text:
A guide to self reliant
Kerosene heaters and
8. Wood
cooking and heating
9. Communi-cations
10. Essential
11. Home
built items
Electrical; generators
and power
13. War
Miles Stair's SURVIVAL
Miles Stair's
Is the
US Navy vulnerable in the Gulf?
The Myth of US Invincibility
by Mark H. Gaffney April 17, 2005
During the summer of 2002, in the run-up to President
Bush's invasion of Iraq, the US military staged the
most elaborate and expensive war games ever conceived.
Operation Millennium Challenge, as it was called, cost
some $250 million, and required two years of planning.
The mock war was not aimed at Iraq, at least, not
overtly. But it was set in the Persian Gulf, and
simulated a conflict with a hypothetical rogue state.
The "war" involved heavy use of computers, and was also
played out in the field by 13,500 US troops, at 17
different locations and 9 live-force training sites.
All of the services participated under a single joint
command, known as JOINTFOR. The US forces were
designated as "Force Blue," and the enemy as OPFOR, or
"Force Red." The "war" lasted three weeks and ended
with the overthrow of the dictatorial regime on August
Later, Van Riper also aired his frustrations in a
taped-for-television interview: "There were accusations
that Millennium Challenge was rigged. I can tell you it
was not. It started out as a free-play exercise, in
which both Red and Blue had the opportunity to win the
game. However, about the third or fourth day, when the
concepts that the command was testing failed to live up
to their expectations, the command at that point began
to script the exercise in order to prove these
concepts. This was my critical complaint. You might
say, 'Well, why didn't these concepts live up to the
expectations?' I think they were fundamentally flawed
in that they. leaned heavily on systems analysis of
decision-making. I'm angered that, in a sense, $250
million was wasted. But I'm even more angry that an
idea that has never been truly validated, that never
really went through the crucible of a real experiment,
is being exported to our operational forces to use.
What I saw in this particular exercise and the results
from it were very similar to what I saw as a young
second lieutenant back in the 1960s, when we were
taught the systems engineering techniques that Mr.
[Robert] McNamara [Secretary of Defense under
Presidents John F. Kennedy and Lyndon Johnson] had
implemented in the American military. We took those
systems to the battlefield, where they were totally
inappropriate. The computers in Saigon said we were
winning the war, while out there in the rice paddies we
knew damn well we weren't winning. That's where we went
astray, and I see these new concepts potentially being
equally ill-informed and equally dangerous."
"We didn't put you in harm's way purposely. It just...
As a result of Van Riper's criticism, Gen. Kernan, the
JOINTFOR commander, faced some pointed questions at a
subsequent press briefing. In defending the operation,
the general explained the embarrassing outcome as due
to the unique environment in which the war simulation,
by necessity, had been conducted:
Q: General, one thing that Van Riper made much of was
the fact that at some point the blue fleet was
Gen. Kernan: True, it was.
Q: I want to set-aside for a moment the allegation that
the game was rigged because the fleet was "re-floated."
I mean, I understand, I've been told that happens in
war games.
Gen. Kernan: Sure.
Q: And I'm curious. In the course of this experiment or
exercise, your fleet was sunk. I'm wondering if that
did teach you anything about the concepts you were
testing or if that showed anything relevant.
Gen. Kernan: I'll tell you one of the things it taught
us with a blinding flash of the obvious, after the
fact. And of course, it goes back to live versus
simulation, and what we were doing. There are very
prescriptive lanes in which we conduct sea training and
amphibious operations, and these are very, obviously,
because of commercial shipping and a lot of other
things, just like our air lanes. The ships that we used
for the amphibious operations, we brought them in
because they had to comply with those lanes. Didn't
even think about it.
Now you've got basically, instead of being over the
horizon like the Navy would normally fight, and at
stand-off ranges that would enable their protective
systems to be employed, now they're sitting right off
the shore, where you're looking at them. I mean, the
models and simulation that we put together, it couldn't
make a distinction. And we didn't either, until, all of
a sudden, whoops, there they are. And that's about the
time he attacked. You know?
The Navy was just bludgeoning me dearly because, of
course, they would say, 'We never fight this way.' Fair
enough. Okay. We didn't mean to do it. We didn't put
you in harm's way purposely. I mean, it just, it
happened. And it's unfortunate. So that's one of the
things that we learned."3
Gen. Kernan's nuanced defense was that the simulation
had necessarily been conducted in the vicinity of busy
sea lanes, hence, in the presence of live commercial
shipping; and this required the Navy to "turn off" some
of its defenses, which it would not have done in a real
wartime situation. All of which is probably true, but
the general's remark that in a real Gulf war the fleet
would be deployed differently, in a stand-off manner,
with its over-the-horizon defenses fully operable, was
a misrepresentation of the actual situation in the
Persian Gulf, today. The US Navy's biggest problem
operating in Gulf waters are the constraints that the
region's confined spaces impose on US naval defenses,
which were designed for the open sea. The Persian Gulf
is nothing but a large lake, after all, and in such an
environment the Navy's over-the-horizon defenses are
seriously compromised. 4 Nor can the Navy withdraw to a
safe distance, so long as its close-in presence is
required to support the US occupation forces in Iraq.
The serious implications of this simple fact for a
possible future conflict, for instance, involving Iran,
have never, to my knowledge, been discussed in the US
Gen. Kernan's remark was not a misstatement. He
repeated himself again, later in the same interview,
while fielding another question:
Q: As a follow-up... Van Riper also said that most of
the blue Naval losses were due to cruise missiles. Can
you talk about that and say how concerned you are about
Gen. Kernan: "Well, I don't know. To be honest with
you, I haven't had an opportunity to assess... what
happened. But that's a possibility, once again, because
we had to shut off some of these self-defense systems
on the models that would have normally been employed.
That's a possibility. I think the important thing to
note is that normally the Navy would have been
significantly over-the-horizon. They would've been
arrayed an awful lot differently than we forced them to
because of what they had to do for the live-exercise
piece of it.... Yeah, I think we learned some things.
The specifics of the cruise-missile piece... I really
can't answer that question. We'd have to get back to
Safely Over-the-Horizon?
Gen. Kernan's remarks are surprising, because at the
time he made them, in August 2002, as he well should
have known, at least two separate studies, one by the
US Government Accounting Office (GAO,) based on the
Navy's own data, and another by an independent
think-tank, had already warned the Office of the Navy
about the growing threat to the US fleet posed by
anti-ship cruise missiles. 6 As recently as 1997 some
forty different nations possessed these awesome
weapons. By 2000 the number had jumped to 70, with at
least 100 different types identified, and a dozen
different nations actively pursuing their own
production and research/development programs.
While the numbers are not available for 2004, there is
little doubt that the technology has continued to
spread rapidly. And why are anti-ship cruise missiles
so attractive? The answer is that they are relatively
simple to develop, especially in comparison with
ballistic missiles. Cruise missiles can be constructed
from many of the same readily available parts and
components used in commercial aviation. They are also
reliable and effective, easy to deploy and use, and are
relatively inexpensive. Even poor nations can afford
them. One cruise missile represents but a tiny fraction
of the immense expenditure of capital the US has
invested in each of its 300 active warships. Yet, a
single cruise missile can sink or severely disable any
ship in the US Navy.
According to the GAO report, "the key to defeating
cruise missile threats is in gaining additional
reaction time," so that ships can detect, identify and
destroy the attacking missiles. The thorny problem, as
I've pointed out, is that the Navy's long-range AWACs
and intermediate-range Aegis radar defense systems are
significantly less effective in littoral (or coastal)
environments, the Persian Gulf being the prime
The other important factor is that cruise missile
technology itself is racing ahead. The GAO report
warned that the next generation of anti-ship missiles
that will begin to appear by 2007 will be faster and
stealthier, and will also be equipped with advanced
target-seekers, i. e., advanced guidance systems. In
fact, one of these advanced anti-ship cruise missiles
is already available: the Russian-made Yakhonts
missile. It flies at close to Mach 3 (three times the
speed of sound), can hit a squirrel in the eye, and has
a range of 185 miles: enough range to target the entire
Persian Gulf (from Iran), shredding Gen. Kernan's glib
remark that in a real war the US expeditionary force
will stand-off in safety "over the horizon" while
mounting an amphibious attack. Nonsense. Henceforth, in
a real Gulf war situation there will be no standing off
in safety. The Yakhonts missile has already erased the
concept of the horizon, at least, within the Persian
Gulf, and it has done so without ever having been fired
in combat---yet.
Gen. Kernan should have known also that, according to
Jane's Defense Weekly and other sources, Iranian
government officials were in Moscow the previous year
(2001), shopping for the latest Russian anti-ship
missile technology. 7 By their own admission the
Russians developed the Yakhonts missile for export. No
doubt, it was high on Iran's shopping list.
The 2000 GAO report's conclusions were not favorable.
It stated that for a variety of reasons the Navy's
forecasts for upgrading US ship defenses against cruise
missile attack are overly optimistic. The Navy's own
data shows that there will be no silver bullet. The
technology gap is structural, and will not be overcome
for many years, if at all. US warships will be
vulnerable to cruise missile attack into the
foreseeable future, perhaps increasingly so.
But the GAO saved its most sobering conclusion for
last: It so happens that the most vulnerable ship in
the US fleet is none other than the flagship itself,
the big Nimitz-class carriers. This underscores the
significance of Force Red's victory during Millennium
Challenge. Just think: If Van Riper could accomplish
what he did with Silkworms, the lowly scuds of the
cruise missile family, imagine what could happen if the
US Navy, sitting in the Gulf like so many ducks, should
face a massed-attack of supersonic Yakhonts missiles, a
weapon that may well be unstoppable.
It would be a debacle.
So we see that the 2002 US war games afforded a glimpse
of the same military hubris that gave us the Viet Nam
War and the current quagmire in Iraq. The difference is
that the peril for the world today in the "Persian
Lake" is many times greater than it ever was in the
Gulf of Tonkin.


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Let's talk about Deutsche Bank (DB). Deutsche Bank is the 11th largest bank in the world. It has assets of $1.8 trillion and over ~$60 trillion in derivatives on its books. From a balance sheet perspective, DB's balance sheet is 50% the size of Germany's GDP. By way of comparison,
The post I Don't See How Germany Can Contain the Deutsche Bank Collapse appeared first on Gains Pains & Capital.

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text: Schlumberger N.V. Company Profile (NYSE:SLB) Ratings Earnings Estimates Dividends Insider Trades Headlines Social Company Profile FAQ Charts About Schlumberger N.V. Schlumberger N.V. is a supplier of technology, integrated project management and information solutions to the international oil and gas exploration and production industry. The Company operates in the oilfield service markets through three groups: Reservoir Characterization, Drilling and Production. Reservoir Characterization Group consists of the principal technologies involved in finding and defining hydrocarbon resources. These include WesternGeco, Wireline, Testing Services and Schlumberger Information Solutions. Drilling Group consists of the principal technologies involved in the drilling and positioning of oil and gas wells and consist of Bits & Drilling Tools, M-I SWACO, Drilling & Measurements, Land Rigs and Integrated Drilling Services. Production Group consists of the principal technologies involved in the lifetime production of oil and gas reservoirs and includes Well Services, Water Services, Integrated Production Services and Schlumberger Production Management. Industry, Sector and Symbol: Sector: Oils/Energy Industry: Oil & Gas Equipment & Services Sub-Industry: Oil & Gas Equipment & Services Exchange: NYSE Symbol: SLB CUSIP: 80685710 Key Metrics: Previous Close: $80.4750 Day Moving Average: $83.64200 Day Moving Average: $81.6552-Week Range: $70.65 - $87.84Trailing P/E Ratio: N/AForeward P/E Ratio: 23.60P/E Growth: -54.67Market Cap: $111.97BOutstanding Shares: 1,391,475,000Beta: 1.06Profitability:Net Margins: -6.07%Return on Equity: 3.81%Return on Assets: 2.01%Debt:Debt-to-Equity Ratio: 0.40%Current Ratio: 1.59%Quick Ratio: 1.31% Additional Links: Visit Schlumberger N.V.'s Official WebsiteView SLB on Google FinanceView SLB on Yahoo FinanceView SLB's Company Profile on ReutersSearch for Schlumberger N.V. on Google Companies Related to Schlumberger N.V.:Halliburton Company (NYSE:HAL)Baker Hughes Incorporated (NYSE:BHI)National-Oilwell Varco (NYSE:NOV)Tesoro Logistics LP (NASDAQ:TLLP)Weatherford International PLC (NYSE:WFT)Key Energy Services (NYSE:KEG)Core Laboratories N.V. (NYSE:CLB)RPC (NYSE:RES)FMC Technologies (NYSE:FTI)Oceaneering International (NYSE:OII) Analyst Ratings Consensus Ratings for Schlumberger N.V. (NYSE:SLB) (?) The ratings breakdown includes the most recent rating from each analyst that has rated the stock within the last twelve months. The ratings score is a calculation of the average number of sell, hold, buy and strong buy ratings (0-1.5 = Sell, 1.5-2.5 = Hold, 2.5-3.5 = Buy, >3.5 = Strong Buy). The consensus price target is a mean average of the most recent price target set by each analyst that has set a price target for the stock in the last twelve months.Ratings Breakdown: 5 Hold Ratings, 23 Buy RatingsConsensus Rating:Buy (Score: 2.82)Consensus Price Target: $95.64 (18.85% upside) Analysts' Ratings History for Schlumberger N.V. (NYSE:SLB) Show: Only the Most Recent Rating From Each Brokerage All Ratings For This Stock DateFirmActionRatingPrice TargetDetails2/22/2017FBR & CoBoost Price TargetOutperform -> Outperform$105.00 -> $107.001/31/2017Evercore ISIReiterated RatingBuy$99.001/27/2017Jefferies Group LLCBoost Price TargetBuy$96.00 -> $99.001/23/2017Deutsche Bank AGSet Price TargetBuy$113.00 -> $101.001/23/2017StephensDowngradeOverweight -> Equal Weight1/23/2017Credit Suisse GroupBoost Price TargetOutperform$94.00 -> $95.001/18/2017SunTrust Banks, Inc.Initiated CoverageHold$92.001/12/2017BMO Capital MarketsReiterated RatingBuy$96.0012/1/2016Sanford C. BernsteinInitiated CoverageMarket Perform$92.0011/10/2016GuggenheimReiterated RatingBuy10/11/2016Citigroup Inc.Boost Price TargetBuy$89.00 -> $93.009/30/2016Loop CapitalInitiated CoverageBuy$90.008/19/2016Seaport Global SecuritiesReiterated RatingBuy8/16/2016NomuraSet Price TargetBuy$88.00 -> $91.007/26/2016ScotiabankReiterated RatingSector Outperform$80.00 -> $90.007/25/2016SimmonsReiterated RatingOverweight$84.00 -> $97.007/25/2016Howard WeilBoost Price TargetSector Outperform$80.00 -> $90.007/25/2016Cowen and CompanyBoost Price TargetOutperform$85.00 -> $92.007/25/2016Goldman Sachs Group, Inc. (The)Set Price TargetBuy$94.00 -> $100.007/22/2016J P Morgan Chase & CoReiterated RatingBuy7/18/2016Societe GeneraleUpgradeHold -> Buy$86.00 -> $91.005/10/2016Griffin SecuritiesUpgradeSell -> Neutral4/26/2016Barclays PLCLower Price TargetOverweight$93.00 -> $92.004/25/2016KLR GroupBoost Price TargetBuy$103.00 -> $106.004/25/2016Morgan StanleyReiterated RatingOverweight$105.00 -> $110.004/20/2016Standpoint ResearchDowngradeBuy -> Hold4/15/2016Royal Bank Of CanadaReiterated RatingOutperform$95.002/25/2016Susquehanna Bancshares IncLower Price TargetPositive$88.00 -> $86.002/19/2016DA DavidsonInitiated CoverageBuy$100.00 -> $94.001/25/2016Oppenheimer Holdings, Inc.Lower Price TargetOutperform$94.00 -> $92.001/21/2016Robert W. BairdLower Price Target$99.00 -> $82.001/21/2016Clarkson CapitalLower Price Target$90.00 -> $78.001/3/2016Sterne Agee CRTReiterated RatingBuy12/18/2015Iberia CapitalReiterated RatingBuy$94.0012/18/2015William BlairUpgradeMarket Perform -> Outperform10/20/2015ArgusReiterated RatingBuy$112.00 -> $92.0010/19/2015Capital One Financial CorporationLower Price TargetOverweight$87.00 -> $82.0010/16/2015S&P Equity ResearchReiterated RatingBuy9/9/2015MacquarieReiterated RatingNeutral$89.00 -> $81.009/3/2015HSBC Holdings plcLower Price TargetBuy$101.00 -> $96.007/20/2015Tigress FinancialDowngradeBuy -> Neutral7/20/2015Wells Fargo & CompanyUpgradeMarket Perform -> Outperform6/12/2015RS PlatouReiterated RatingSell$70.006/5/2015Atlantic SecuritiesInitiated CoverageOverweight$110.004/13/2015Raymond James Financial, Inc.DowngradeOutperform -> Market Perform(Data available from 2/24/2015 forward) Earnings Earnings History for Schlumberger N.V. (NYSE:SLB)DateQuarterConsensus EstimateActual EPSRevenue EstimateActual RevenueRelease LinkConference CallDetails4/19/2017 1/20/2017Q416$0.27$0.27$7.11 billionViewListen10/20/2016Q316$0.22$0.25$7.24 billion$7.00 billionViewListen7/21/2016Q216$0.21$0.23$7.09 billion$7.16 billionViewListen4/21/2016Q116$0.39$0.40$7.04 billion$6.52 billionViewN/A1/21/2016Q415$0.63$0.65$7.94 billion$7.74 billionViewListen10/15/2015Q315$0.77$0.78$8.58 billion$8.47 billionViewListen7/16/2015Q215$0.79$0.88$9.19 billion$9.01 billionViewListen4/16/2015Q115$0.97$1.06$10.55 billion$10.25 billionViewListen1/15/2015Q414$1.46$1.50$12.64 billionViewListen10/16/2014Q314$1.47$1.49$12.65 billion$12.60 billionViewListen7/17/2014Q214$1.36$1.37$11.94 billion$12.05 billionViewListen4/17/2014Q114$1.20$1.21$11.49 billion$11.24 billionViewListen1/17/2014Q413$1.35$1.35$12.06 billion$11.91 billionViewListen10/18/2013Q313$1.24$1.29$11.58 billion$11.61 billionViewListen7/19/2013Q2 2013$1.11$1.15$11.15 billion$11.18 billionViewListen4/19/2013Q1 2013$1.01$0.94$10.75 billion$10.67 billionViewListen1/18/2013Q4 2012$1.13$1.08$10.82 billion$11.17 billionViewListen10/19/2012$1.07$1.08ViewN/A7/20/2012$1.00$1.05ViewN/A4/20/2012$0.98$0.98ViewN/A1/20/2012$1.09$1.11ViewN/A10/21/2011$1.01$0.98ViewN/A7/22/2011$0.85$0.87ViewN/A4/21/2011$0.76$0.71ViewN/A1/21/2011$0.78$0.85ViewN/A(Data available from 1/1/2011 forward) Estimates Earnings Estimates for Schlumberger N.V. (NYSE:SLB)Current Year EPS Consensus Estimate: $1.79 EPSNext Year EPS Consensus Estimate: $3.41 EPSQuarterNumber of EstimatesLow EstimateHigh EstimateAverage EstimateQ1 201616$0.34$0.62$0.48Q2 201612$0.16$0.64$0.39Q3 201610$0.19$0.68$0.27Q4 201611$0.25$0.76$0.31Q1 201711$0.23$0.90$0.40Q2 201711$0.33$1.05$0.51Q3 201711$0.46$1.18$0.63Q4 201710$0.54$1.07$0.70Q1 20183$0.62$0.73$0.67Q2 20183$0.76$0.82$0.78Q3 20183$0.93$1.02$0.98Q4 20183$1.09$1.18$1.14(Data provided by Zacks Investment Research) Dividends Current Dividend Information for Schlumberger N.V. (NYSE:SLB)Annual Dividend:$2.00Dividend Yield:2.49%Dividend Growth:18.20% (3 Year Average)Payout Ratio:-169.49% (Based on Trailing 12 Months of Earnings) 111.73% (Based on Current Year Consensus EPS Estimate)58.65% (Based on Next Year Consensus EPS Estimate)Track Record:6 Years of Consecutive Dividend GrowthDividend History for Schlumberger N.V. (NYSE:SLB)AnnouncedPeriodAmountYieldEx-Dividend DateRecord DatePayable Date1/20/2017quarterly$0.502.37%2/13/20172/15/20174/17/201710/20/2016quarterly$0.502.36%12/5/201612/7/20161/13/20177/21/2016quarterly$0.502.48%9/2/20169/7/201610/14/20164/22/2016Quarterly$0.502.7%5/27/20166/1/20167/8/20161/21/2016quarterly$0.503.16%2/12/20162/17/20164/8/201610/15/2015quarterly$0.5011/30/201512/2/20151/8/20167/16/2015quarterly$0.508/31/20159/2/201510/9/20154/16/2015quarterly$0.502.16%6/1/20156/3/20157/10/20151/15/2015quarterly$0.502.49%2/9/20152/11/20154/10/201510/16/2014quarterly$0.401.66%12/1/201412/3/20141/9/20157/17/2014quarterly$0.408/29/20149/3/201410/10/20144/17/2014quarterly$0.401.57%6/2/20146/4/20147/11/20141/16/2014quarterly$0.402/14/20142/19/20144/11/201410/17/2013quarterly$0.311.34%12/2/201312/4/20131/10/20147/18/2013quarterly$0.319/4/201310/11/20134/18/2013quarterly$0.316/5/20137/12/20131/17/2013quarterly$0.312/20/20134/12/2013(Data available from 1/1/2013 forward) Insider Trades Insider Trading History for Schlumberger N.V. (NYSE:SLB)Insider Ownership Percentage: 0.36%Institutional Ownership Percentage: 78.66%Transaction DateInsider NameTitleBuy/SellNumber of SharesAverage Share PriceTotal TransactionDetails12/21/2016Ashok BelaniEVPSell46,577$85.50$3,982,333.50 12/20/2016Gerard MartellozoVPSell5,000$84.83$424,150.00 12/14/2016Mark DantonVPSell2,430$86.09$209,198.70 12/12/2016Imran KizilbashVPSell134,091$86.35$11,578,757.85 12/8/2016Simon AyatCFOSell40,000$84.00$3,360,000.00 11/18/2016Mark DantonVPSell10,000$79.99$799,900.00 11/15/2016Tore I SandvoldDirectorSell5,000$81.00$405,000.00 10/27/2016Stephane BiguetVPSell3,000$79.73$239,190.00 9/30/2016Tore I SandvoldDirectorSell2,500$78.09$195,225.00 8/29/2016Michael E MarksDirectorSell13,600$81.19$1,104,184.00 8/18/2016Simon AyatCFOSell50,000$83.68$4,184,000.00 8/2/2016Stephane BiguetVPSell4,227$78.52$331,904.04 7/27/2016Robert Scott RoweInsiderSell8,001$80.65$645,280.65 7/25/2016Howard GuildInsiderSell11,900$81.32$967,708.00 6/9/2016Paal KibsgaardCEOSell32,857$80.00$2,628,560.00 6/7/2016Patrick SchornPresidentSell9,128$80.27$732,704.56 5/31/2016Lubna S OlayanDirectorBuy1,500$77.07$115,605.00 4/25/2016Sherif FodaInsiderSell3,500$78.92$276,220.00 3/3/2016Sherif FodaInsiderSell197$74.09$14,595.73 2/29/2016Sherif FodaInsiderSell1,000$72.54$72,540.00 1/25/2016Alexander C JudenGeneral CounselSell19,000$65.80$1,250,200.00 1/25/2016Howard GuildCAOSell2,305$65.86$151,807.30 1/25/2016Mark DantonDirectorSell2,294$65.92$151,220.48 8/27/2015Darkes V Maureen KempstonDirectorBuy3,000$72.24$216,720.00 7/21/2015Lubna S OlayanDirectorBuy5,000$83.82$419,100.00 6/26/2015Tore I SandvoldDirectorSell2,000$86.37$172,740.00 4/22/2015Mark DantonDirectorSell8,557$91.86$786,046.02 4/20/2015Aaron Gatt FloridiaPresidentSell11,400$93.65$1,067,610.00 4/20/2015Gerard MartellozoVPSell2,000$93.27$186,540.00 4/20/2015Sherif FodaInsiderSell5,000$93.43$467,150.00 3/23/2015Gerard MartellozoVPSell8,000$82.35$658,800.00 1/21/2015Mogharbel Khaled AlInsiderSell3,392$80.00$271,360.00 1/20/2015Alexander C JudenGeneral CounselSell12,445$80.36$1,000,080.20 1/20/2015Gerard MartellozoVPSell8,000$80.08$640,640.00 1/20/2015Howard GuildCAOSell1,588$80.13$127,246.44 1/20/2015Jean-Francois PoupeauEVPSell14,738$79.12$1,166,070.56 1/20/2015Mark DantonDirectorSell1,982$79.50$157,569.00 1/20/2015Paal KibsgaardCEOSell22,000$80.36$1,767,920.00 10/27/2014Michael E MarksDirectorBuy3,250$92.59$300,917.50 8/28/2014Gerard MartellozoVPSell12,000$110.60$1,327,200.00 8/25/2014Mark DantonDirectorSell7,612$110.01$837,396.12 8/7/2014Jean-Francois PoupeauEVPSell42,316$107.01$4,528,235.16 7/25/2014Simon AyatCFOSell54,566$112.37$6,131,581.42 6/30/2014Ashok BelaniEVPSell230,032$117.49$27,026,459.68 4/29/2014Mark DantonDirectorSell16,579$102.84$1,704,984.36 4/25/2014Stephanie CoxVPSell19,522$101.44$1,980,311.68 4/24/2014Sherif FodaInsiderSell10,000$102.31$1,023,100.00 4/23/2014Alexander JudenGeneral CounselSell55,601$101.93$5,667,409.93 4/23/2014Paal KibsgaardCEOSell143,800$101.61$14,611,518.00 4/21/2014Howard GuildCAOSell30,000$100.25$3,007,500.00 2/24/2014Patrick SchornPresidentSell52,000$92.18$4,793,360.00 2/21/2014Paal KibsgaardCEOSell208,800$91.05$19,011,240.00 1/21/2014Alexander JudenGeneral CounselSell3,327$92.00$306,084.00 1/21/2014Howard GuildCAOSell3,528$92.00$324,576.00 1/21/2014Jean-Francois PoupeauEVPSell14,175$92.00$1,304,100.00 1/21/2014Mark DantonDirectorSell1,484$92.00$136,528.00 1/21/2014Patrick SchornPresidentSell2,990$92.00$275,080.00 11/8/2013Mark DantonDirectorSell6,900$93.72$646,668.00 11/6/2013Malcolm TheobaldVPSell5,565$93.17$518,491.05 10/22/2013Sherif FodaInsiderSell13,200$94.00$1,240,800.00 10/21/2013Alexander C JudenGeneral CounselSell55,299$93.66$5,179,304.34 8/7/2013Sherif FodaInsiderSell4,980$81.07$403,728.60 5/16/2013Paal KibsgaardCEOSell61,681$75.78$4,674,186.18 2/15/2013Satish PaiEVPSell13,235$80.47$1,065,020.45 2/5/2013Jean-Francois PoupeauEVPSell8,000$79.88$639,040.00 2/5/2013Patrick SchornPresidentSell2,177$79.88$173,898.76 2/5/2013Stephen OrrInsiderSell2,569$79.88$205,211.72 (Data available from 1/1/2013 forward) Headlines Latest Headlines for Schlumberger N.V. (NYSE:SLB)DateHeadlineWill Upstream Operators' Capexes Affect SLB's 1Q17 Margin? (NYSE:SLB)us.rd.yahoo.com - February 23 at 8:02 PMWill Schlumberger's Debt Be a Concern in 2017? (NYSE:SLB)us.rd.yahoo.com - February 23 at 8:02 PMColor-changing hair dye is the flawless product for commitment phobes (NYSE:SLB)eleganthomesinla.com - February 22 at 8:04 PMSmart Money Buying the Price Weakness of Schlumberger NV (SLB) (NYSE:SLB)techknowbits.com - February 22 at 8:04 PMWhat Does Schlumberger's Historical Valuation Suggest? (NYSE:SLB)us.rd.yahoo.com - February 22 at 8:04 PMHome Depot, Wal-Mart, Halliburton, Schlumberger PTs Raised (NYSE:SLB)us.rd.yahoo.com - February 22 at 9:56 AMSchlumberger (SLB) Down 7.5% Since Earnings Report: Can It Rebound? (NYSE:SLB)finance.yahoo.com - February 21 at 5:02 PMComparing Relative Valuations among 4 Oilfield Services Companies (NYSE:SLB)marketrealist.com - February 20 at 8:53 AMOil Services, Equipment Stocks To Watch As U.S. Shale Revives (NYSE:SLB)us.rd.yahoo.com - February 19 at 8:54 AMCrazy Volume Spikes for: Schlumberger Limited (NYSE:SLB) (NYSE:SLB)www.graffiotech.com - February 17 at 7:33 PMEPS Growth overview of Schlumberger Limited (NYSE:SLB) (NYSE:SLB)oakridgeobserver.com - February 17 at 7:33 PMROA of Schlumberger Limited (NYSE:SLB) stands at -2.2 (NYSE:SLB)prensariotiretail.com - February 16 at 7:35 PMStock Price of Schlumberger NV (SLB) Decreases -0.41% - Morning Outlook (NYSE:SLB)www.morningoutlook.com - February 13 at 8:20 AMSg Americas Securities Cuts Position in Schlumberger Limited. (SLB) by $55107251 (NYSE:SLB)emfizz.com - February 11 at 2:21 AMRelative Strength Index Pointing to Overbought Range for Schlumberger Limited (NYSE:SLB) (NYSE:SLB)brassale.net - February 11 at 2:21 AMAnalyst Forecast Changes: Schlumberger Limited (SLB) (NYSE:SLB)prensariotiretail.com - February 11 at 2:21 AMThe Schlumberger NV (SLB) Stake Raised by Intrust Bank NA (NYSE:SLB)mlbinjurynews.com - February 10 at 3:57 AMNuance Investments Boosts Position by $51344366 in Schlumberger Limited. (SLB) (NYSE:SLB)techknowbits.com - February 10 at 3:57 AMEx-Dividend Reminder: DuPont, Materion and Schlumberger (NYSE:SLB)www.forbes.com - February 9 at 12:10 PMSchlumberger Limited (SLB) Stock Could Be a Gusher. Tap It! (NYSE:SLB)investorplace.com - February 9 at 8:12 AMSchlumberger Shares Enter Oversold Territory (NYSE:SLB)www.forbes.com - February 8 at 11:51 AMUnusual Volume Spikes For: Schlumberger Limited (NYSE:SLB) (NYSE:SLB)mundoaguaysaneamiento.net - February 8 at 6:08 AMSchlumberger's Pullback Could Lead to a Rebound: Charts (NYSE:SLB)us.rd.yahoo.com - February 8 at 6:08 AMSchlumberger Announces First-Quarter 2017 Results Conference Call (NYSE:SLB)uk.finance.yahoo.com - February 8 at 6:08 AMStock Price of Schlumberger NV (SLB) Decreases -2.37% - Highland Mirror (NYSE:SLB)www.highlandmirror.com - February 6 at 8:23 AMStocks Favored by Analysts: Schlumberger NV (NYSE:SLB), Whole Foods Market, Inc. (NASDAQ:WFM) - The Standard (NYSE:SLB)6milestandard.com - February 5 at 1:27 AMAs Schlumberger LTD (SLB) Share Value Declined, Altrinsic Global Advisors LLC Has Upped by $23.18 Million Its Holding (NYSE:SLB)randolphguide.com - February 4 at 1:37 AMFeatured Stock to Focus: Schlumberger Limited (NYSE:SLB) (NYSE:SLB)xboxonezone.com - February 4 at 1:37 AMWhy Did Weatherford International's Stock Price Jump? (NYSE:SLB)marketrealist.com - February 4 at 1:37 AMState Farm Mutual Automobile Insurance Company Position in Schlumberger LTD (SLB) Has Raised as Shares Declined (NYSE:SLB)randolphguide.com - February 3 at 5:10 AMSchlumberger LTD (SLB) Holder Stevens Capital Management LP Increased Its Position by $35.95 Million as Stock Price Declined (NYSE:SLB)randolphguide.com - February 2 at 2:36 AMSchlumberger LTD (SLB) Holder Bank Of New York Mellon Corp Trimmed Stake as Share Value Declined (NYSE:SLB)randolphguide.com - February 1 at 5:03 AMAs Schlumberger LTD (SLB) Market Valuation Declined, Manning & Napier Advisors LLC Increased Stake by $10.18 Million (NYSE:SLB)randolphguide.com - January 30 at 9:38 PMSchlumberger NV : SLB-US: Dividend Analysis : December 07th, 2016 (record date) : By the numbers : January 30, 2017 (NYSE:SLB)www.capitalcube.com - January 30 at 9:38 PMIs There Inherent Value in Schlumberger N.V. (NYSE:SLB ... - Wall Street Beacon (NYSE:SLB)wsbeacon.com - January 30 at 1:50 AMNorth American Management Corp Cuts Position in Schlumberger Limited. (SLB) by $17334502 (NYSE:SLB)flapship.com - January 28 at 7:59 PMSchwartz Investment Counsel Inc. Sells 47500 Shares of Schlumberger N.V. (SLB) (NYSE:SLB)xboxonezone.com - January 28 at 7:59 PMSCHLUMBERGER LIMITED/NV Financials (NYSE:SLB)finance.yahoo.com - January 28 at 7:59 PMCambiar Investors LLC Stake in Schlumberger LTD (SLB) Has Increased by $80.76 Million (NYSE:SLB)randolphguide.com - January 28 at 6:37 AMPost Earnings Coverage as Schlumberger Top and Bottom-line Exceeded Estimates (NYSE:SLB)us.rd.yahoo.com - January 27 at 3:27 AM5 Things Schlumberger Management Wants You to Know About the Oil Market in 2017 (NYSE:SLB)www.fool.com - January 26 at 11:43 AMSCHLUMBERGER LIMITED/NV Files SEC form 10-K, Annual Report (NYSE:SLB)us.rd.yahoo.com - January 26 at 5:20 AMSchlumberger Ends The Year On A Good Note, Expects Drilling Demand To Increase In 2017 (NYSE:SLB)www.forbes.com - January 25 at 9:53 AMThe Retirement Systems of Alabama Cuts Position in Schlumberger NV (SLB) (NYSE:SLB)instantcrickets.com - January 25 at 5:42 AMThe Schlumberger NV (SLB) Shares Sold by Ingalls & Snyder LLC (NYSE:SLB)nflnewsdesk.com - January 25 at 5:42 AMETFs with exposure to Schlumberger NV : January 24, 2017 (NYSE:SLB)www.capitalcube.com - January 25 at 5:42 AMSchlumberger May Slump in 2017 (NYSE:SLB)realmoney.thestreet.com - January 25 at 5:42 AMShale Frackers' Weak Sales Leave Investors Asking What Growth? (NYSE:SLB)www.bloomberg.com - January 25 at 5:42 AMEarnings in Full Force, Analysts Take Aim at Schlumberger N.V. (NYSE:SLB) - Wall Street Beacon (NYSE:SLB)wsbeacon.com - January 24 at 1:15 AMHoward Capital Management Boosts Position by $14386533 in Schlumberger Limited. (SLB) (NYSE:SLB)lasignare.com - January 23 at 8:14 PM Social What is Schlumberger N.V.'s stock symbol? Schlumberger N.V. trades on the New York Stock Exchange (NYSE) under the ticker symbol "SLB."How often does Schlumberger N.V. pay dividends? What is the dividend yield for Schlumberger N.V.? Schlumberger N.V. announced a quarterly dividend on Friday, January 20th. Stockholders of record on Wednesday, February 15th will be given a dividend of $0.50 per share on Monday, April 17th. This represents a $2.00 dividend on an annualized basis and a dividend yield of 2.49%. The ex-dividend date is Monday, February 13th. Where is Schlumberger N.V.'s stock going? Where will Schlumberger N.V.'s stock price be in 2017? 28 analysts have issued 1 year price targets for Schlumberger N.V.'s shares. Their predictions range from $86.00 to $110.00. On average, they anticipate Schlumberger N.V.'s share price to reach $95.64 in the next year.When will Schlumberger N.V. announce their earnings? Schlumberger N.V. is scheduled to release their next quarterly earnings announcement on Wednesday, April, 19th 2017.Who owns Schlumberger N.V. stock? Schlumberger N.V.'s stock is owned by a variety of of retail and institutional investors. Top institutional shareholders include State Street Corp (5.15%), FMR LLC (1.94%), Franklin Resources Inc. (0.77%), Fiduciary Management Inc. WI (0.67%), Loomis Sayles & Co. L P (0.55%) and Sands Capital Management LLC (0.39%). Company insiders that own Schlumberger N.V. stock include Aaron Gatt Floridia, Alexander C Juden, Ashok Belani, Darkes V Maureen Kempston, Gerard Martellozo, Howard Guild, Imran Kizilbash, Lubna S Olayan, Mark Danton, Michael E Marks, Paal Kibsgaard, Patrick Schorn, Robert Scott Rowe, Sherif Foda, Simon Ayat, Stephane Biguet and Tore I Sandvold.Who sold Schlumberger N.V. stock? Who is selling Schlumberger N.V. stock? Schlumberger N.V.'s stock was sold by a variety of institutional investors in the last quarter, including FMR LLC, Aberdeen Asset Management PLC UK, Sands Capital Management LLC, Thrivent Financial for Lutherans, GLG Partners LP, Systematic Financial Management LP, Quest Investment Management Inc. OR and Cadinha & Co. LLC. Company insiders that have sold Schlumberger N.V. stock in the last year include Ashok Belani, Gerard Martellozo, Howard Guild, Imran Kizilbash, Mark Danton, Michael E Marks, Paal Kibsgaard, Patrick Schorn, Robert Scott Rowe, Sherif Foda, Simon Ayat, Stephane Biguet and Tore I Sandvold.Who bought Schlumberger N.V. stock? Who is buying Schlumberger N.V. stock? Schlumberger N.V.'s stock was purchased by a variety of institutional investors in the last quarter, including State Street Corp, Russell Investments Group Ltd., Asset Management One Co. Ltd., Aviva PLC, Congress Asset Management Co. MA, Elkfork Partners LLC, Tyers Asset Management LLC and Loomis Sayles & Co. L P. Company insiders that have bought Schlumberger N.V. stock in the last two years include Darkes V Maureen Kempston and Lubna S Olayan.How do I buy Schlumberger N.V. stock? Shares of Schlumberger N.V. can be purchased through any online brokerage account. Popular online brokerages include Vanguard Brokerage Services, TD Ameritrade, E*TRADE, Scottrade, Fidelity and Charles Schwab. How much does a share of Schlumberger N.V. stock cost? One share of Schlumberger N.V. stock can currently be purchased for approximately $80.47. Schlumberger N.V. (NYSE:SLB) Chart for Friday, February, 24, 2017Institutional Ownership ChartEarnings History ChartDividend History Chart Last Updated on 2/24/2017 by MarketBeat.com Staff


text:
|Publication number
|Publication type
|Application number
|Publication date
|May 2, 1989
|Filing date
|Jul 16, 1987
|Priority date
|Jul 16, 1987
|Fee status
|Publication number
|Peter Kokayeff, Suheil F. Abdo
|Original Assignee
|Union Oil Company Of California
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (30), Non-Patent Citations (8), Referenced by (59), Classifications (20), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
The invention relates to a desulfurization process and a catalytic isomerization process for hydrocarbons, particularly paraffin-containing hydrocarbon feedstreams.
Natural or straight run gasoline, i.e., naphthas, contain chiefly normal paraffins (n-paraffins) which have relatively low octane numbers. In the catalytic isomerization of paraffins, such as n-hexane and n-pentane, to equilibrium mixtures of branched chain isomers, the octane rating of the paraffins is substantially increased. Previous processes directed to paraffin isomerization have employed acidpromoted aluminum chloride catalysts, Y-type crystalline zeolite catalysts containing an elemental metal of Group VIII of the Periodic Table (U.S. Pat. Nos. 3,236,761 and 3,236,762), synthetic mordenite catalysts containing highly-dispersed platinum or palladium in the presence of hydrogen (U.S. Pat. Nos. 3,527,835 and 3,299,153), stabilized Y-sieve hydrogen zeolite compositions (U.S. Pat. No. 3,354,077), and the like. Commonly used commercial isomerization catalysts contain significant proportions of relatively expensive platinum or palladium metal components.
The hydrocarbon feedstream to an isomerization reactor is generally treated (hydrotreated) to remove sulfur and nitrogen compounds that rapidly deactivate (even poison) the relatively expensive isomerization catalyst. A common method of treating the feedstream to reduce the sulfur content is by hydrodesulfurization wherein the feed is contacted with a sulfur-tolerant hydrogenation catalyst in the presence of hydrogen. Although good sulfur removal may be achieved with hydrodesulfurization units operating under severe conditions, the efficiency of such units is ultimately limited by equilibrium and/or kinetic considerations and further desulfurization is often necessary in downstream processes.
Downstream processes employing relatively inexpensive, catalytically active materials further reduce the sulfur content of a hydrocarbon by "absorbing" sulfur therefrom under either hydrogenative or nonhydrogenative conditions. Usually, the absorbent material contains a metal component, such as nickel, copper, or silver, and the feedstocks generally treated are reformer feedstocks, particularly naphthas. Typical of such processes are that disclosed in U.S. Pat. No. 2,755,226 to Annable wherein a bed of copper molybdate pellets is used to reduce the sulfur content of naphthas. Similarly, in U.S. Pat. No. 4,224,191 to Bishop III, U.S. Pat. No. 4,204,947 to Jacobson et al. and U.S. Patent 4,582,819 to Miller, the use of copper components supported on conventional carriers is disclosed for reducing the sulfur content of reformer feedstreams. Also, processes disclosed in U.S. Pat. No. 4,419,224 to Miller include reducing the sulfur content of reformer feedstreams with promoted nickel components on alumina carriers.
Reformer feedstreams typically contain substantial proportions of hydrocarbons boiling at a temperature higher than that of n-hexane. When the sulfur content of feedstreams containing substantial portions of lighter hydrocarbons, such as n-hexane and n-pentane, is too large, appreciable loss in a catalyst's n-pentane and n-hexane isomerization activity is observed. In the present invention, it has been discovered that the isomerization activity of these relatively expensive catalysts may be improved substantially by reducing the sulfur content in the isomerization feed to below 5 ppmw, more particularly below 2 ppmw, and most particularly below 1 ppmw. Such improved activity allows a petroleum refiner to operate at milder conditions and expend less energy to produce the desired isomerized products.
Accordingly, it is an object of the invention to reduce the concentration of sulfur in a hydrocarbon feedstream to be contacted with an isomerization catalyst, particularly a catalyst useful for isomerizing feedstreams containing n-hexane and/or n-pentane, to levels at which the activity of the catalyst is significantly improved.
Furthermore, in addition to protecting the isomerization catalyst from sulfur poisoning, the petroleum refiner may also desire an increase in the capacity of an isomerization unit. Therefore, another objective of the present invention is to simultaneously reduce the sulfur concentration and isomerize n-paraffins.
The invention relates to the removal of sulfur from an isomerization feedstock. In a two-stage embodiment of the invention, a sulfur-containing hydrocarbon feedstock is successively desulfurized and isomerized (or hydroisomerized). Typically the feedstock sulfur concentration is reduced to less than 5 ppmw by contact with a catalytic absorbent. The sulfur-deficient feedstock subsequently contacts an isomerization (or hydroisomerization) catalyst under suitable conditions producing an increased yield of pentane and/or hexane isomer compounds.
In another two-stage embodiment, the feedstock is simultaneously desulfurized and isomerized (or hydroisomerized) in an upstream reaction zone and subsequently further isomerized (or hydroisomerized) in a downstream reaction zone. In the upstream reaction zone a dual-function (desulfurization and isomerization) catalyst containing at least one metal component in combination with an acidic support component is contacted by the feedstock to produce a product hydrocarbon containing a reduced amount of sulfur, normal pentane and/or normal hexane compounds.
In single-stage embodiments, the paraffin-containing feedstock is isomerized (or hydroisomerized) by contact with the dual-function catalyst in either the presence or absence of sulfur in the feedstock. Although the dual-function catalyst is active for isomerization (or hydroisomerization) in the presence of sulfur in the feedstock, such activity is better when less than 5 ppmw, and preferably no sulfur is present in the feedstock.
The invention provides a process for reducing the sulfur content of a hydrocarbon oil containing n-paraffins to less than 5 ppmw, preferably less than 2 ppmw, and most preferably to less than 1 ppmw, usually by contact with a catalytic absorbent active for removing sulfur. Such desulfurization occurs either prior to, or simultaneously with, contacting the oil with a catalyst useful for isomerizing n-pentane and/or n-hexane compounds.
It will be understood that, although the term "catalytic absorbent" is used herein to describe the material of the present invention with which the hydrocarbon feedstock were contacted, and the term "absorbed" is used to describe the mechanism by which the sulfur is held thereon, the invention embraces whatever mechanism, including adsorption, absorption, deposition, chemical reactions, etc., or some combinations of such mechanisms, by which the sulfur is removed from the hydrocarbon feedstock and retained by the catalytic absorbent.
It will be further understood that the "catalytic absorbent" referred to herein, although useful for removing sulfur from hydrocarbon feedstocks, may also, in some embodiments of the invention, function as a "dual-function catalyst" for simultaneously promoting the desulfurization and isomerization (or hydroisomerization) of feedstocks containing n-pentane and/or n-hexane.
The hydrocarbon feeds isomerized and/or desulfurized in the present invention include straight run petroleum distillates obtained from crude oil, hydrocracked feedstocks, coker products and the like. Examples include straight run naphthas, coker naphthas, hydrocracked naphthas, thermally cracked or catalytically cracked naphthas and blends thereof. The feedstock to the process may boil in the range from about 50� F. to about 200� F. and preferably entirely boils at temperatures less than about 175� F. The feedstock will usually comprise pentane and hexane predominantly in the forms of n-pentane and n-hexane. Usually the feedstock contains a mixture of at least 20, and typically at least about 35 weight percent n-pentane or n-hexane and may consist only of pentane and/or hexane. A highly preferred feedstock is a light gasoline fraction (i.e., boiling in the range from about 50� F. to about 185� F.) having an octane rating needing improvement. Also, the feedstock may contain sulfur largely in the form of organosulfur compounds, such as mercaptans, disulfides, thiophenes, and the like.
The process of the invention is preferably utilized in conjunction with a catalytic hydrotreating operation. That is, the feedstock to be subjected to desulfurization and isomerization or hydroisomerization in the process of the invention most usually comprises the effluent from a catalytic hydrotreater. In the hydrotreating process, the sulfur and nitrogen components in a hydrocarbon-containing liquid are converted by reaction with hydrogen at elevated temperatures and pressures to hydrogen sulfide and ammonia, respectively, in the presence of a hydrotreating catalyst usually comprising Group VIII and VIB metal components on a porous non-cracking refractory oxide, such as a sulfided catalyst containing nickel and/or cobalt components plus molybdenum and/or tungsten components on alumina. In a preferred method of operation, hydrotreating a feed containing a straight run gasoline will precede desulfurization and isomerization, and the feedstock most usually subjected to desulfurization and isomerization in the process of the present invention will be the effluent from such a hydrotreating method after the hydrogen sulfide and ammonia have been removed. Such a hydrotreated feedstock typically contains organonitrogen compounds in a concentration less than about 10 ppmw, usually less than 1 ppmw, and preferably less than about 0.1 ppmw, calculated as N, and contains organosulfur compounds in a concentration less than about 30 ppmw, usually about 0.05 to about 5 ppmw, preferably about 0 to about 2 ppmw, and most preferably in the range between 0 and 1 ppmw, calculated as S. Generally speaking, however, the hydrotreated feedstock will contain at least about 0.01 ppmw of sulfur.
Although the sulfur content of the feedstock may be reduced to the desired level by such desulfurization processes as caustic scrubbing, hydrodesulfurization and the like, the preferred process employs a catalytic absorbent. The catalytic absorbent in the process must be capable of removing sulfur upon contact with a sulfur-containing fluid, particularly a liquid and/or gaseous hydrocarbon feedstock. The catalytic absorbent ordinarily contains one or more metal components supported on an amorphous, porous refractory oxide having sufficient surface area for absorption of sulfur impurities and preferably having essentially all pores of diameter greater than 20 angstroms. The absorbent may contain any metal capable of reacting with organosulfur compounds at an elevated temperature, e.g., about 600� F. The support material is usually a calcined, amorphous refractory oxide and generally contains no crystalline molecular sieve. The amorphous, porous refractory oxide support is typically calcined at a temperature greater than 500� F. and ordinarily greater than 800� F., prior to being employed in the method z of the invention. Preferred amorphous, porous refractory oxide supports include alumina, silica, silica-alumina, zirconia, titania, boria, magnesia and combinations thereof. The most preferred support is gamma alumina having a surface area above 100 m2 /gram. Typical metal components are copper, zinc, nickel, platinum, cobalt, iron and molybdenum, particularly in the oxide or reduced form. The most preferred metal components contain nickel or copper. Typical catalytic absorbents treated in the present invention are disclosed in U.S. Pat. Nos. 4,204,947, 4,582,819, and 4,336,130, which are herein incorporated by reference in their entirety.
A preferred catalytic absorbent of the invention is prepared by first comulling a copper component, such as copper(II) carbonate, or a nickel component, such as nickel carbonate, with alumina to form an extrudable paste, and then extruding the paste through a die and calcining the extrudate at a temperature greater than 700� F. to produce a coppergamma alumina or nickel-gamma alumina extrudate having a circular cross-sectional diameter from about 1/4 to about 1/20 inches, preferably about 1/8 inch, containing about 10 to about 80 weight percent of copper oxide, calculated as Cu, or about 10 to about 80 weight percent of nickel, calculated as Ni, and having essentially all pores of diameter greater than about 20 angstroms. The absorbent may also be prepared by aqueous impregnation if the copper compound, such as copper nitrate, is soluble in water. The surface area of the absorbent is about 100 to about 350 m2 /gram, the compact bulk density is about 0.5 to about 0.9 grams/ml, and the crushing strength is about 5 to about 30 lbs/1/8 inch length. (Crushing strength in "lbs/1/8 inch length" is determined for an extrudate or other absorbent sample of cylindrical shape having a 1/8 inch length and a 1/8 inch diameter, using metal jaws having a width of 1/8 inch and with the force applied on the circumferential surface of the cylinder.)
The invention also provides for a "dual-function catalyst" simultaneously useful (1) in the removal of organosulfur compounds from a hydrocarbon oil in the liquid and/or gaseous phase and (2) in the production of a high yield of pentane and/or hexane isomer compounds from a hydrocarbon oil containing n-pentane and/or n-hexane. The dual-function catalyst contains at least one active metal component combined with at least one acidic component. Preferably, the dual-function catalyst contains at least one non-noble Group VIII active metal component, preferably nickel metal components. In addition to Group VIII metals, the dual-function catalysts may also contain a Group VIB metal component, for example, tungsten and/or molybdenum components. As will be shown hereinafter, the dual-function catalyst utilized in the present invention proves highly superior for simultaneously isomerizing (or hydroisomerizing) and desulfurizing sulfur-containing feedstocks as compared to a commercial isomerization catalyst.
The dual-function catalyst comprises an acidic component having sufficient acidity to impart activity for isomerizing a hydrocarbon feedstock, particularly a feedstock containing n-pentane and/or n-hexane. Suitable acidic components include silica-aluminas and crystalline molecular sieves having isomerizing activity. Crystalline molecular sieves are preferred acidic components. The term "crystalline molecular sieve" as used herein refers to any crystalline acidic component capable of separating atoms or molecules based on their respective dimensions. Crystalline molecular sieves may be zeolitic or nonzeolitic. The term "nonzeolitic" as used herein refers to molecular sieves whose frameworks are not formed of substantially only silica and alumina tetrahedra. The term "zeolitic" as used herein refers to molecular sieves whose frameworks are formed of substantially only silica and alumina tetrahedra such as the framework present in ZSM-5 type zeolites, Y zeolites, and X zeolites. Examples of zeolitic crystalline molecular sieves which can be used as an acidic component of the catalyst include Y zeolite, fluorided Y zeolites, X zeolites, zeolite beta, zeolite L, mordenite and zeolite omega. Examples of nonzeolitic crystalline molecular sieves which may be used as an acidic component of the catalyst include silicoaluminophosphates, aluminophosphates, ferrosilicates, titanium aluminosilicates, borosilicates and chromosilicates.
The most preferred zeolitic crystalline molecular sieves for the dual-function catalyst are crystalline aluminosilicate Y zeolites. U.S. Pat. No. 3,130,007, the disclosure of which is hereby incorporated by reference in its entirety, describes Y-type zeolites having an overall silica-to-alumina mole ratio between about 3.0 and about 6.0, with a typical Y zeolite having an overall silica-to-alumina mole ratio of about 5.0. It is also known that Y-type zeolites can be produced, normally by dealumination, having an overall silica-to-alumina mole ratio above 6.0. Thus, for purposes of this invention, a Y zeolite is one having the characteristic crystal structure of a Y zeolite, as indicated by the essential X-ray powder diffraction pattern of Y zeolite, and an overall silica-to-alumina mole ratio above 3.0, and includes Y-type zeolites having an overall silica-to-alumina mole ratio above about 6.0.
Typical Y zeolites in the sodium (or other alkali metal) form have few or no acid sites and, thus, have little or no cracking or isomerizing activity. The acidity of the Y zeolite may be increased by exchanging the sodium in the Y zeolite with ammonium ions, polyvalent metal cations, such as rare earth-containing cations, magnesium cations or calcium cations, or a combination of both, thereby lowering the sodium content. Such an ion-exchange may reduce the stability of the Y zeolite and (typically in the case of ammonium exchanges) the Y zeolite is then steam-treated at a high temperature (i.e., about 600� C. to about 800� C.) followed by further ion-exchange. For sufficient cracking or isomerizing activity, the sodium (or other alkali metal) content of the zeolite is generally reduced to less than about 1.0 weight percent, preferably less than about 0.5 weight percent and most preferably less than about 0.3 weight percent, calculated as Na2 O. Methods of carrying out the ion exchange are well known in the art.
A preferred Y zeolite for the dual-function catalyst is one prepared by first ammonium exchanging a Y zeoiite to a sodium content between about 0.6 and 5 weight percent, calculated as Na2 O, calcining the ammonium exchanged zeolite in the presence of at least 0.2 p.s.i. water vapor partial pressure at a temperature between 600� F. and 1,650� F. to reduce the unit cell size to a value in the range between 24.40 and 24.64 Angstroms, and then ammonium exchanging the zeolite once again to replace at least 25 percent of the residual sodium ions and obtain a zeolite product of less than 1.0 weight percent sodium and preferably less than 0.6 weight percent sodium, calculated as Na2 O. Such a Y zeolite is highly stable and maintains a high activity. The zeolite is described in detail in U.S. Pat. No. 3,929,672, the disclosure of which is hereby incorporated by reference in its entirety. A preferred member of this group is known as Y-82, a zeolitic aluminosilicate molecular sieve available from the Linde Division of the Union Carbide Corporation.
Another group of Y zeolites which may be used as a molecular sieve in the dual-function catalyst is comprised of zeolites normally having an overall silica-to-alumina mole ratio above about 6.0, preferably between about 6.1 and about 15. The zeolites of this group are prepared by dealuminating a Y-type zeolite having an overall silica-to-alumina mole ratio below about 6.0 and are described in detail in U.S. Pat. No. 4,503,023 issued to Breck et al., and European Patent Application No. 84104815.0 published on Nov. 7, 1984 as Publication No. 0 124 120 by Best et al., the disclosures of which are hereby incorporated by reference in their entireties. A preferred member of this group is known as LZ-210, a zeolitic aluminosilicate molecular sieve available from the Linde Division of the Union Carbide Corporation. LZ-210 zeolites and the other zeolites of this group are conveniently prepared from a Y zeolite starting material in overall silica-to-alumina mole ratios between about 6.0 and about 15, although higher ratios are possible. Preferred LZ-210 zeolites have an overall silica-to-alumina mole ratio of about 6.1 to about 13.0. Typically, the unit cell size is at or below 24.65 Angstroms and will normally range between about 24.20 and about 24.65 Angstroms. LZ-210 zeolites having an overall silica-to-alumina mole ratio below 20 generally have a sorptive capacity for water vapor at 25� C. and 4.6 mm mercury water vapor partial pressure of at least 20 weight percent based on the anhydrous weight of the zeolite. Normally, the oxygen sorptive capacity at 100 mm mercury and -183� C. will be at least 25 weight percent. The LZ-210 class of zeolites have a composition expressed in terms of mole ratios of oxides as:
(0.85-1.1)M2/n O:Al2 O3 :xSiO2
wherein "M" is a cation having the valence "n" and "x" has a value greater than 6.0.
In general, LZ-210 zeolites may be prepared by dealuminating Y-type zeolites using an aqueous solution of a fluorosilicate salt, preferably a solution of ammonium hexafluorosilicate. The dealumination is accomplished by placing a Y zeolite, normally an ammonium exchanged Y zeolite, into an aqueous reaction medium such as an aqueous solution of ammonium acetate, and slowly adding an aqueous solution of ammonium fluorosilicate. After the reaction is allowed to proceed, a zeolite having an increased overall silica-to-alumina mole ratio is produced. The magnitude of the increase is dependent at least in part on the amount of fluorosilicate solution contacted with the zeolite and on the reaction time allowed. Normally, a reaction time of between about 10 and about 24 hours is sufficient for equilibrium to be achieved. The resulting solid product, which may be separated from the aqueous reaction medium by conventional filtration techniques, is a form of LZ-210 zeolite. In some cases this product may be subjected to a steam calcination by contacting the product with water vapor at a partial pressure of at least 0.2 p.s.i.a. for a period of between about 1/4 to about 3 hours at a temperature between about 900� F. and about 1,500� F. in order to provide greater crystalline stability.
In addition to the zeolitic crystalline molecular sieves disclosed herein and used in the Example, other examples of acidic components that may be combined with nickel or other active metals and their combinations include noncrystalline acidic materials such as silica-alumina or silica-alumina in an alumina dispersion. The latter is described in U.S. Pat. No. 4,097,365, the disclosure of which is incorporated by reference in its entirety.
An example of non-zeolite crystalline molecular sieves also useful as an acidic component in the dual-function catalyst is a silicoaluminophosphate, known by the acronym "SAPO," described in detail in U.S. Pat. No. 4,440,871, the disclosure of which is hereby incorporated by reference in its entirety. Another useful class of nonzeolitic crystalline molecular sieves is generally referred to as crystalline aluminophosphates, designated by the acronym "AlPO4." The structure and preparation of the various species of aluminophosphates are discussed in U.S. Pat. Nos. 4,310,440 and 4,473,663, the disclosures of which are hereby incorporated by reference in their entirety. Yet another class of nonzeolitic molecular sieves suitable for use is known as ferrosilicates, designated by the acronym "FeSO." A preferred ferrosilicate denominated as FeSO-38 is disclosed in European Patent Application No. 83220068.0 filed on Oct. 12, 1982 and published on May 16, 1984 as Publication No. 0 108 271 A2, the disclosure of which application is hereby incorporated by reference in its entirety. Still other examples of nonzeolitic sieves include borosilicates, chromosilicates and crystalline silicas. Borosilicates are described in U.S. Pat. Nos. 4,254,247, 4,264,813 and 4,327,236, the disclosures of which are hereby incorporated by reference in their entireties. Chromosilicates are described in detail in U.S. Pat. No. 4,405,502, the disclosure of which is also hereby incorporated by reference in its entirety. A preferred crystalline silica, essentially free of aluminum and other Group IIIA metals, is a silica polymorph, i.e., silicalite, which may be prepared by methods described in U.S. Pat. No. 4,061,724, the disclosure of which is hereby incorporated by reference in its entirety.
In preparing the dual-function catalyst, the acidic component may be combined with a binder or matrix material comprising a porous, inorganic refractory oxide component having essentially no cracking or isomerizing activity. The acidic component is combined with the porous, inorganic refractory oxide component, or a precursor thereof, such as alumina, silica, titania, magnesia, zirconia, borilia, silica-magnesia, silica-titania, other such combinations and the like, with alumina being the most highly preferred. Examples of precursors that may be used include peptized alumina, alumina gel, hydrated alumina, hydrogels, and silica sols. Normally, the porous, inorganic refractory oxide component or its precursor is mixed or comulled with an acidic component in amounts such that the final dry catalyst mixture will comprise (1) between about 2.5 weight percent and about 80 weight percent acidic component, preferably between about 15 weight percent and about 80 weight percent, and (2) between about 5 weight percent and about 90 weight percent of porous, inorganic refractory oxide, preferably between about 10 weight percent and about 40 weight percent. The comulled mixture is then formed into particulates, usually by extrusion through a die having openings of a cross sectional size and shape desired in the final catalyst particles. For example, the die may have openings therein in the shape of three-leaf clovers so as to produce an extrudate material similar to that shown in FIGS. 8 and 8A of U.S. Pat. No. 4,028,227, the disclosure of which is hereby incorporated by reference in its entirety. Among preferred shapes for the die openings are those that result in particles having surface-to-volume ratios greater than about 100 reciprocal inches. After extrusion, the catalyst particles are cut into lengths of from 1/16 to 1/2 inch. The resulting particles are subjected to a calcination at an elevated temperature, nrmally between about 600� F. and about 1600� F., to produce catalytic particles of high crushing strength.
The dual-function catalyst contains at least one Group VIII metal component, such as the oxides or sulfides thereof, typically in an amount from about 1 to about 40 weight percent, preferably between 10 and 25 weight percent, calculated as the metal. The dual-function catalyst may also contain one or more additional metal components, in particular, the metals, oxides and sulfides of the Group VIB elements. When the Group VIB metals are present in the catalyst, the Group VIII metals are contained in a mole ratio greater than 5 to 1, preferably greater than about 9 to 1, more preferably greater than about 18 to 1, and most preferably greater than about 25 to 1, as compared to the Group VIB metal (Group VIII to Group VIB metal). A mole ratio of Group VIII to Group VIB metal in the range from about 9 to 1 to about 60 to 1 is highly preferred. Suitable metal components are non-noble Group VIII metals such as nickel, cobalt and iron, and Group VIB metals including tungsten and molybdenum. Nickel is the most preferred metal. However, Group IB metals, such as copper, and Group IIB metals, such as zinc and cadmium, may replace the Group VIII metal. The Group IB, IIB and non-noble Group VIII metals are most preferably employed in proportions between 13 and about 30 weight percent, calculated as the monoxide, and the Group VIB metals in a proportion between about 0.05 and 3.0 weight percent, calculated as the trioxide. Furthermore, when Group VIB metals are present, the catalyst preferably contains at least an equal weight percent, and more preferably, a greater weight percent of Group VIII metal components, calculated as the monoxide, than that of the Group VIB components, calculated as the trioxide. When the metal components consist essentially of nickel and molybdenum metal components, the nickel component is usually present in proportions sufficient to ensure that the catalyst contains between 13 and about 30 weight percent of the nickel component, calculated as NiO, and the molybdenum component between about 0.05 weight percent and about 3.0 weight percent, calculated as MoO3.
Although nickel and other metal components may be supplied from essentially any convenient source, the typical inorganic compounds for use herein include nickel nitrate, nickel acetate, nickel carbonate, nickel oxide, ammonium heptamolybdate, molybdic trioxide, copper nitrate, copper carbonate, and the like. Organometallic compounds may be utilized such as cyclopentadienyl or carbonyl nickel compounds.
The metal components may be impregnated into the extruded catalyst particles from a liquid solution containing the desired component. Another method of combining the metal components with the acidic component is by mulling or comulling the metal compounds with the acidic components and binding materials. In a preferred embodiment, the extruded particles containing acidic components are impregnated with an aqueous solution containing dissolved nickel components.
The metals contained in the catalytic absorbent or dual-function catalyst, which will largely be present in their oxide forms after calcination in air, may be converted to their reduced forms, if desired, by contact at elevated temperatures in a reducing gas atmosphere comprising, for example, hydrogen. Most commonly, the reduction is accomplished by placing the absorbent or catalyst in its oxide form in the reactor vessel(s) wherein the isomerization and desulfurization reactions are to be performed and then passing gaseous hydrogen through the bed of materials under conditions of elevated temperature. The reducing agent may be present in the feedstock, or it may be a reducing gas added from an external source such as fresh or recycled hydrogen gas which has been stripped free of hydrogen sulfide. Alternatively still, the hydrogen may accompany the feedstock itself, as would be the case, for example, if the isomerization operation is performed immediately after hydrotreating. These and other equivalent methods for activating the catalytic absorbent or dual-function catalyst by conversion to the reduced form may be utilized in the invention.
The isomerization catalyst employed in the process of the invention includes any catalyst having the property of promoting the isomerization or hydroisomerization of n-paraffins in a hydrocarbon feedstock, and more particularly the isomerization of n-pentane and/or n-hexane compounds. Typical isomerization catalysts contain a noble metal such as platinum and/or palladium on a cracking or acidic component as hereinbefore described. A preferred acidic component for the isomerization catalyst is a zeolitic crystalline molecular sieve such as hydrogen mordenite. A highly preferred isomerization catalyst contains platinum and hydrogen mordenite. Examples of useful isomerization or hydroisomerization catalysts are disclosed in U.S. Pat. Nos. 4,232,181 and 4,182,692 issued to Kiovsky et al., U.S. Pat. No. 3,925,503 issued to Parthasarathy, and U.S. Pat. No. 4,238,319 issued to Hauschildt et al., all of which are incorporated by reference in their entireties herein. Preferred isomerization catalysts include those promoting the isomerization reactions in the presence of added hydrogen (hydroisomerization) and particularly those catalysts promoting isomerization of a gaseous hydrocarbon feedstock.
The conditions employed to isomerize (or hydroisomerize) a hydrocarbon feedstock will vary depending upon the particular process embodiment in which the catalytic absorbent and/or dual-function catalyst and/or isomerization catalyst is used and the nature of the feedstock. Most usually, a fixed bed of the isomerization catalyst is contacted by the feedstock in a reactor operated at a temperature in the range from about 50� F. to about 600� F., preferably an elevated temperature from about 450� F. to about 550� F., and most preferably from about 480� F. to about 520� F. The feedstock passed to the isomerization catalyst may be in the liquid phase, but preferably is in the gaseous phase when it contacts the isomerization catalyst. Typical pressures maintained during such contacting are in the range from atmospheric to about 500 p.s.i.g., preferably less than about 400 p.s.i.g. and most preferably about 200 p.s.i.g. to about 350 p.s.i.g. The weight hourly space velocity (WHSV) of the feedstock over the isomerization catalyst is about 0.1 to about 5.0, preferably about 0.5 to about 3.0, and most preferably about 1.0 to about 2.0. In the presence of hydrogen, the hydrocarbon feed contacts the isomerization catalyst under hydroisomerization conditions wherein a hydrogen recycle rate of usually about 1,000 to about 8,000, and preferably about 1,500 to about 4,500 standard cubic feet per barrel (scf/bbl).
It has been observed that the activity of the isomerization catalyst for producing a hydrocarbon product of high octane quality from a feedstock containing normal parafins, particularly n-pentane and/or n-hexane, is diminished in an unusual manner when the sulfur content of the feedstock is varied from 0 to 1, 1 to 2, or 2 to 5 ppmw of sulfur. As the feedstock sulfur content is increased from 0 to 1 ppmw, the activity of the isomerization catalyst decreases as evidenced by an increase in the n-hexane content of the product as well as by a decrease in the product octane, pentane isomer product, dimethyl butanes and methyl pentanes. In a typical situation wherein a feedstock consisting of an equimolar mixture of n-pentane and n-hexane is treated with the isomerization catalyst, the loss in activity is manifested by an increase in the mole percent of n-hexane product remaining from the total hexane product by 5.0 to 10.0 mole percent and by decreases in research octane number by 1.0 to 3.0 numbers. Also, the mole percent of pentane isomer product in the total pentane product is increased by 2.0 to 8.0 mole percent, the mole percent of dimethyl butane in the total hexane product by 1.0 to 3.0 mole percent, and the mole percent of methyl pentane in the total hexane product by 1.0 to 10.0 mole percent. An increase in the sulfur level from 1 to 2 ppmw results in an additional decline in activity of about the same magnitude as experienced when the sulfur level increases from 0 to 1 ppmw. A further increase in the amount of sulfur, from 2 to 5 ppmw, on the other hand, results in only a very small additional decline in activity. When the amount of sulfur in the feedstock is greater than 5 ppmw, little change has been observed in the activity. Clearly, it is the first 2 ppmw increment in sulfur that results in a major part of the activity decline. Such relationships between feedstock sulfur content and activity have been observed particularly at isomerization temperatures in the range from about 450� F. to about 575� F., and more particularly in the range from about 470� F. to about 520� F.
In one embodiment of the invention, a liquid hydrocarbon feedstock containing greater than 2 ppmw, and usually greater than 5 ppmw of sulfur, calculated as S, and normal paraffins contacts a catalytic absorbent or dual-function catalyst in one or more upstream reaction zones under desulfurization conditions, e.g., a temperature in the range from about 200� F. to about 600� F. and a pressure in the range from about 100 p.s.i.g. to about 750 p.s.i.g. and a space velocity of about 0.1 to about 5.0 (WHSV). The feedstock contacts the catalytic absorbent or dual-function catalyst in either the liquid or gaseous phase and in the presence or absence of hydrogen, depending upon which environment is most effective for sulfur removal by the particular active metal component in the absorbent or catalyst at the conditions of sulfur removal. The effluent from the upstream reaction preferably less than 2 ppmw of sulfur, and more preferably in the range from 0-1 ppmw, and most preferably nil; i.e., less than 0.1 ppmw, calculated as S. Hydrogen is usually added to the effluent (if not already present in sufficient amount) and the effluent then passed over an isomerization (hydroisomerization) catalyst in at least one downstream reaction zone at isomerization (hydroisomerization) conditions including a temperature in the range from about 450� F. to about 575� F. Due to the isomerization (hydroisomerization) reactions, the product hydrocarbon obtained from the downstream reaction zone(s) contains a reduced concentration of normal paraffins and an increased concentration of isomerized paraffin compounds. More particularly, when the feedstock contains n-pentane and n-hexane compounds, the reactions in the isomerization (hydroisomerization) zone yield product hydrocarbons containing a reduced amount of n-pentane and n-hexane, usually at least about 30 percent reduction of at least one, and an increased amount of pentane isomers (such as methyl butane and neopentane) and/or hexane isomers (such as dimethyl butanes and methyl pentanes). Such yields of isomers are usually at least about 1.2 times higher, and in some cases higher by a factor of two, than yields obtained from a process wherein essentially the same hydrocarbon feedstock contacts the isomerization catayst without benefit of sulfur removal in the upstream reaction zones(s) containing the catalytic absorbent.
In a modified process of the preceding embodiment, it is preferred that the operating conditions in both the upstream and downstream reaction zones be essentially equivalent and that the contacting with the catalytic absorbent or dual-function catalyst in the upstream reaction zone and contacting the hydroisomerization catalyst in the downstream reaction zone(s) be in the gaseous phase. Accordingly, operating conditions in both the upstream and downstream reaction zones are those disclosed hereinbefore for the bed of isomerization catalyst, i.e., a temperature in the range from about 450� F. to about 550� F., a pressure in the range from about 200 p.s.i.g. to about 350 p.s.i.g., a space velocity in the range from about 0.5 to about 3.0 WHSV, and the presence of hydrogen. Such a scheme eliminates the need for heat-exchange means between the upstream and downstream reaction zone(s) in order to provide a gaseous effluent to the downstream reaction zone. Furthermore, when the dual-function catalyst is employed in the upstream reaction zone(s), the conditions must be such that isomerization occurs in both the upstream and downstream reaction zones.
In the modified process just described, the dual-function catalyst is employed in the upstream reaction zone(s) so as to simultaneously desulfurize and isomerize the feedstock. The effluent from the upstream reaction zone(s), in addition to containing less than 1 ppmw and preferably essentially no sulfur, also contains an increased amount of pentane isomers and/or hexane isomers as compared to that in the feedstock. Such isomerization in the upstream reaction zone(s) supplements the isomerization in the downstream reaction zone(s) to yield a product hydrocarbon from the overall process (i.e., effluent from the downstream reaction zone(s)) that contains essentially no sulfur, a reduced content of n-pentane and n-hexane, and an increased amount of pentane and hexane isomers.
Although a typical flow scheme involves successively passing a hydrocarbon feedstock through at least one desulfurization reactor containing a catalytic absorbent and subsequently through at least one isomerization reactor containing the isomerization catalyst, the process of the invention is not limited to this particular flow scheme. For example, in one embodiment of the invention, two or more separate reaction zones may be utilized in series in one reactor, with at least one upstream reaction zone containing the catalytic absorbent and at least one downtream reaction zone containing the dual-function catalyst. Furthermore, the dual-function catalyst can be utilized alone in one or more reaction zones at isomerization conditions disclosed hereinbefore. In this latter embodiment the feedstock usually contains less than 5 ppmw, preferably less than 2 ppmw and most preferably in the range from 0-1 ppmw of sulfur, calculated as S.
The invention is further illustrated by the following example which is illustrative of specific modes of practicing the invention and is not intended as limiting the scope of the invention defined by the appended claims.
A conventional isomerization catalyst designated as "HS-10" and commercially available from the Linde Division of the Union Carbide Corporation is contacted in 7 separate runs with a hydrocarbon feedstock consisting of equimolar mixture of n-pentane and n-hexane and doped with thiophene in concentrations varied as hereinafter described.
During start-up of the process, hydrogen gas contacts the isomerization catalyst for 4 hours at 300� C. and the feedstock contacts the isomerization catalyst in the presence of hydrogen in a stainless steel reactor (designated as R-2 herein) in each run for 24 hours under the conditions in Table I:
TABLE I______________________________________Temperature 250� C.Pressure 300 p.s.i.g.Space Velocity 3.0/hr WHSVHydrogen/Feedstock 4/1 molar______________________________________
In run numbers 2 and 3 a catalytic absorbent, designated as Catalyst A (containing a nominal 20 weight percent of copper oxide, calculated as CuO, on gamma alumina), is contacted with the feedstock in an upstream separate stainless steel reactor (designated as R-1 herein) under the above mentioned conditions in Table I. In these runs the feedstock is passed serially over the materials in R-1 and R-2 and the effluent from R-1 analyzed for sulfur content and the effluent from R-2 analyzed for octane rating and for the products set forth in Table II:
TABLE II______________________________________R-2 Hydrocarbon Products______________________________________i-C5 mole percent of pentane isomer product in the total pentane productDMB mole percent of dimethyl butane product in the total hexane productMP mole percent of methyl pentane in the total hexane productn-C6 mole percent of n-hexane product remain- ing from the total hexane productRONC calculated research octane number of the C5 + isomers in the product______________________________________
In runs 6 and 7, R-1 contains Catalyst DF, a dual-function catalyst containing a nominal 15.0 weight percent of nickel oxide, calculated as NiO, 68 weight percent of LZ-210 zeolite (having a silica-to-alumina ratio of 9.0), and 17 weight percent of alumina. Catalyst DF is prepared by comulling the LZ-210 zeolite with sufficient alumina hydrogel. The comulled paste is extruded in particulate form having a cross-sectional cylindrical shape. The particulates are of a length between about 1/4 and 1/2 inch, are dried and calcined in air. The extrudates are then impregnated with sufficient aqueous solution of nickel nitrate. In runs 8 and 9, Catalyst DF is contacted with the feedstock in R-2.
The following Table III summarizes (1) the sulfur content of the feedstock (doped with n-butyl mercaptan) or effluent from R-1 for each run and (2) the isomerized products and octane values obtained from the effluent of R-2. Note that in runs 1, 4, 5, 8 and 9, the feedstock is passed through only one reactor vessel, R-2, and contacts either the catalytic absorbent or dual-function catalyst as shown in Table III.
TABLE III__________________________________________________________________________Feedstock Sulfur, ppmw S Effluent Isomer- Catalytic from R-1 Feed- izationFeedstock Absorbent that passes stock Catalyst R-2 Product AnalysisRun No.to R-1 in R-1 to R-2 to R-2 in R-2 I-C5 DMB MP n-C6 RONC__________________________________________________________________________1 -- -- -- 0 HS-10 15.0 3.4 43.2 53.4 56.62 0 Cat. A 0 -- HS-10 15.7 3.9 40.7 55.4 56.73 5 Cat. A 0 -- HS-10 15.7 3.9 39.8 56.9 56.24 -- -- -- 5 HS-10 7.9 2.8 18.0 79.2 49.45 -- -- -- 100 HS-10 9.7 3.6 20.9 75.4 50.66 0 Cat. DF 0 -- HS-10 34.8 13.3 62.3 24.3 68.37 100 Cat. DF 0 -- HS-10 31.2 9.6 60.6 29.8 66.08 -- -- -- 0 Cat. DF 12.0 4.0 45.6 50.4 57.09 -- -- -- 100 Cat. DF 10.1 2.8 36.0 61.1 53.8__________________________________________________________________________ -- not applicable
The data in Table III demonstrate that in run no. 4, 5 ppmw of sulfur causes a substantial decline in isomer product yields as compared to the yields in run nos. 1, 2 and 3 from the sulfur-free feedstocks. The process of the invention in run no. 3 provides a sulfur-free feedstock contacting the isomerization catalyst and results in isomerization products of essentially the same yields as in run nos. 1 and 2 wherein the sulfur-free feedstocks also contact the isomerization catalyst.
In run no. 5, a feedstock containing 100 ppmw of sulfur contacting the isomerization catalyst in R-2 also causes substantial decline in the activity of the isomerization catalyst as compared to that when a sulfur-free feedstock contacts the catalyst (see run nos. 1-3). However, when the dual-function Catalyst DF is utilized in the upstream reactor, R-1, in the process of the invention (run nos. 6 and 7), a substantial increase in isomerization results in the products from R-2 as compared to that in run no. 5. Such an increase in isomerization occurs when 0 or 100 ppmw of sulfur are contained in the feedstock supplied to R-1 It is clearly shown in run no. 7 that the dual-function catalyst provides substantial desulfurization.
Furthermore, the dual-function catalyst (run nos. 6 and 7) also provides substantial isomerization. In runs nos. 6 and 7 the mole percent of pentane isomer product (i-C5) is more than doubled and the mole percent of n-hexane product remaining (n-C6) is essentially reduced by at least a factor of two, when compared against run nos. 1-3 wherein sulfur-free feedstocks also contact the isomerization catalyst in R-2. Thus, isomerization occurs in both R-1 and R-2 in run nos. 6 and 7 whereas in run nos. 1-3- isomerization only occurs in R-2.
In run nos. 8 and 9 wherein the dual-function Catalyst DF is employed in R-2 as the only catalyst in the process, the yield of isomerization products is at least equivalent, or in the case of n-hexane isomerization, substantially greater than that in respective run nos. 1 and 5. In the comparison of run no. 8 with run no. 1, both the isomerization catalyst, HS-10, and the dual-function catalyst are contacted with the sulfur-free feedstock to produce similar yields of isomerized products. However, when the feedstock is doped with 100 ppmw of sulfur in run nos. 9 and 5, the process of the invention (employing Catalyst DF in run no. 9) produces a substantially increased yield of isomerized hexane compounds and improved product octane compared to run no. 5 employing the conventional catalyst. Catalyst DF is clearly more sulfur tolerant than Catalyst HS-10.
In view of the foregoing description of the invention including the Example thereof, it is evident that many alternatives, modifications, and variations can be made by those skilled in the art without departing from the concept of the present invention. Accordingly, it is intended in the invention to embrace all such alternatives, modifications, and variations as may fall within the scope of the appended claims.
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|U.S. Classification
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|International Classification
|Cooperative Classification
|European Classification
|Jul 16, 1987
Owner name: UNION OIL COMPANY OF CALIFORNIA, LOS ANGELES, CALI
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|Jul 15, 1997
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