OTTAWA — Canada’s privacy watchdog is warning marijuana users who are worried about their personal information being collected to pay with cash rather than plastic.Privacy Commissioner Daniel Therrien gives the advice in a statement on his website trying to help pot sellers and buyers understand their privacy rights.The statement says marijuana remains illegal in most countries making the personal information of Canadian marijuana users even more sensitive.Some countries could bar entry to individuals if they know they have purchased cannabis, even lawfully.Therrien suggests you can avoid the collection of your personal information by using cash instead of credit cards when buying pot from legal retail outlets.However this option is not available to many Canadians, as some provinces have only a limited number of retail stores and in Ontario, legal cannabis is only available for purchase online for several more months.The Canadian Press
Amsterdam – Morocco topped the favorite travel destinations for Dutch tourists, according to a survey conducted by Dutch leading travel website, Riksja Travel.Morocco came ahead of Ecuador and Thailand in the survey that included around 14,000 participants.The twelve-question survey aimed at unveiling the choices and expectations of Dutch travelers. The website noted that Morocco stands as an attractive travel destination with its rich and diversified offer and its proximity to Europe.According to figures released by the Moroccan tourism office (ONMT), around 560,000 Dutch tourists visited Morocco in 2013, that is a 3.7% rise compared to 2012. A rate of 41% of Dutch tourists visited Marrakech, followed by Agadir with 31% and Essaouira 23%.
United People’s Freedom Alliance (UPFA) Parliamentarian Priyankara Jayarathne was sworn in today as the State Minister of Local Government and Provincial Councils, before President Maithripala Sirisena at the Presidential Secretariat.Meanwhile Dushmantha Mithrapala was sworn in as the Deputy Minister of Buddha Shasana before the president. Mithrapala is also the current Deputy Minister of Justice.
In his message marking the Day, Secretary-General Kofi Annan drew attention to the ongoing preparations at UN Headquarters on the recently established Permanent Forum on Indigenous Issues, which he called “a pioneering initiative that aims at giving indigenous peoples the chance to bring their concerns to the attention of the international community.” The Forum, which will meet for the first time in May 2002, will include 16 independent experts – half of them nominated by indigenous peoples.During a press conference today in New York, the Secretary of the UN Working Group on Indigenous Populations, Julian Burger, said the Forum would be reporting at a high level, directly to the Economic and Social Council. “From our point of view, that’s a very interesting development: that indigenous people will be high up in the hierarchy in our system in the UN,” he said, adding that another unique feature is that the Forum has a very broad mandate beyond human rights issues – covering such areas as development, health, education and culture. At the same press conference, Marciel Arias, a Kuna Indian from Panama, said it had been difficult in the past for indigenous people to participate in UN meetings. “Indigenous associations would like to go even further, but we understand that this [Forum] constitutes the first step as we move to a higher level within the UN,” he said. “We hope that this Forum will play a role – an important one – to make governments more aware, and indigenous organizations more aware as well, so that they will be more interested in participating.” In his message commemorating the Day, the President of the UN General Assembly, Harri Holkeri of Finland, said an important goal of the International Decade of the World’s Indigenous People (1995-2004) was to strengthen global cooperation on the challenges facing indigenous societies. Making consultation an integral part of the planning and implementation of programmes would enhance the outcome of such endeavours and encourage concerned groups to become involved, he said. To mark the Day, special activities are scheduled in New York, with performances by the Mohawk Singers and Dancers and a traditional Sacred Pipe Ceremony carried out by Dr. Arvol Looking Horse – the 19th generation keeper of the Sacred White Buffalo Calf Pipe.
In a process supervised by Afghan elders, the weapons are being delivered to collection points in Sholgareh district – the scene of four separate conflicts over the past six months – by members of the Jamiat, Jumbesh and Hizb-e-Wahdat factions.They are then transported to military depots outside Mazar-i-Sharif, to be registered and kept under guard by Jamiat and Jumbesh forces – with the UN Assistance Mission in Afghanistan (UNAMA) empowered to monitor their safekeeping.The process is taking place under the auspices of the multi-party Security Commission in Mazar-i-Sharif, observed and facilitated by UNAMA. The UN Mission reports unanimous support for the exercise by the people of Sholgareh district, as well as widespread agreement on expanding disarmament in the region.
According to a news release issued by the ICC, the Appeals Chamber found, by majority, that the Court’s Trial Chamber III – which delivered the original sentence – had “erred on two important issues”, including the wrongful conviction of Mr. Bemba “for specific criminal acts that were outside the scope of the charges as confirmed.”It added that the Trial Chamber made serious errors in its assessment of whether Mr. Bemba took all necessary and reasonable measures to prevent, repress or punish the commission by his subordinates of the other crimes within the scope of the case.“More specifically, the Trial Chamber erred in its evaluation of Mr. Bemba’s motivation and the measures that he could have taken in light of the limitations he faced in investigating and prosecuting crimes as a remote commander sending troops to a foreign country; in whether he made efforts to refer the allegations of crimes to the Central African Republic (CAR) authorities; and in whether he intentionally limited the mandate of commissions and inquiries that he established,” added the news release.Furthermore, in the view of the Appeals Chamber majority, there was an apparent discrepancy between the limited number of crimes within the case’s scope for which Mr. Bemba was held responsible and the Trial Chamber’s assessment of which measures he should have taken.Mr. Bemba will, however, remain in detention on account of a different case in which he has been convicted of offences against the administration of justice, pending a decision of Trial Chamber VII, within the ICC.In 2016, Mr. Bemba was originally sentenced to 18 years in prison, after the Chamber found him “guilty beyond reasonable doubt” as a military commander responsible for two counts of crimes against humanity (murder and rape) and three counts of war crimes (murder, rape, and pillaging) committed in the Central African Republic between October 2002 and March 2003.
Chicago Bears linebacker Lance Briggs (right) sacks New York Giants quarterback Eli Manning at Soldier Field Oct. 10. The Bears won, 27-21.Credit: Courtesy of MCTTwelve dollars. That’s all I spent on a New York Giants football sweatshirt that I’m truthfully too scared to wear at the risk of being ridiculed. It’s hard enough being a fan of a football team in a different state, but it’s even harder when that team has yet to win one of its six games this season.I was born and raised in New Jersey, so being a New York Giants fan is all I’ve ever known. I was taught that the Giants are the best and that I’m supposed to hate the Philadelphia Eagles … which I do. Being a fan of the G-men has never been a problem until this season.Coach Tom Coughlin is 67 and is in his 10th year coaching the team. He’s one of the oldest NFL coaches ever, but after earning a pair of Super Bowl rings for the Giants, it doesn’t appear he’ll be going away anytime soon.The Giants have won two Super Bowls in the last six years (2008 and 2012). With a history like that, you would think that they would be a team to fear. This year, not so much. They’ve had their worst start to a season since 1976 and quarterback Eli Manning has had arguably the worst season of his career, currently leading the league in interceptions with 15. Ouch. That’s gotta be rough while his big brother Peyton and the Broncos are having an awesome season, winning their first six games and leading the league in total offense, passing yards and points scored.Since I’m a fan of Ohio State football as well, I can’t imagine how current Giant players, former Buckeyes Jonathan Hankins and Jim Cordle feel right now. Playing on the OSU football team has spoiled them into not really knowing what a losing consistently feels like. In Cordle’s five years at OSU (he redshirted in 2005), the team was a combined 54-10, and in Hankins’ three years, the Buckeyes were 30-8, including the 12 vacated wins in 2010.My goal is not to bash the team I’ve grown up watching, it’s to share a little bit of my disappointment OSU fans might not understand. This is the first time my friends who are Cleveland Browns (3-3) fans are laughing at me.In my mind, this season is over for the Giants. Will I still watch the games? Yes. Will I still have hope that they can win a game? Of course. Will I wear that $12 sweatshirt anytime soon? To be determined. But I’m pretty sure it’s impossible to come anywhere close to the playoffs at this point, so my heart is a little broken for them.
Complete schedule of the EHF EURO 2014 Preliminary Round:Group A1 Denmark2 Czech Republic3 Macedonia4 AustriaCzech Republic – Austria (January 12th , 1800 )Denmark – Macedonia (12 January at 20:30 )Macedonia – Czech Republic (January 14, at 18:15 )Austria – Denmark (14 January at 20:30 )Macedonia – Austria (January 16, at 18:15 )Denmark – Czech Republic (January 16, at 20:30 )Group B1 Spain2 Iceland3 Hungary4 NorwayIceland – Norway ( January 12 at 16:00 )Spain – Hungary (January 12, at 18:15 )Hungary – Iceland (January 14 , 1800 )Norway – Spain (January 14, at 20:15 )Spain – Iceland (January 16 , 1800 )Hungary – Norway (January 16, at 20:15 )Group C1 Serbia2 France3 Poland4 RussiaSerbia – Poland (January 13 , 1800 )France – Russia (January 13 at 20:15 )Russia – Serbia (January 15 , 1800 )Poland – France (January 15, at 20:15 )Poland – Russia (January 17th , 1800 )Serbia – France (17 January at 20:30 )Group D1 Croatia2 Sweden3 Belarus4 MontenegroCroatia – Belarus (January 13 , 1800 )Sweden – Montenegro ( 13th January at 20:15 )Montenegro – Croatia (January 15 , 1800 )Belarus – Sweden (January 15, at 20:15 )Croatia – Sweden (January 17th , 1800 )Belarus – Montenegro (17 January at 20:30 ) ← Previous Story EHF EURO 2014 TOP 10 missing stars Next Story → Anders Eggert to miss the opener against Macedonia
SWIMMERS HAVE BEEN warned about getting into the water at Cork beaches today.Cork County Council has advised would-be bathers to take precautions at Youghal Front Strand, Tragumna, Barleycove and The Warren.The local authority has told beach-goers not to swim at Youghal beach due to the elevated levels of bacteria found in the water, warning that swimming could lead to illness.Localised heavy rain is believed to have affected wastewater infrastructure in the area, the council said.The swimming ban will remain in place until the quality of the water improves. A new sample is to be taken on Monday to assess the situation. A map showing the current bathing restrictions at Ireland’s beaches Source: splash.epa.ieBathers have also been warned about bacteria at the three other beaches, but a swimming ban is not in place.Instead, beach users have been cautioned to avoid swallowing water, to avoid swimming with an open cut or wound, and to stay out of the water if they are pregnant or have a weakened immune system.The warning is expected to be lifted tomorrow.Read: Coast Guard warns swimmers against “literally jumping into the unknown” > Read: It’s official… Hottest day of the year so far >
This week is the Build conference being held in Anaheim, California. Microsoft is using it as the official unveiling of Windows 8 to the world. Usually, an unveiling such as this is followed with calls for “when can I play with it?” Well, the answer to that question is “tonight”.When Microsoft was desperately trying to make up for the car wreck that was Windows Vista, they decided to release previews of Windows 7 really early for anyone to download and try. It worked really well. Microsoft got loads of feedback with which to improve their next-gen operating system, and anyone interested got a new OS to play with.That same mentality is being continued with Windows 8, and later today a developer preview of the new OS will become available. More specifically, at 8pm PST you will be able to download either a 32-bit or 64-bit ISO from the Microsoft Dev Center website. Which you choose to get depends on whether you are a developer or not: only the 32-bit version will come with development tools.Now we must stress that this is by no means final software, but the presentation currently streaming live on the Build Windows website shows an OS that looks very usable already. Microsoft has also promised to include a number of sample applications for developers to play with.You won’t be able to install this developer preview alongside another OS as it requires a clean install. I take that to mean you can still install it as a virtual machine, however, using software like that offered by VMWare or VirtualBox. Microsoft also intends to roll out regular updates and drivers, so if your install doesn’t work out tonight, keep checking the developer site as next week it may have the drivers you need.For those desperate to see the new Metro style applications and interface first hand, there is no better way to experience it at the moment.Read more at Building Windows 8
Wolverhampton Wanderers boss Nuno Espirito Santo has reportedly emerged as a potential candidate to replace Jose Mourinho at Manchester UnitedThe Red Devils have lost both of their opening four games of the 2018/19 Premier League campaign.This has led to a great deal of uncertainty surrounding Mourinho’s future at Old Trafford.Former Real Madrid manager Zinedine Zidane had been touted as the most likely man to replace Mourinho at United.Vidic: “Ronaldo is the most professional footballer I’ve seen” Andrew Smyth – September 14, 2019 Nemanja Vidic opened up on how a 21-year-old Cristiano Ronaldo’s professionalism left him stunned at Manchester United.But One Football reports that another shock name has emerged in Nuno.The Portuguese coach has impressed the 20-time English champions in his spell in charge of Wolves.The 44-year-old led Wolves to the Championship title last season and the club have had a strong start in their return to the English top-flight.United will next face Watford away in the Premier League, while Wolves will host Burnley.
Runners compete in Worlds Fastest 5K races in downtown Carlsbad Elizabeth Alvarez, Categories: Good Morning San Diego, Local San Diego News FacebookTwitter 00:00 00:00 spaceplay / pause qunload | stop ffullscreenshift + ←→slower / faster ↑↓volume mmute ←→seek . seek to previous 12… 6 seek to 10%, 20% … 60% XColor SettingsAaAaAaAaTextBackgroundOpacity SettingsTextOpaqueSemi-TransparentBackgroundSemi-TransparentOpaqueTransparentFont SettingsSize||TypeSerif MonospaceSerifSans Serif MonospaceSans SerifCasualCursiveSmallCapsResetSave SettingsA race renowned for fast runners and world records once again welcomes a stellar field for the elite invitational at the 33rd annual Carlsbad 5000 on Sunday, March 25, 2018. Leading the way will be a world class field of elite athletes ready to run a fast time along the scenic oceanfront streets in downtown Carlsbad.The spring running season is in full swing as a contingent of international runners will travel to the event, known as the ‘World’s Fastest 5K’ road race as the home of 16 world records, 8 U.S. records and 11 world wheelchair bests. Race day begins at 6:58 am with the Masters Men (40 years old and over), the first of six races to take place throughout the day. The women’s elite race will begin at 10:15 am and the men’s elite race is scheduled for 10:40 am.Saturday’s Junior Carlsbad will kick off a weekend of family fun, hosting a morning of kids’ races as a precursor to the main event Sunday morning. Both events will feature post-race refreshments, prizes, live entertainment and a free outdoor Health & Fitness Expo that will run throughout the two days of exercise and excitement.“The Carlsbad 5000 is the premiere 5k road race in the world and we are guaranteed new champions this year as both 2017 winners are unavailable to compete,” said Matthew Turnbull, elite athlete coordinator for the event. “To stand on top of the podium at the Carlsbad 5000 is a great honor and on Sunday morning two new athletes will be joining some of the greatest athletes of all time who have their names engraved on the Mike Long Trophy.”Sweden’s Kalle Berglund, the national record holder for 1500m who recently represented his country at the IAAF World Indoor Championships last month, and Denmark’s Nick Jensen, a 7-time National Champion over 800m and 1500m, headline the men’s field for the elite invitational which will take place at 10:45am.The Europeans will be joined by a pair of Berlund’s countrymen, Johan Rogestedt, a former Youth World Champion over 800m who is making his 5k debut, and Emil Blomberg, who has an 8:32.27 personal best for the Steeplechase and ran a 1500m best indoors earlier this year.Pushing the Swedish contingent will be Ethiopia’s Gebrekidan Abadi and Americans Louis Seferini, who recently became the 514th U.S. athlete to break 4 minutes in the mile, running 3:59.33 at the Boston University Last Chance meet, Dan Nestor, who ran a 3.55 road mile in Boulder and 29.50 over 10km cross country at the end of last year and Samuel Atkin, a two-time NAIA Champion who has a personal best of 13.56 from the Silicon Valley Turkey Trot last year.The women’s field for Carlsbad is equally as competitive. Emelia Gorecka of Great Britain, will look to continue the recent success for U.K. runners including 2014 Champion Julia Bleasdale. Gorecka was a 2013 European Junior Champion over 3000m and has a 5000m best of 15:07. Her top challengers include Jessica O’Connell, who represented Canada at the Commonwealth Games in Glasgow and finished was 4th in Carlsbad in 2015. They will be joined by Mexico’s Brenda Flores Munoz, a gold and silver medal from the 2015 Pan Am Gameswho owns a 15.30.87 personal best for 5000m.Top Americans will be joining the field on the women’s side led by Sarah Brown, a nine-time track and cross country All-American at the University of Tennessee and Alycia Cridebring, who has a personal best of 15.35.34 for 5000m. Other notables in the elite invitational include a trio of local triathetes: Ellie Abrahamson, a NCAA D1 All-American at Wake Forest University; Carlsbad’s Mary Alex England, who has a 5K best of 16.10; and Sophie Chase who ran 16.19.77 for 5000m at the Stanford Cardinal Classic last year. Chelsey Totten and Natasha La Beaud round out the American entrants.While hosting the “World’s Fastest 5K” for elite athletes, the Carlsbad 5000 welcomes runners and walkers of all ages and abilities to a series of four competitive age group races. The event is renowned for its scenic course, healthy competition and a weekend of fun for participants of all ages and skill levels. Kicking off the weekend of family fun is the Junior Carlsbad, which takes place Saturday, March 24 and offers 9 different races specifically designed for kids age 12 and under.Race weekend registration is available for all events. A free outdoor Health & Fitness Expo takes place on race weekend, running from 7 a.m. to 1 p.m. Saturday and 6:30 a.m. to 1 p.m. on Sunday. The expo will serve as race registration headquarters on Saturday, allowing participants to pick up their race number, timing chip, t-shirt and goodie bag. The interactive expo, located on Roosevelt Street between Grand and Carlsbad Village Drive, will feature vendors showcasing running apparel and shoes, fitness gear and health and nutrition items. 00:00 00:00 spaceplay / pause qunload | stop ffullscreenshift + ←→slower / faster ↑↓volume mmute ←→seek . seek to previous 12… 6 seek to 10%, 20% … 60% XColor SettingsAaAaAaAaTextBackgroundOpacity SettingsTextOpaqueSemi-TransparentBackgroundSemi-TransparentOpaqueTransparentFont SettingsSize||TypeSerif MonospaceSerifSans Serif MonospaceSans SerifCasualCursiveSmallCapsResetSave Settings Elizabeth Alvarez Posted: March 25, 2018 March 25, 2018
After reporting a $191.7 million net loss for 2008, printer R.R. Donnelley announced that it had been awarded a $500 million multi-year agreement from newspaper magazines publisher the Publishing Group of America.Under terms of the agreement, Donnelley will provide printing, logistics and premedia services for PGA’s magazines, including American Profile, Relish and Spry. The magazines are distributed within roughly 1,100 weekly and smaller market newspapers.Donnelley Wednesday reported a $191.7 million year-end net loss, down considerably from a $48.4 million net loss in 2007. The company reported a $686.9 million net loss for the fourth quarter.Year-end revenue was $11.58 billion, flat over sales in 2007. Donnelley’s results included $1.18 billion in restructuring and impairment fees, the company said.
The Katmai National Park and Preserve wants to build a new viewing platform on the Research Bay Overlook Trail.Proposed project site in Katmai National Park & Preserve. (Image credit National Park Service)During the summer, a Valley of Ten Thousand Smokes bus tour runs daily. It offers visitors views of the valley formed by the Novarupta volcanic eruption in 1912, the largest volcanic eruption in the 20th century. Along the way, visitors can disembark to enjoy scenic views near the road.One key stop along the way overlooks the valley, Naknek Lake and islands in Research Bay.“Over the last 10 or 20 years, the visitors have just been developing what we call a ‘social trail,’” explained Brian Smith, the park’s environmental protection specialist. “There is no improvement to the area. So they just get off the bus, and they walk into the forest a little ways into a clearing. And repeatedly, over time, that has kind of compacted the soils down and created a social trail out to the viewing spot. And the social trail kind of terminates at a really steep drop off.”Katmai has identified several problems with the current set up. Because no formal trail exists, the overlook is not accessible to people with limited mobility. The “social trails” also speed erosion in the area and pose a risk to visitors.“We haven’t had any injuries out there,” said Smith. “But there is a risk [of] injuries because of the tree roots and the rutting of the trail and unimproved nature of the surface. And what we’re looking at—this project is kind of like a mitigating factor to hopefully prevent those kind of injuries, slips, trips and falls, from hopefully happening in the future.”The park proposes to build a 150-foot long trail to a 12 by 20-foot viewing platform. The public comment period for the project’s Draft Environmental Assessment is open until Feb. 18.If the project is approved, Katmai plans to begin construction in August and anticipates the project will take about 20 days. It plans to contract with the Student Conservation Association, a nonprofit that aims to connect youth with public lands, for the installation of the trail and platform.Comments on the project can be submitted online, by mail or in person at Katmai’s visitor center in King Salmon.
Domestic e-commerce company Snapdeal has acquired mobility solutions firm Letsgomo Labs as part of its efforts to strengthen its mobile platform. The deal value was not disclosed.Letsgomo Labs, which offers end-to-end mobile solutions, is currently providing services to other major online retailers, helping them to improve their mobile capabilities. It was founded by Manav Kamboj and Vikas Banga.”Mobile is one of our key focus areas and in a span of just 2 years, the medium has proved to be one of the biggest growth drivers for the company. Delivering a great user experience across varying data connections and numerous handsets being used in the country is the guiding principle for our mobile initiatives,” said Rohit Bansal, Co-Founder, Snapdeal.”Over 75% of our sales now come through mobile platforms and Letsgomo team becoming a part of our family will further propel our efforts in this direction,” he added.Snapdeal has forayed into digital bill and utility payment services following the acquisition of mobile recharge services firm Freecharge in April for ₹Rs 2,900 crore.Last month, Snapdeal acquired Hyderabad-based mobile technology startup MartMobi, aimed at matching up with rivals’ move to switch to app-only format.Online fashion retailer Myntra already switched to app-only mode from 15 May. Flipkart, its parent company, also plans to gradually shift advertisements from desktop website to mobile platform, after seeing a 10-fold increase in mobile traffic in less than 18 months.By shifting to app-only format, online retailers hope to reduce costs, gain more exclusive customers and limit dependence on technology giants such as Google Inc. and Facebook Inc. for marketing. Snapdeal, which received $627 million in funding from Japan’s SoftBank Group in November last year, is expected to make acquisitions worth $1 billion this year.Investment banker Goldman Sachs expects India to become the second-largest digital market globally by 2030, next to China. It estimates the country’s e-commerce market to grow 15 times to $300 billion by then, accounting for 2.5 percent of the country’s gross domestic product (GDP), The Economic Times reported.
Activists and DACA recipients march up Broadway during the start of their ‘Walk to Stay Home,’ a five-day 250-mile walk from New York to Washington DC, to demand that Congress pass a Clean Dream Act, in Manhattan, New York on 15 February. Photo: ReutersA federal judge on Friday ruled that the Trump administration must fully restore a program that protects from deportation some young immigrants who were brought to the United States illegally as children, including accepting new applications for the program.US District Judge John Bates in Washington, DC, said he would stay Friday’s order, however, until 23 August to give the administration time to decide whether to appeal.Bates first issued a ruling in April ordering the federal government to continue the Deferred Action for Childhood Arrivals, or DACA, program, including taking applications. He stayed that ruling for 90 days to give the government time to better explain why the program should be ended.On Friday Bates, who was appointed by former president George W Bush, a Republican, said he would not revise his previous ruling because the arguments of President Donald Trump’s administration did not override his concerns.Under DACA, roughly 700,000 young adults, often referred to as “Dreamers”, were protected from deportation and given work permits for two-year periods, after which they must re-apply to the program.The program was created in 2012 under former President Barack Obama, a Democrat.Two other federal courts in California and New York had previously ordered that DACA remain in place while litigation challenging Trump’s decision to end it continued. Those rulings only required the government to process DACA renewals, not new applications.Another lawsuit in a Texas federal court is seeking to end DACA.A spokesman for the US Department of Justice said on Friday that the government would continue to defend its position that it “acted within its lawful authority in deciding to wind down DACA in an orderly manner.”Congress so far has failed to pass legislation to address the fate of the Dreamers, including a potential path to citizenship.Friday’s ruling came in lawsuits filed by several groups and institutions, including the National Association for the Advancement of Colored People and Princeton University.
Reaction profile for methane sulfonation. Pressure of CH4 is plotted versus time under (A) standard conditions using 0.9 mol % electrophilic initiator (Figure 2, entry 2) and (B) successive additions of CH4 (Fig 2, entry 3). The inset in (A) shows a zoomed-in view of region i. Credit: Science, doi: 10.1126/science.aav0177. Direct functionalization of methane to form value-added products is a challenge due to potential overoxidation in many reaction environments and sulfonation is an attractive approach to achieve the selectivity of interest. In the practical process, Díaz-Urrutia and Ott produced methanesulfonic acid (MSA) using only two main reactants; methane and sulfur trioxide. They achieved 99 percent selectivity and yield of MSA in the work. The scientists based the electrophilic initiator on a sulfonyl peroxide derivative, which they protonated under superacidic conditions to produce a highly electrophilic oxygen atom capable of activating a C-H bond of methane. They proposed mechanistic studies to support the formation of a cation methenium (CH3+)as a key intermediate during the reaction. The proposed method is scalable with reactors connected in a series to prospectively produce up to 20 metric tons of MSA per year. While large-scale fracking techniques and biogas production has provided access to large quantities of inactive methane, the largest chemical transformation of methane remains confined to the highly energy demanding Fischer-Tropsch processes. At present, methane is industrially converted to Syngas, a mixture of carbon monoxide and hydrogen, to form useful products including methanol and Fischer-Tropsch hydrocarbons, which are synthesized in subsequent steps. The production of syngas is severely cost-limiting, however; “MegaMethanol” plants or the Fischer-Tropsch pearl complex in Qatar exceed 10 million metric tons (MT) of the total annual hydrocarbon production. As a result, the direct conversion of methane to valuable products on an economically viable technique are of extreme interest. Methane is a major component in natural gas and one of the most difficult molecules for controlled activation, since most of the product results in carbon dioxide. The industrial conversion of methane to alcohol derivatives is typically based on a circuitous route that begins with overoxidation to carbon monoxide. Although more direct approaches have shown promise in highly acidic media at a small scale, they are not quite cost-effective. In a recent study now published in Science, Christian Díaz-Urrutia and Timo Ott at the R&D department of Grillo-Werke AG Company describe a reaction at a pilot-plant scale that directly combined methane (CH4) and sulfur trioxide (SO3) in sulfuric acid (H2SO4) to form methanesulfonic (CH4O3S) acid without by-products. The reaction appeared to proceed via a cationic chain mechanism initiated by adding a low concentration of sulfonyl peroxide, propagated by methenium (CH3+) molecules. To afford pure MSA, Díaz-Urrutia and Ott completed the process by a final distillation step. They then recycled the remaining mixture of sulfuric acid and MSA to the first reactor for continued regeneration of sulfur trioxide and sulfuric acid (SO3 and H2SO4). Using the four reaction chambers of the setup, the scientists were able to produce 200 kg of pure MSA per week, amounting to two to three metric tons in 80 days. In this way, the demonstrated combination of high selectivity, conversion and atom economy made the process ideal for large-scale valorization of the readily available methane and sulfur trioxide reagents. If this new process of methanesulfonic acid becomes successful in the market, cheaper reagents will be able to replace the mineral acids presently in use. However, even if the production of MSA were to increase dramatically, the amount of methane consumed in the process would still be dwarfed by the amounts flared. Nevertheless, the work of Díaz-Urrutia and Ott predicts a new synthetic chemical process to synthesize an interesting chemical, allowing the scientists to envision a range of value-added products to be derived from methane or higher alkanes using this route of superacid chemistry in the future. GC-FID Chromatograms. A) GC-FID chromatogram of the gas phase of the reactor (100 bar) before sulfonation of methane has occurred. B) GC-FID chromatogram of the gas phase after (~40 bar) the sulfonation of methane has occurred (16 h, fuming sulfuric acid 36%, 500C). Credit: Science, doi: 10.1126/science.aav0177. More information: Christian Díaz-Urrutia et al. Activation of methane to CH3+: A selective industrial route to methanesulfonic acid, Science (2019). DOI: 10.1126/science.aav0177 Ferdi Schüth. Making more from methane, Science (2019). DOI: 10.1126/science.aaw7738 Christopher D. Elvidge et al. The potential role of natural gas flaring in meeting greenhouse gas mitigation targets, Energy Strategy Reviews (2018). DOI: 10.1016/j.esr.2017.12.012 Eric C. D. Tan et al. Reduction of greenhouse gas and criteria pollutant emissions by direct conversion of associated flare gas to synthetic fuels at oil wellheads, International Journal of Energy and Environmental Engineering (2018). DOI: 10.1007/s40095-018-0273-9 (A) Proposed ionic reaction mechanism for the C–H activation of CH4 in the selective production of MSA (Methanesulfonic acid). (B) Advantages of the cationic pathway over the radical pathway. T, temperature. Credit: Science, doi: 10.1126/science.aav0177 Explore further Making methane into more than fuel. Different commercialization pathways for methane, including the new process by Díaz-Urrutia and Ott. Commercial demand for products that would use the amount of methane that is flared exists only for compounds usable as fuels (methanol or higher hydrocarbons). Credit: Science, doi: 10.1126/science.aav0177 This document is subject to copyright. Apart from any fair dealing for the purpose of private study or research, no part may be reproduced without the written permission. The content is provided for information purposes only. Sulfonation of methane to MSA. (A) Schematic of the Díaz-Urrutia and Ott process. The reaction proceeds as a cascade through reactors connected in series. The pilot plant could produce up to 20 metric tons of MSA per year. The excess SO3 is quenched in reactor Q, the CH4 excess stream and the MSA/H2SO4 sump stream are recycled back to reactor 1, and the MSA-enriched mixture is distilled in column D to obtain pure MSA. (B) The concentration of MSA increases as it passes through the reactors. (C) Oblong quartz window reactor with gas impeller, for improved CH4 mixing. Credit: Science, doi: 10.1126/science.aav0177. © 2019 Science X Network Citation: Methane oxidation on the plus side – A selective industrial route to methanesulfonic acid (2019, April 2) retrieved 18 August 2019 from https://phys.org/news/2019-04-methane-oxidation-side-industrial-route.html In this context, the potential to sulfonate methane (CH4) to methanesulfonic acid (CH4O3S, MSA) has achieved substantial attention due to the abundance of both raw materials and the ability for its rapid integration into existing industrial chemical processes. MSA is biodegradable and nonoxidizing with potential applications in metal recycling, energy storage and biodiesel production. Preceding work on methanesulfonation suffered from low yields and conversions, due to free-radical recombination, resulting in undesired side-products such as ethane, rendering the methods unsuitable for large-scale production. Technically, the balance between reactivity and selectivity required by an industrial process can be provided by superacid chemistry. Díaz-Urrutia and Ott reported on the treatment of oleum (20 to 60 percent sulfur trioxide) with CH4 at approximately 500C using less than 1 mol percentage of the electrophilic initiator to form MSA with 99 percent yield and 99 percent selectivity. CH4(g) + SO3(l) → CH3SO3H(l) Journal information: Science Since the initial results were very promising, the scientists built a pilot plant facility and tested the economic and technical feasibility of industrial scale MSA production. Díaz-Urrutia and Ott constructed the plant with a projected capacity of 20 metric tons/year of MSA production, based on their laboratory-scale batch reactions, and accounted for methane solubility and recycling, as well as for the concentration of sulfur trioxide and methane. This configuration allowed the scientists to constantly increase the concentration of MSA as the reaction mixture passed through the reactors. When they used gas chromatography with flame-ionization detection (GC-FID) to monitor the samples, they did not detect the presence of higher alkanes in the recycled stream of methane or any other radical recombination products, allowing its direct use as feedback stock for the cascade reaction. The scientists first studied the reaction in a batch system to optimize experimental conditions and gain further insight into the reaction mechanism. For the electrophilic initiator, they used monomethylsulfonylperoxide sulfuric acid (MMSP) to improve technical feasibility. For increased productivity, they used a four-liter reactor instead of a 400-mL reactor, owing to larger quantities of CH4 forming in the headspace of the larger reactor. The scientists were thus able to maintain constant amounts of methane throughout the reaction for higher yields of MSA. They used an optimal temperature of 500C to achieve more than 99 percent selectivity towards MSA, whereas previous radical pathways had similar results at higher temperatures (850C) due to thermal decomposition of the sulfonyl peroxide electrophilic initiator. Low-temperature experiments could also offer high conversion and MSA selectivity, but required longer reaction times. Díaz-Urrutia and Ott comparatively provided insights to support a non-radical mechanism in the present work. When the scientists examined the reaction profile of the experiment, they observed an induction period immediately after addition of the electrophilic reactor, where the amount of MSA (product) was proportional to the initial quantity of MMSP (initiator). At stage two of the reaction profile, they observed the solubility of CH4 decrease with increasing pressure in the reactor. The activation energy of the process was determined to be 111±1 kJ/mol, similar to those previously reported. The described cationic pathway occurred under very specific conditions. The researchers achieved high selectivity through electronic changes in electrophilic substitutions, as opposed to the previously reported free-radical based atom abstraction reactions. A new way to directly convert methane to methanol using gold-palladium nanoparticles
Share Tweet Submit Anker deals are here, and this time the company has some interesting discounts on its Roav lineup of products featuring car chargers and dash cams. That’s not all, Anker has discounted its best Bluetooth speakers for 10 days.This Week’s Anker Deals are All About Your Car and Audio ListeningKicking things off is a discount on everyone’s favorite Roav 30W Spectrum car charger which features Quick Charge 3.0, car locating functionality, battery health checker and more. Usually is retails for $19.99, but it’s now discounted to just $15.99 for today only. That’s not all, the Roav Dash Cam C1 is discounted too, with the price falling down to $50.99 from $69.99. If that doesn’t please you, then you’ll be surprised to learn that the Roav Dash Cam C2 is discounted too and the price is just $44.99 for today only, falling down from the regular $57.99.Looking for a plain and simple car charger? Then you can pick up the PowerDrive+ 2 from Anker for just $14.89. This usually retails for 20 bucks on a regular day and it packed with many great features, including Quick Charge 3.0, PowerIQ including safety measures to keep your device cool and prevent overcharging.Anker is holding a sale on its Bluetooth lineup of speaker too, with discounts lasting 10 days, starting right now.First and foremost is the discount on everyone’s favorite SoundCore 2 speaker, with price coming down to just $29.99 from $39.99. If you are interested in picking this one up in Blue or even Red, then you have those options available to you as well.Last but not the least, the SoundCore Mini 2 is discounted to $34.99 from $41.99. But remember, don’t let the mini name fool you as it packs big sound under its apparently tiny exterior.
Wednesday, April 5, 2017 << Previous PostNext Post >> Tags: Costa Cruises, Family Travel, Promotions Posted by Travelweek Group Kids sail free with Costa Cruises this fall and winter HOLLYWOOD, Fla. — Costa Cruises is making it easier for families to travel on a budget with its Kids Sail Free promotion, valid on select voyages this fall and winter.With this promotion, kids sail free when travelling together as a family this fall and winter on select cruises into 2018. The cabin also receives an onboard credit up to US$200 per cabin, which can be used towards gift shop purchases, shore excursions, alternative dining and more.For example, a family of four can enjoy a Costa Diadema cruise from Barcelona for $998, plus port charges and gratuities. For Costa Favolosa’s Nov. 2 departure from Barcelona, rates start at $447 per person for the first and second person in the cabin, with kids cruising free as the third and fourth guests.Costa offers a wide range of family-friendly amenities and services to ensure the most exciting vacation experiences for families. Its Squok Club gives junior cruisers an endless selection of activities, including sport competitions, pool parties, face painting, dance lessons, themed dinners and the Princess and Captain for a Day programs.More news: Venice to ban cruise ships from city centre starting next monthFor the youngest passengers, the beloved character Peppa Pig makes every moment onboard fun. Many of the line’s Squok Clubs have been redecorated with Peppa images, while the outdoor swimming pool area reserved for children has been completely redesigned based on a Peppa pirate theme.Meanwhile, the Teen Junior Club for ages 12-15 and Teen Club for ages 15-17 features activities like music and dance courses, karaoke, talent shows, painting t-shirts, evening pool parties and sports tournaments. Share
in Headlines, News, Technology Pavaso’s VP of Partner Strategies, Government Affairs Elected to Co-Chair MISMO Workgroup Nancy G. PrattNancy G. Pratt, VP of Partner Strategies, Government Affairs at Pavaso, was elected to serve as co-chair of the Mortgage Industry Standards Maintenance Organization (MISMO) eMortgage Workgroup at the organization’s Winter Summit in January.The eMortgage Workgroup develops voluntary technical standards and business and technical guidance for the advancement of electronic mortgages and paperless technology in the mortgage industry and also provides general education about the legal framework for the use of eMortgages and related standards.“I’m elated to serve as part of the MISMO leadership. I’ve been active with MISMO for quite some time, so when the opportunity to co-chair a group that aligns so well with my endeavor to implement widespread eClosings, I jumped at the chance,” Pratt stated.Current projects for the eMortgage Workgroup include an Implementation Guide for SMART Docsâ, a report on warehouse lender interests and concerns with eNotes, and an eMortgage Glossary.“We have high expectations of everything that we can accomplish with this group and have strict objectives set to ensure that we achieve everything we set forth at the Winter Summit,” Pratt added.Pratt has been in the mortgage/title industry for over 32 years and has over 12 years’ experience specifically in the eMortgage/eClosing space. Highlights of her career include industry milestones of performing the first complete eMortgage with lenders and conducting the first ever FHA and VA eClosings. At Pavaso, Pratt manages the firm’s strategic partnerships and is responsible in maintaining relationships at the federal and state level, as well as understanding key regulatory issues and laws that pertain to the operations of Pavaso.She has been invited to speak at various Industry Conventions as an eClosing/eMortgage subject expert and is a member of the ALTA Government Affairs, Public Relations, State Regulatory Action and Technology Committee. Pratt is also a member of the MBA MISMO Residential Technology Committee. She is a member of PRIA, MBA, MISMO, ESRA, RESPRO, National eNotarization Board and served on the eMortgage FNMA Innovation Team. February 26, 2016 621 Views Share Pavaso VP of Partner Strategies and Government Affairs 2016-02-26 Staff Writer