday through Friday. To purchase tickets in person, fans can visit the Athletics Ticket Office located on the northeast corner of TDECU Stadium, just outside of Gate 1 off Cullen Boulevard. Parking is available in the TDECU Stadium parking garage with the first 30 minutes free of charge.
Single-game tickets for Houston Men's Basketball's 2015-16 season begin at only $5 per game. Fans can purchase General Admission single-game tickets for only $5, while Reserved 2 seating is available for only $10 per game. Fans may buy Reserved 1 single-game tickets for $15 per ticket.
Fans can purchase single-game tickets by clicking here.
Fans should note that single-game tickets for the Cougars' Dec. 13 showdown against LSU inside Hofheinz Pavilion will not be available.
Instead, fans can purchase tickets for the LSU game as part of a 3-Point Pack, which includes a ticket to the LSU game and tickets to two other Houston home games inside Hofheinz Pavilion. Reserved 1 seating for the 3-Point Pack can be purchased for $40 with Reserved seating available for only $30.
Fans can purchase the 3-Point Pack by clicking here.
Tickets for groups of 10-24 or more can be purchased for as low as $12 per ticket in Reserved 2 for 18 regular-season home games inside Hofheinz Pavilion. Groups of more than 25 people can buy Reserved 2 tickets for only $10 per ticket
Groups of 10 -24 can buy tickets for only $10 per ticket in Reserved 2 with prices plummeting to only $6 per ticket for groups of 25 or more.
Administrators can find more information about group tickets seating and pricing by clicking here.
Fans can receive the latest news and notes by following @UHCougarMBK on Twitter. Fans also can discuss the latest Houston Men's Basketball news and notes on the team's Facebook page by clicking LIKE at HoustonCougarMensHoops.


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There is constant propaganda in BNW. The cute sayings and quips are meant to reinforce the ideology of the party. Consider:
"you do look glum! What you need is a gramme of soma."
"..there is always soma, delicious soma, half a gramme for a half-holiday, a gramme for a week-end, two grammes for a trip to the gorgeous East, three for a dark eternity on the moon..."
"Never put of till tomorrow the fun you can have today."