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212-065 - Sun Certified Programmer for the Java 2 Platform SE 6.0 - Dump Information

Vendor : SUN
Exam Code : 212-065
Exam Name : Sun Certified Programmer for the Java 2 Platform SE 6.0
Questions and Answers : 287 Q & A
Updated On : March 22, 2018
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212-065 Sun Certified Programmer for the Java 2 Platform SE 6.0

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Retirement dream — greater cash for go back and forth, much less for fitness care? | killexams.com real questions with brain dumps

traditionally, retirement has a intended a shift in household budgets from the necessary to the indulgent — from mortgages payments, work fits and fuel to unique journeys, golf and upscale eating places.

however while older americans would like to tremendously ramp up spending on indulgences like shuttle and dining out when they retire, many are downsizing these visions, in line with an Ipsos/united states of america nowadays survey.

for instance, a quarter of forty five- to 65-yr-olds wish to set apart 21 p.c to forty percent of their post-retirement budgets for go back and forth, however most effective 13 % think they’ll be in a position to do so, in keeping with the September survey of 1,one hundred seventy people in that age bracket. just 2 percent of these surveyed currently earmark that lots for journeys, with ninety eight % spending zero to 20 p.c.

at the equal time, fifty three percent wish to commit lower than a fifth of their outlays to residing fees — issues like groceries, utilities and healthcare — of their golden years. but just 37 p.c consider they’ll attain that goal, with fifty seven percent expecting to allocate a fifth to a few-fifths of their budgets to those fundamentals, the same component that spends that amount these days.

now not holding paceThe gap between center-aged and older american citizens’ wants and expectations is at least partly a byproduct of the terrific Recession and its aftermath, which left many with shrunken nest eggs and stagnating incomes, economic planners say.

“youngsters the stock market has finally recovered, many americans don’t consider like they did 10 years ago,” earlier than the 2007-09 recession, says Sheryl Garrett, a certified economic planner and founder of Garrett Planning community. “Their salary isn't up and it’s no longer conserving tempo with inflation.”

Wages have risen about 2 p.c a 12 months for the regular American and many of the practically 9 million laid off all the way through the downturn had been compelled to take lessen-paying jobs for which there were overqualified.

also, lots of the middle-type clients Garrett serves sharply reduced their stock holdings throughout the 2008 crash and so haven’t benefited as tons from the eight-year-ancient bull market. An Ipsos/united states today survey past this 12 months found that 27 percent of forty five- to 65-12 months-olds don't have any retirement mark downs or investments and an additional 22 % have under $one hundred,000.

meanwhile, Congress is because repealing or scaling again the good value Care Act and reducing Medicare advantages to whittle down the ballooning country wide debt — measures that might swell older americans’ health care expenses.

“fitness care is the massive unknown,” Garrett says. due to this fact, while fundamental costs, just like the day by day work travel and lunch with a co-employee, may additionally disappear in retirement, rising scientific expenses may with ease take their region, tempering spending on greater gratifying actions.

looking ahead to some thing unhealthy to happenVeronica Ybarra, fifty four, of Albuquerque, N.M., turned into laid off from her technical writing job for a executive contractor in 2013, an event she says was a delayed response to the outcomes of the recession. despite the fact Ybarra is freelancing, her earnings is much lower than her old salary.

“I really hunkered down,” she says. “I haven’t had a real holiday due to the fact i will’t bear in mind when.”

Ybarra used to take weeklong journeys to California and to discuss with family in Denver and Chicago. When she retires at age sixty six to 70, she figures she’ll resume her prior shuttle sample as Social safety kicks in and he or she begins drawing from her 401(k) money. however ideally, she would want to take extended trips, spending three weeks in Europe, for example, and devoting as a great deal as 40% of her finances to travel as opposed to the 10% she’s planning. That will be viable, she says, however simplest if she will reclaim her former income through freelancing or another full-time job.

Ybarra similarly has cut returned on leisure, meeting a chum for dinner or coffee as soon as per week in its place of two to thrice as she used to – a tradition she would like to resume in retirement. nine percent of the older american citizens surveyed by means of Ipsos/u . s . these days predict to dedicate 21 percent to 40 percent of their budgets to amusement and eating out after they stop working — up from the four p.c who achieve this now — however 18 p.c would want to allocate that a lot.

Ybarra is additionally being conservative in her planning because she concerns the frothy stock market might crash, pummeling her retirement fund. “I simply maintain looking ahead to some thing dangerous to ensue,” she says. and she fears Congress will dial returned fitness insurance necessities. “Is my top class going to double?” she asks.

On the shiny aspect, she has paid off the loan on her three-bed room townhouse and she has no other debt.

focal point on debt reduction“some of the things we motivate is to do the most reliable which you could to get rid of any and all debt” earlier than retirement, says Sterling Raskie, a certified monetary planner at Blankenship financial Planners in Illinois. “It frees money circulation for different things.”

Forty-six p.c of the older american citizens surveyed at present spend 20% or less of their budgets on housing charges, although sixty two% predict to be in that place after they retire and conclude paying off mortgages. but seventy seven% would like to devote that little to housing. thousands and thousands of individuals lost their homes to foreclosures throughout the housing meltdown and both rented or at last purchased new homes that extended their personal loan payments into retirement. Others took out home fairness strains of credit all through the housing run-up that additionally extended their housing charge burdens, Garrett says.

Gary Gross, fifty seven, of Dillwyn, Va., retired in 2010 after working 25 years in public works for a city in southern New Jersey. His wife, Teresa, retired from a job within the identical city presently after and both bought pensions. They are expecting to spend 10% of their budget on shuttle and 15 % on entertainment in coming years however would favor to spend 30 % and 25 percent, respectively. as an alternative of two-day trips to Washington, D.C., or the Blue Ridge Mountains, they’d want to go to Las Vegas or Orlando — for a week or so.

Gary is being cautious partly because he has about $9,000 in bank card debt.

“I are looking to pay off the credit playing cards,” he says. “I don’t like having a lot of debt.”

Paul Davidson, united states nowadays

Vangochip know-how promises Wi-SUN (wireless smart Utility community) licensed Sub-GHz RF Platform | killexams.com real questions with brain dumps

HSINCHU, Taiwan--(company WIRE)--Vangochip know-how, an international-category fabless semiconductor business providing smart grid and IIoT conversation solution, nowadays introduced its first-gen sub-GHz RF family VC7000 handed the Wi-SUN® Alliance PHY Certification.

Wi-SUN Alliance PHY Certification application contains:

  • PHY Conformance checking out in accordance with IEEE 802.15.4g.
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  • The certification signifies Vangochip’s VC7000 family is formally validated and validated to have seamless interoperability and conformity to the business-agreed IEEE 802.15.4g specifications.

    VC7000 low vigour sub-GHz RF transceiver facets a extremely wide selection of RF bands from 169 to 960MHz. State-of-the-art sensitivity and selectivity with block-resilient IIP3 of -10dBm make it an important answer for robust smart utility networks. adjoining channel rejection can achieve more desirable than 40dB even at statistics rate > 50kbps. With a dual energy amplifier of +20/+13dBm and T/R change integrated, RBOM is tremendously decreased.

    VC7000 family is developed for battery-powered programs with quick wake-up and built-in false wake-up detection algorithm. forms of vigor-saving modes are delivered to mirror traits of IoT networks and cut back power consumption at system level. VC7300 of the household is a SoC integrating a Cortex M0 CPU and VC7000 with embedded flash and RAM for mission specific purposes. Mesh network application stack is supplied as part of the competent-to-use IoT radio answer to prolong insurance while tight integration of hardware and utility enhances device efficiency at different verbal exchange layers.

    As a Wi-solar Alliance contributor member, Vangochip expertise is dedicated to bringing values to valued clientele with continuous development of interoperable products based on open requisites. Vangochip technology gifts dual mesh (PLC + Wi-solar) verbal exchange SoCs for wise Utility community, together with box area community (FAN) and computer-to-machine (M2M) communications, with professional connectivity and efficiency.

    About Vangochip know-how

    Vangochip technology is a fabless IC design business offering industrial IoT and smart grid communique ICs, providing least expensive low vigor PLC and Wi-SUN twin mesh SoCs for functions in sensible Grid, sensible city, and wise domestic markets. www.vangochip.com.tw

    About Wi-solar Alliance

    Wi-SUN Alliance is an association of businesses working collectively to enable authentic, low-vigour wireless Utility items in line with open global standard IEEE 802.15.4g. www.wi-SUN.org

    holiday fitness: three the way to retain exercising all through the season | killexams.com real questions with brain dumps

    If exercise in't your element, there are a few weird issues which you could do to burn energy with out tying your footwear. Sean Dowling (@seandowlingtv) has extra. Buzz60

    Susan Nemiroff of Brick pushes a weight sled at Meridian health in Brick.(photo: Michael L. Diamond)

    If she desired, Susan Nemiroff has loads of excuses to skip her daily exercise hobbies given the time she should spend constructing her chiropractor follow, elevate her 6-year-historic daughter and put together for a busy break season.

    but there she turned into at Meridian fitness in Brick, New Jersey, throughout a fresh lunch hour, pushing a weight sled throughout the health club flooring.

    "It’s in my calendar to return figure out," Nemiroff, forty three, of Brick, noted. "It’s truly a scheduled time. My cell dings at me, I say, 'Oh, good enough, I have to go to the fitness center.'”

    Time-starved New Jerseyans are seeking the right way to retain their exercise routines going, even because the holiday season threatens to book their schedule.

    It brought on trainers and coaches to present suggestions, noting that recreation may still be a priority even with the browsing and events that the vacations convey.

    "you're the priority," referred to Kathleen Malachowski, chairwoman of the health and human efficiency branch at Ocean County college in Toms River. "the vacations are awesome and we need to do all the parties, but if you’re now not in an outstanding mind set or good fitness since you don't seem to be exercising, they in reality will also be depreciated."

    Brian Bocker of Avon-with the aid of-the-Sea, bottom, stretches out with Dan (top) and Mary Kiningham of Little Siver. Kyle Kim of Integrative wellbeing community holds a category instructing people appropriate foundation of endeavor. Belmar, NJ Wednesday, November 15, 2017 @dhoodhood  (image: Doug Hood)

    preserving an undertaking routine all through the vacations is never the easiest task. after all, the SUN goes down earlier and the weather receives colder, making a half-hour stroll backyard a chore.

    but Nemiroff, for one, has come to depend on both days every week of weight training and three days a week of cardio.

    Kyle Kim of Integrative health community holds a category teaching people suitable foundation of pastime. Belmar, NJ Wednesday, November 15, 2017 @dhoodhood  (picture: Doug Hood)

    She noted she's no longer a morning grownup. Or a night person, for that matter. So she has deploy her schedule to look customers from 9:30 a.m. to noon and from 3 p.m. to six p.m.

    It leaves her with an hour daily to activity.

    She pointed out it took her six weeks or so for the hobbies to be ingrained. but now that it has taken hold, she cannot pass over it.

    How does she feel after her every day exercise activities?

    "starving," she mentioned, before sensing that wasn't what the reporter desired to listen to. "I feel respectable. If i'd take time to do errands and paperwork (instead of activity), I’d have less power after I get returned in the workplace. This just continues me going.”

    experts are not stunned. They mentioned pastime can assist individuals lessen their stress, enhance their energy and control the results of ingesting and ingesting.

    Kyle Kim of Integrative wellness group holds a class instructing americans relevant basis of endeavor. Belmar, NJ Wednesday, November 15, 2017 @dhoodhood  (photo: Doug Hood)

    How can you do it in case you have a different holiday adventure on the calendar?

    listed below are some tips:

    1. Write it down

    you set your appointments, conferences, dinners and events on your calendar, why now not activity courses?

    It helps americans treat undertaking as a precedence, observed Dana Ferraro, a licensed electricity and conditioning professional at Meridian health, pointed out.

    "simply in typical in our day and age we're unfold so skinny and we’re so busy, discovering time to get to the health club is a daunting assignment," Ferraro talked about. "If my consumers don’t have scheduled appointments, they could now not make it in for the week."

    2. energy in numbers

    remember your annual holiday get-along side friends on the native restaurant or bar? Why now not consist of a hike, spin type or yoga type as a part of it?

    Ali Caulfield, a yoga and pilates instructor from Rumson, talked about she regularly goes on hikes with chums, giving her a chance to socialize and burn energy at once.

    "you've got your time to celebration, as adverse to going out and ingesting greater energy," she mentioned.

    three. store til you drop

    There are the right way to encompass activity to your holiday routines. as a substitute of looking online from the comfort of your couch, force to the mall, park in the furthest spot in the lot and walk.

    For shoppers of Kyle Klim, a chiropractor at  Integrative health community in Belmar, it is a chance to take the basis that they learned and put it into practice.

    His courses teach proper biomechanics, a way to hinge from the pelvis and hips, as an instance, in its place of straining their lessen lower back, bringing aid to seasonal tasks like carving a turkey or carrying searching luggage.

    "Or on the mall with youngsters, I can decide upon up my child from stroller in an easy way so it’s now not inserting stress on my returned," Klim said.

    There are a whole lot of different chances to flex your muscle mass. Race for the best deal on Black Friday, as an example, whereas nonetheless displaying courtesy to your fellow purchasers.

    "Don’t sit down as a whole lot and stand whereas they're wrapping your gifts," Malachowski at Ocean County college, observed. "You’re burning more energy. You continuously have to be thinking in terms of, how I may also be more lively although i am stuck interior.”

    Michael L. Diamond; @mdiamondapp; 732-643-4038; mdiamond@gannettnj.com



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    Clarksville man drowns in Deam Lake | killexams.com real questions with brain dumps

    The physique of a 32-12 months-historical man turned into recovered at Deam Lake on Tuesday afternoon, a victim of a drowning that came about Monday night.

    in response to witness reviews, Clarksville resident Thomas King left the lake’s targeted swimming area with a raft and about halfway throughout the lake he lost control of the raft or it floated away. 

    “A witness saw him basically yell for support after which he went below,” said department of natural components Conservation Officer Jim Schreck.

    King’s mother, Charlotte King, lower back to the lake as divers looked for Thomas on Tuesday.

    She spoke of she had tried to dissuade her son from swimming across the lake, however he bought on a raft and headed across anyway.

    although his family unit pointed out he turned into a capable swimmer, he went under water earlier than he reached the other side of the lake.

    Schreck talked about Thomas King was not wearing a life jacket and become outside the swimming area, however no foul play is suspected and it is not going that an investigation should be conducted.

    Indiana Conservation officers all started the quest at about 5:30 p.m. Monday, earlier than they had been pressured to droop the hunt at about 2:30 a.m. the search resumed Tuesday morning once early-morning storms abated.

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    “It’s only a tragic accident,” he introduced.

    The drowning is the first incident at Deam Lake this 12 months, which stated two drownings in a 5-day span final summer season.

    “How repeatedly is a person going to ought to drown out here earlier than they get a lifeguard to drive [people] to live within the swimming area?” asked Francis King, Thomas King’s sister.

    The department of natural substances has no longer staffed its seashores with lifeguards because 2001.

    Ray needs potent conclude at TMS | killexams.com real questions with brain dumps

    fort price (AP) - Greg Ray clinched final season's IRL elements championship at Texas Motor Speedway, just miles from his domestic. he's back desiring a strong conclude simply to have a chance for one more title.

    Heading into Saturday nighttime's on line casino Magic 500, the midpoint of the Indy Racing League's nine-race season, Ray is seventeenth within the features standings and coming off a latest-vicinity finish at the Indianapolis 500 after successful the pole there.

    "Now that Indy is behind us, it is vital for us to focal point on every lap of each race," pointed out Ray, who is from local Plano. "here's very important, having a restricted number of races."

    Ray was set to start within the front row for the on line casino Magic 500, however his 2nd-optimum qualifying lap of 212.022 mph was wiped out when rain Friday prevented 10 of the 27 drivers from qualifying. The starting lineup become then set via season elements, pushing Ray back to 17th on the inner of the row 9.

    Worse than having his streak of 15 consecutive precise-5 starts ended, Ray lost two IRL elements that could have come had his front-row birth stood.

    Mark Dismore, who become sitting on the provisional pole at 212.065 mph when the rain all started, will beginning on the third row. Dismore gained the Mall.com 500 at TMS final October, however his most effective IRL victory became overshadowed with the aid of local favorite Ray claiming the season title.

    The casino Magic pole as an alternative went to IRL features leader buddy Lazier, whose handiest different pole became within the league's inaugural race at Disney World in 1996. On his aspect may be Robbie Buhl, whose handiest other front-row beginning become at the first IRL race in Texas three years ago.

    Lazier, who went from ultimate to first to win at Phoenix this season, had completed qualifying with a lap of 209.873 mph. That became seventh-foremost amongst those qualifying, five spots superior than Buhl's lap of 209.043 mph.

    "the manner we now have been qualifying this year, it was already a a hit qualifying run," referred to Lazier, who has started 16th or worse the remaining three races. "we'll definitely take it, however we consider unhealthy for Mark and some of the guys."

    Scott Goodyear, the defending race champion, will birth third in accordance with aspects. He had run a qualifying lap of 210.929 mph that was fifth-most beneficial.

    ultimate June, Ray become in reality in an analogous condition when he bought to Texas for the first of both IRL races there. He had finished 21st in three straight races, despite starting within the front row every time, and changed into twentieth within the element standings.

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    Baseball: Onedia tops NYM, Hamilton routs Waterville, VVS beats Rome Free Academy, Canastota, Madison and M-E fall | killexams.com real questions with brain dumps

    ROME -- Thanks in colossal half to Brandon Inman's pitching, Oneida's baseball group posted its second win of the spring Monday. Inman fanned three and walked none while scattering nine hits in a 5-2 win against ny Mills at Delutis container.

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    Oneida 200 one hundred 2 5-7-3


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    Sauquoit Valley 30, M-E 1

    MORRISVILLE -- Morrisville-Eaton's baseball team dropped its third online game of the 12 months on Monday. Sauquoit Valley scored seven runs in the first inning and certainly not seemed lower back in racing to a 30-1 victory.

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    M-E 000 01 1-5-9

    Slivinski (W); Alec Diable (L).

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    VVS 9, Rome 4

    ROME -- Vernon-Verona-Sherrill's baseball team scored 4 runs within the fourth inning to show a one run deficit into three run lead in a 9-four win over Rome Free Academy Monday.

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    SUN 212-065 Exam (Sun Certified Programmer for the Java 2 Platform SE 6.0) Detailed Information

    Article by ArticleForge

    Labonte Grabs Kmart 400 Pole With Track Record

    June 10, 2000|By Chris Kuc.

    It was Jeff Gordon's to lose. Then it was Ricky Rudd's to sit on while time ran out.

    But it was NASCAR Winston Cup points leader Bobby Labonte's to drive away with Friday before a sun-soaked crowd of 40,000 at Michigan Speedway. "Man, where did that come from?" Gordon asked after Labonte's NASCAR track-record lap of 189.883 m.p.h. took the pole for Sunday's Kmart 400.

    Labonte, whose record run in a Pontiac was achieved on the day's 44th attempt, became the 10th driver to win poles in this year's 14 Winston Cup events.

    - Mark Dismore's blistering lap of 212.065 m.p.h. at Texas Motor Speedway was washed out with only five drivers yet to qualify, costing Dismore a chance at his fourth career Indy Racing League pole. Cars will line up for the start of Saturday night's Casino Magic 500 based on the season point standings, with current leader Buddy Lazier starting from the pole.

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    Dashboard & Steering Column

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    Immunological aspects of congenital disorders of glycosylation (CDG): a review

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    Production of a Biofuel that Keeps the Glycerol as a Monoglyceride by Using Supported KF as Heterogeneous Catalyst †

    1. Introduction

    Oil is currently indisputably the main source of energy, with a demand of about 12 million tons per day, and a projected increase to 16 million tons per day by 2030 [1]. It is estimated that within 50 years, some oil reserves in some countries will be depleted, and many of the remaining sites (located at great depth andor in oceans) will be inaccessible, which will inevitably cause rising oil prices as well as increasing anthropogenic emissions of greenhouse gases (GHG) causing the global warming effect. Thus, the research efforts on different renewable fuels have grown in the last years [2]. However, is widely accepted that this target will not be easy to implement, and it will require a major coordinated effort by many groups—political forces, scientific organizations, economic and social actors, and of course the citizens—to access and develop new economic and social scenarios where the energy and commodities will not be, as currently happens, completely dependent on fossil oil and consequently GHG producers [3].

    The term biodiesel is currently reserved for those biofuels made of a mixture of monoalkyl esters of long chain fatty acids, derived from renewable lipids such as vegetable oils or animal fats, that can be used in the current combustion engines without any modification, as they have physicochemical properties similar to conventional fuels. Besides, they offer additional advantages, like being renewable, biodegradable and nontoxic compounds, that are essentially free of sulfur and aromatics so that it represents an added value due to their environmental safety [4,5].

    The benefits of biofuels over traditional fuels include also greater energy security, reduced environmental impact, foreign exchange savings, and positive socioeconomic issues related to the rural sector. The use of waste oils and fats in biodiesel production also reduces many environmental complications and could be friendly energy drivers for all countries [6]. Thus, in recent years biodiesel production has become a very important potential alternative to partially fulfill the expected future energy demands in the transport sector [7,8]. In this connection, the most usual technology to process vegetable oils or animal fats is based on the conversion of the triglycerides (TG) to fatty acids methyl esters (FAME) by a transesterification reaction with methanol. However, there are also several alternative routes to use vegetable oils or animal fats like a biofuel, including direct use of vegetable oil, microemulsions and emulsifications [9].

    Regardless of the procedure used to obtain the so-called conventional biodiesel (homogeneous or heterogeneous, acid or basic catalysts, lipases, supercritical conditions, etc.), in all cases the glycerol is formed as a by-product, representing a notable performance loss in the process, given that the market is already virtually flooded with the produced glycerine, obtained precisely as a by-product in the current manufacture of biodiesel [10,11]. Thus, this current method supposes a decreased yield of the process, always higher than nominal 12 wt%, due to the glycerol obtained as a reaction product, which in very small amount is also incorporated to the biodiesel (FAME, Fatty Acid Methyl Ester) phase. In this respect, the cleaning of glycerol is necessary, because of its ability to react with oxygen inside the engine at high temperature, where it could produce dehydration forming acrolein, that can be polymerised causing several problems, including coking of fuel. This coking can also generate deposits of carbonaceous compounds on the injector nozzles, pistons and valves in standard engines, thus reducing their efficiency and even their service life [1,8].

    To avoid the problems associated with the generation of glycerol in the conventional process, a series of alternative methods are considered to get the highest atom efficiency by avoiding the production of glycerin. Thus, a target of great interest currently is the production, in only one reaction, of new biofuels that integrate the glycerol as a derivative product, miscible with the fatty acid methyl or ethyl esters (FAME or FAEE) obtained in the same transesterification process. Basically, this is possible by using some alternative esters, instead of the alcohol usually employed in the conventional process. Thus, if some glycerol derivative compound is obtained at the same time that FAME (or FAEE) in an interesterification process, a new biofuel is obtained in only one reaction avoiding the presence of glycerol, that is, instead of glycerol its corresponding ester is obtained, together to the FAME mixture. These new biofuels not only prevent the generation of waste glycerol, but also increase the yields of the process, always higher than nominal 12 wt%, by incorporating some glycerol derivatives into the reaction products. In this way, the highest atom efficiency, practically 100 wt%, is obtained. Novel methodologies to prepare esters from lipids using different acyl acceptors which directly afford alternative co-products are currently under development [12].

    The interesterification processes can be performed with the same catalysts applied in the standard transesterification processes (homogeneous or heterogeneous, acid or basic catalysts, lipases, supercritical conditions, etc.), although at present most of these processes, when applied to the production of biofuels, are carried out using different lipases [12], where instead of using methanol, the lipase-catalyzed synthesis of fatty acid alkyl esters can also be performed using alternative alcohol donors such as methyl or ethyl (alkyl) acetate and dimethyl or diethyl carbonate. These mixtures including glycerol derivative molecules have relevant physical properties to be employed as novel biofuels. The atom efficiency is also improved as all the atoms involved in the reaction become part of the final mixture. Even the reactants used remain together to the obtained reaction products to be directly used as biofuels [12,13,14,15,16,17,18]. Thus, the transesterification reaction of triglycerides with dimethyl carbonate (DMC) [13,14] generates a mixture of FAME and glycerol carbonate (GC), which is soluble in FAME and has physical properties suitable for use as fuel, so it has been introduced as a new biofuel called DMC-BIOD [15]. Similarly, the transesterification of methyl acetate with some vegetable oils generates Gliperol® (Warsaw, Poland), a new patented biofuel [16,17,18] constituted by three molecules of FAME and one molecule of triacetin or glycerol triacetate.

    In recent studies an alternative methodology is implemented that avoids the generation of glycerol by developing a partial enzymatic ethanolysis of the triglyceride molecules, that generates two molecules of fatty acid ethyl esters (FAEE) and a molecule of monoacylglycerol (MG). This enzymatic method using pig pancreatic lipase (PPL) to cause the enantioselective ethanolysis of sunflower oil has shown promising results [19,20,21,22,23,24] in the preparation of a new biofuel patented by University of Cordoba, named Ecodiesel-100 [22]. This method takes advantage of the 1.3-selective nature of many lipases, which allows stopping the process in the second step of the alcoholysis reaction to obtain a mixture of two moles of FAEE and one MG. In this respect it is interesting to point out in this respect that according to recent studies the presence of MG enhances the lubricating properties of the biofuel [25,26]. So far this process is being developed not only with PPL but also with some microbial lipases, both in free and immobilized forms [19,20,21,22,23,24].

    The current existing limitations to the use of lipases are mainly associated with their high costs, so that in order to achieve an increase in viability and competitiveness respect to the enzymatic process, the present study aims to achieve the partial transesterification reaction, through the kinetic control of the chemical reaction, to obtain the same results previously described in stereoselective enzymatic processes. Thus, now is intended to obtain the same new biodiesel that contains monoacylglycerol, by using KF as alkaline heterogeneous catalyst, as an alternative to the more expensive lipases (Figure 1).

    Figure 1. Representative scheme of the production of Ecodiesel, a biofuel, by partial methanolysis of sunflower oil.

    Figure 1. Representative scheme of the production of Ecodiesel, a biofuel, by partial methanolysis of sunflower oil.

    In this respect, some promising results have been previously obtained by using CaO as an alkaline heterogeneous catalyst [27]. In the present research, a series of supported KF catalysts, previously applied as basic catalysts in some organic synthetic processes [28], are investigated in the methanolysis reaction of sunflower oil to obtain the desired selective transesterification, through the kinetic control of the consecutive chemical process, to get the same biodiesel without glycerol generation, as an alternative to the more expensive lipases.

    Taking into account that the transesterification reaction is a sequential process consisting in three successive methanolysis steps, where a molecule of TG (triglyceride) and three molecules of methanol lead to a molecule of glycerol and three of FAME, it is conceivable that some kinetic parameters like amount of catalyst, molar oilmethanol ratio, reaction temperature and the reaction time could be critical parameters to control in order to develop a selective process with only two successive methanolysis steps to keep the glycerol as a monoglyceride (Figure 1).

    On the other hand, heterogeneous catalysts, unlike to homogeneous ones, are environmentally benign and could operate in continuous processes. Moreover, they can be reused and regenerated. Among them, supported-KF catalysts seems to have a promising place according to the increasing number of research works devoted to its capability to catalyze the triglyceride methanolysis reaction [29,30,31,32,33,34,35,36]. In contrast, no reports have been found regarding the catalytic behaviour of supported CsF, NaF or LiF in transterification reactions of oils or fats to obtain biodiesel [37].

    However, despite the success obtained with supported KF catalysts [29,30,31,32,33,34,35,36,37], one always gets a marked decrease in the catalytic activity, as compared to homogeneous catalysis, which requires operating at higher temperatures and pressures, with higher oilmethanol proportions, which so far has discouraged their implementation on an industrial scale for the conventional biodiesel production.

    Nevertheless, this weaker basic character of supported KF catalysts could be an important advantage to achieve a selective methanolysis, where the process is stopped in the second step (like in Figure 1), after optimizing the experimental conditions (catalyst weight, oilmethanol relative concentration, temperature, reaction time, etc.) to achieve the kinetic control of the selective methanolysis process. In this way, the use of heterogeneous low cost catalysis to produce a biofuel without glycerol generation, could solve many of the problems of conventional homogeneous catalysts (NaOH or KOH), because the yields of the process are increased (10–12 wt%), the neutralization step of the reaction products is avoided, as well as the cleaning process after the synthesis of biodiesel and the waste management of glycerol generated.

    2. Results and Discussion 2.1. Influence of the Inorganic Solid Used as KF Support on Process Performance

    Among the different inorganic solids described in the literature as supports of KF to obtain heterogeneous basic catalysts useful in the production of conventional biodiesel [29,30,31,32,33,34,35,36,37], in the current study Al2O3, ZnO and MgO have been evaluated as supports of KF at 10 wt%. These were obtained following the experimental methodology previously described [28]. To determine the comparative behaviour of the different supported KF systems, Table 1 collects the results obtained when operating under the standard conditions previously determined with CaO heterogeneous catalysts [27]. Thus, reactions were carried out with 0.8 g of 10 wt% supported KF on the three inorganic solids, Al2O3, ZnO and MgO, at 65 °C reaction temperature with 12 mL of sunflower oil (32 cSt, kinematic viscosity) and 2.43 mL of methanol.

    Table 1. Reactions performed under standard conditions, using 12 mL of sunflower oil (viscosity 32.0 cSt) 2.43 mL of methanol, reaction time 60 min, temperature 65 °C and 0.8 g of KF 10 wt% supported on various inorganic solids weight Al2O3, ZnO and MgO.

    Table 1. Reactions performed under standard conditions, using 12 mL of sunflower oil (viscosity 32.0 cSt) 2.43 mL of methanol, reaction time 60 min, temperature 65 °C and 0.8 g of KF 10 wt% supported on various inorganic solids weight Al2O3, ZnO and MgO. Support Viscosity (cSt) Conversion (%) Selectivity (%) Al2O3 4.62 100 94.95 ZnO 8.40 100 83.54 MgO 5.88 100 92.40

    According to the results, with all the three KF supported catalysts studied, under the indicated experimental conditions, similar results to those achieved in the enzymatic processes were obtained [19,20,21,22,23,24], where instead of glycerol monoacylglycerols that are soluble in the FAME mix are obtained. The experimental conditions currently applied were clearly milder than those required for the production of conventional biodiesel with supported KF catalysts [29,30,31,32,33,34,35,36,37]. These results are also similar to those obtained with CaO [27,38] in regard to the values of conversion and selectivity parameters; however are better respect to the kinematic viscosity values obtained.

    Taking into account the best results obtained with Al2O3 as support of KF, this basic heterogeneous catalyst was chosen to obtain an improved set of reaction parameters like the amount of catalyst, molar oilmethanol ratio and temperature, to optimize as much as possible the experimental conditions to improve the selective methanolysis process of sunflower oil. Thus, although similar values of kinematic viscosity are obtained to those of conventional biodiesel derived from sunflower oil, that presents values in the range 4–6 cSt, it seems necessary to better optimize the experimental operating conditions, since the proposed objective is to determine the experimental conditions that allow to obtain a viscosity as low as possible, without producing glycerol, under milder and greener operation conditions.

    2.2. Influence of Catalyst KFAl2O3 Weight on Process Performance

    Under the determined operating conditions (temperature, oilmethanol ratio and reaction time) in a heterogeneously catalyzed process, the amount of catalyst used determines whether the operating conditions are kinetically controlled or not. In such a case, the catalytic activity is directly proportional to the weight of catalyst used. Outside this region, in which the weight of the catalyst does not affect the performance of the process, the results are not related to the catalytic properties of the solid studied, indicating that the kinetic control of the consecutive methanolysis reaction, passes from the catalyst to the reactants, so that the higher amounts of catalyst will remain practically inactive (the active sites of catalyst surface are starved of reactants). Thus, first of all it is necessary to confirm that the standard conditions previously indicated in Table 1, allows one to operate under kinetic control of the methanolysis process studied.

    In this respect, to evaluate the influence of the weight of the catalyst, different amounts of KFAl2O3 catalysts (from 0.2 to 1 g) have been used under the same standard experimental conditions indicated in Table 1, (65 °C, 12 mL oil, 2.43 mL methanol and 60 min reaction times). Results obtained are collected in Figure 2. These results show that, under the standard experimental conditions, Conversion and Selectivity increasingly grow to practically reach a maximum with KFAl2O3 amounts higher than 0.8 g (7 wt% respect to oil) where the kinematic viscosity values are around 4.5 cSt. The kinematic viscosity values exhibit more clearly the typical behavior of a heterogeneous process developed under kinetic control due to the straight decrease of viscosity values obtained on increasing the catalyst weight.

    Furthermore, the fact that in no case the slightest amount of glycerol was obtained, according to the GC analysis of the reaction products, highlights the undoubtedly selective character of the consecutive methanolysis process. This can be explained as a consequence of the fact that the selective nature of the process is based on the strength of the active basic sites, more than on the number of these active sites. Accordingly it can be concluded that the basic sites of the KF catalysts have enough strength to carry out the methanolysis of the primary hydroxylic bonds of triglycerides, in the 1 and 3 positions of glycerol, but these basic sites on the KF catalysts are not enough strong to be able to promote the transesterification of the less active secondary alcohol, in position 2 of glycerol.

    Figure 2. (a) Viscosity values and (b) Conversion and Selectivity values, obtained in the heterogeneous selective methanolysis of sunflower oil under standard conditions, with different amounts of KFAl2O3, reaction time 60 min, reaction temperature 65 °C, 12 mL of oil and 2.43 mL of methanol.

    Figure 2. (a) Viscosity values and (b) Conversion and Selectivity values, obtained in the heterogeneous selective methanolysis of sunflower oil under standard conditions, with different amounts of KFAl2O3, reaction time 60 min, reaction temperature 65 °C, 12 mL of oil and 2.43 mL of methanol.

    The use of higher catalyst amounts will not promote increasing catalytic activity because under these conditions kinetic control of the reaction does not operate. This indicates that the best experimental conditions are obtained by using 8 wt% of heterogeneous KF catalyst, respect to the amount of oil used.

    2.3. Influence of Molar OilMethanol Ratio on Process Performance

    The influence of the molar (oilmethanol) ratio on the catalytic performance of the methanolysis process was determined operating under the standard experimental conditions previously considered in Table 1 (reaction time 60 min, 65 °C, 0.8 g KFAl2O3 and 12 mL oil) using different amounts of methanol from 1.2 to 2.8 (13 to 17). The results shown in Figure 3 indicate that despite the continuous decrease in kinematic viscosity values, Conversion, and mainly Selectivity, reach a maximum at a molar oilmethanol ratio of 15.

    According to the mass action law governing the chemical equilibrium in reversible processes, the Conversion and Selectivity could be improved by introducing excess quantities of methanol to shift the equilibrium and get a higher amount of FAME. The experimental results, collected in Figure 3, accordingly indicate that the biodiesel yield (Conversion and Selectivity) grew with increasing molar relation oilalcohol until it reached the maximum value (15) but, when this increase continues, the methanolysis reaction yield is then lowered. Thus, the molar ratio of methanol to oil has a significant impact on the viscosity of the obtained biodiesel, where the lowest viscosity value is associated to higher Conversion and Selectivity values, 100% and 98.8%, respectively.

    Figure 3. (a) Viscosity values and (b) Conversion and Selectivity values, obtained in the heterogeneous selective methanolysis of sunflower oil under standard conditions, with different molar oilmethanol ratios, reaction time 60 min, reaction temperature 65 °C, 12 mL oil and 0.8 g of KFAl2O3.

    Figure 3. (a) Viscosity values and (b) Conversion and Selectivity values, obtained in the heterogeneous selective methanolysis of sunflower oil under standard conditions, with different molar oilmethanol ratios, reaction time 60 min, reaction temperature 65 °C, 12 mL oil and 0.8 g of KFAl2O3.

    2.4. Influence of Temperature on Process Performance

    The optimized conditions (weight of catalyst, reaction time and molar oilalcohol ratio) have been established according to an elevated temperature, 65 °C. However, the evaluation of the influence of reaction temperature on reaction performance may provide information of interest in relation to the catalysed reaction mechanism of the sunflower oil methanolysis process. Thus, under the experimental conditions of Table 1 (time reaction 60 min, 0.8 g KFAl2O3, 12 mL oil and 2.43 mL methanol) several reactions were carried out at different temperatures in the 45 to 65 °C range. Results shown in Figure 4 indicate that Conversion and Selectivity reach the highest value, 100% and 99.9% respectively, at 50 °C, however viscosity values exhibit a continuous decrease with increasing temperature.

    Recalling that the Selectivity is connected to those methanolysis products with similar RT (retention time) values to those hydrocarbons that comprise conventional fossil diesel, and in this interval not only the different FAMEs are present, but also the corresponding MGs. Besides, a 99% Selectivity with Conversion of 100% would indicate the presence of at least 1% of DG (diglyceride), so that the viscosity obtained is somewhat higher that corresponding to pure the FAME constituting conventional biodiesel. That is, it is perfectly possible for two reaction samples with similar Conversion and Selectivity values to differ in viscosity values. Thus, it is concluded the greater relevance of the viscosity with respect to the Conversion and Selectivity data, with respect to the information obtained on the consecutive reaction progress of sunflower oil methanolysis.

    In this respect, the viscosity appears as the most sensitive parameter to the progress of the reaction where the Arrhenius equation that fit Equations (1) and (2) it can be applied as can be seen in Figure 5, where the kinematic viscosity is a parameter directly related to the reaction rate constants:

    Lnk = LnA − (EaRT)


    Figure 4. (a) Viscosity values and (b) Conversion and Selectivity values, obtained in the heterogeneous selective methanolysis of sunflower oil carried out under standard conditions, reaction time 60 min, 0.8 g of KFAl2O3 catalyst, 12 mL of oil and 2.43 mL of methanol, under different reaction temperatures in the interval 45–65 °C.

    Figure 4. (a) Viscosity values and (b) Conversion and Selectivity values, obtained in the heterogeneous selective methanolysis of sunflower oil carried out under standard conditions, reaction time 60 min, 0.8 g of KFAl2O3 catalyst, 12 mL of oil and 2.43 mL of methanol, under different reaction temperatures in the interval 45–65 °C.

    Figure 5. Arrhenius plot (Lnk vs. 1T) obtained from the evolution of Lnk values with temperature, where k = viscosity−1; operating under standard conditions, with 12 mL of oil, 2.43 mL of methanol, 0.8 g of catalyst weight, 60 min reaction time and different reaction temperatures in the interval 25–65 °C.

    Figure 5. Arrhenius plot (Lnk vs. 1T) obtained from the evolution of Lnk values with temperature, where k = viscosity−1; operating under standard conditions, with 12 mL of oil, 2.43 mL of methanol, 0.8 g of catalyst weight, 60 min reaction time and different reaction temperatures in the interval 25–65 °C.

    Here we have that A is the Arrhenius pre exponential factor and Ea is the activation energy of the reaction. This equation is linear with respect to 1T. If k is determined for varying temperatures, the plot of Ln k vs. 1T should produce a straight line of slope −EaR. The inverse of kinematic viscosity is used because of this parameter inversely decreases with the progress of the reaction. In this way it is obtained that LnA = 5.37, where A is expressed in cSt−1. Activation energy value Ea = 1.16 Kcalmol is a relative low value that indicates a low influence of temperature on the reaction rate. Thus, it manifests the higher catalytic activity of the KFAl2O3 catalyst.

    It is also important to note how the Selectivity, the Conversion and the inverse of the kinematic viscosity follow a parallel evolution among them, so that is perfectly demonstrated that with the transformation of TG into DG and this in MG, a gradual reduction in the values of kinematic viscosity is obtained, that is, the viscosity decreases more as the concentration of TG and DG is more reduced. The MG concentration does not appear to affect the viscosity of the mixture in a similar measure as those of TG or DG do. Presumably, the influence of these species in the viscosity of reaction mixture will be directly related to the relative values of their respective molecular weights, so that TG ≈ 32 DG ≈ 3 MG ≈ 3 FAME.

    2.5. Influence of the Repeated Used of the Three Catalysts, on the Process Performance

    Taking into account that a main advantage of heterogeneous catalysts is the possibility of their reuse, the catalytic behaviour of repeated uses of the three different KFsupport catalysts was investigated, where as supports Al2O3 ZnO and MgO have been studied. Figure 6, Figure 7 and Figure 8 show the variation of Conversion, Selectivity and viscosity over the five studied reuses.

    To evaluate the reuses of the different catalysts, in the first reaction 12 mL sunflower oil and 2.43 mL methanol (corresponding to a 16 oilmethanol molar ratio), and 0.8 g catalyst (7 wt%) was used, operating at 65 °C for 60 min. In the next successive reactions the same amounts of sunflower oil and methanol were added after withdrawing the previous reaction products. Thus, after allowing the reaction product to be decanted for one hour, the supernatant liquid is removed with a pipette and the supported KF solid catalyst remains deposited in the bottom of the flask reactor, ready to be used again in the next reaction.

    Figure 6. (a) Viscosity values obtained in the successive reuses of heterogeneous selective methanolysis of sunflower oil under standard conditions, with 0.8 g of KFAl2O3, 65 °C, 12 mL of oil and 2.43 mL methanol. (b) Conversion and Selectivity values obtained with identical conditions.

    Figure 6. (a) Viscosity values obtained in the successive reuses of heterogeneous selective methanolysis of sunflower oil under standard conditions, with 0.8 g of KFAl2O3, 65 °C, 12 mL of oil and 2.43 mL methanol. (b) Conversion and Selectivity values obtained with identical conditions.

    Figure 7. (a) Viscosity values obtained in the successive reuses of heterogeneous selective methanolysis of sunflower oil (viscosity 32.0 cSt) under standard conditions, with 0.8 g of KFZnO, 65 °C, 12 mL of oil and 2.43 mL methanol. (b) Conversion and Selectivity values obtained with identical conditions.

    Figure 7. (a) Viscosity values obtained in the successive reuses of heterogeneous selective methanolysis of sunflower oil (viscosity 32.0 cSt) under standard conditions, with 0.8 g of KFZnO, 65 °C, 12 mL of oil and 2.43 mL methanol. (b) Conversion and Selectivity values obtained with identical conditions.

    Figure 8. (a) Viscosity values obtained in the successive reuses of heterogeneous selective methanolysis of sunflower oil (viscosity 32.0 cSt) under standard conditions, with 0.8 g of KFMgO, 65 °C, 12 mL of oil and 2.43 mL methanol. (b) Conversion and Selectivity values obtained with identical conditions.

    Figure 8. (a) Viscosity values obtained in the successive reuses of heterogeneous selective methanolysis of sunflower oil (viscosity 32.0 cSt) under standard conditions, with 0.8 g of KFMgO, 65 °C, 12 mL of oil and 2.43 mL methanol. (b) Conversion and Selectivity values obtained with identical conditions.

    According to the results, with all three supported KF catalysts studied it is obtained that, after the first reaction, Conversion and Selectivity decrease continuously while the kinematic viscosity is increased from 5 to 7 cSt to values close to 20 cSt, corresponding to a lowering in the Conversions and Selectivity from 100% to values lower than 10%. In this respect, KFAl2O3 exhibits the worst catalytic behaviour respect to reuse capability, despite of the fact of being the best heterogeneous KF catalyst studied in the first use. The catalysts KFZnO and KFMgO allow a second reuse, with the same catalytic behavior seen in the first one, and a softer decline in Conversion and Performance that the Al2O3 catalyst. However, the CaO catalyst [27] showed a better performance in regard to the reuse of the heterogeneous catalysts. Catalyst deactivation in no case could be associated to a leaching of the supported KF, according to results obtained after separation of the solid catalysts from the reaction when the reaction was started. These complementary studies, included in the Experimental section, indicate that reaction was always completely interrupted after the separation of supported KF catalyst. Thus, no KF was present in the medium reaction. In this way, deactivation ought to be adscribed to some kind of interaction of reaction products or to impurities, like free fatty acids presents in very little amounts in the sunflower oil.

    3. Experimental Section 3.1. Materials

    Sunflower oil with a kinematic viscosity of 32 cSt was obtained commercially. Chromatographically pure ethyl esters of palmitic acid, stearic acid, oleic acid, linoleic acid and linolenic acid were commercially obtained from Accustandard (New Haven, CT, USA), and the hexadecane (cetane) from Sigma-Aldrich (St. Louis, MO, USA). The catalysts and the methanol were obtained commercially from Panreac (New Delhi, India) and were of a purity >99%.

    3.2. Synthesis of Catalysts: Supported KF

    To synthesise of 10% KF systems supported on three different inorganic solids (Al2O3, ZnO and MgO) an “incipient wetness” impregnation method described previously has been used with a solution of KF (Panreac P.A.), in methanol-water [28]. Thus, support (9 g) and a solution of KF (1 g) mixed in methanol (5 mL) and water (2 mL) were mixed with continuous stirring in a rotary evaporator for one hour. Then the solvent was removed by evaporation to dryness. The solid is heated in an oven at 150 °C for 24 h to remove solvent residues before use.

    3.3. Alcoholysis Reactions

    The transesterification reaction of food-grade sunflower oil was carried out in a stirred batch reactor, consisting of a 25 mL volume round bottom flask, which was placed in a thermostatic bath. The reactor, with controlled temperature and stirring speed, is equipped with a reflux condenser to avoid methanol losses. The stirring speed was set at 700 rpm to prevent mass transfer limitations. Sunflower oil, methanol and the activated solid were introduced into the reactor, trying to avoid as much as possible contact between the catalyst and the room atmosphere. After the temperature is raised to the desired value, the reaction starts with the agitation of reactants and catalyst in the reactor. The reaction mixture comprises sunflower oil (9.4 g, 12 mL, 0.01 mol), a variable oilalcohol molar ratio (12–112), temperatures in the 30–65 °C range and different catalyst amounts in the 0.2–1.0 g range.

    In order to exclude the possibility of leaching of KF into the reaction product, some experiments were conducted by measuring the activity of filtrate after 50% conversion, to prove that the reaction does not go to completion after the supported KF solid catalyst is removed from the reaction medium.

    3.4. Analytical Methods

    Reaction products were monitored at 450 °C with splitless injection at 350 °C by capillary column gas chromatography, using a Varian 430-GC gas chromatograph (Varian Medical Systems, ., Palo Alto, CA, USA), equipped with a FID (Flame Ionization Detector) and connected to a HT5 capillary column (25 m × 0.32 mm ID × 0.1 μm), SGE, Supelco, (Bellefonte, , USA). As carrier gas helium is used, with a flow of 1.5 mLmin. A heating ramp from 50 to 200 °C at a rate of 7 °Cmin has been applied, followed by another ramp from 200 to 360 °C at a rate of 15 °Cmin, maintaining the oven temperature at 360 °C for 10 min using n-hexadecane (cetane) as internal standard to quantify the content of methyl esters and glycerides (-mono, di and triglycerides) with the help of some commercial standard fatty acid esters, respectively. This method allows us to obtain a complete analysis of the sample in a single injection and in a time no longer than 65 min, which simplifies the process and increases the speed of analysis [19,20,21,22,23,24].

    Considering that sunflower oil is constituted by a mixture of fatty acids in variable proportion (mainly linoleic, oleic and stearic acids), reactions results are expressed as the relative amounts of the corresponding FAME, MG and DG, that are integrated in the chromatogram. By difference and respect to the internal standard (cetane), the amount of TG which has not reacted is calculated. The Conversion includes the total amount of triglyceride transformed (FAME + MG + DG) in the methanolysis process and Selectivity makes reference to the relative amount of FAME + MG obtained, which exhibit retention times (RT < 25) similar to conventional diesel fuel [20,21,27].

    3.5. Viscosity Measurements

    Viscosities were determined in an Oswald Proton Cannon-Fenske Routine Viscometer 33200, size 150 capillary viscometer (Sigma-Aldrich). This is based on determining the time needed for a given volume of fluid to pass between two points marked on the instrument. It correlates to the movement restriction suffered by the liquid flow, as a result of its molecules’ internal friction, depending on their viscosity. From the flow time, t, in seconds, the kinematic viscosity (mm2s or centistokes, cSt) can be obtained from the equation: C × t = viscosity, where C is the constant calibration of the measuring system in mm2s × s, which is given by the manufacturer (0.040350 mm2·s−1, at 40 °C) and t the flow time in seconds [19,20,21,22,23,24].

    The sample, previously centrifuged at 3500 rpm for 10 min, is immersed in a thermostatic bath at 40 °C for 15 min, making sure that the temperature is stable. Then, the sample is introduced into the viscometer and this, in turn, in the water bath, making sure that it is in rigorously positioned vertically, with the bottom end at a minimum distance of 2 cm from the floor of the bath.

    4. Conclusions

    In order to improve a new enzymatic methodology developed to obtain a second generation biodiesel that integrates glycerol as monoglyceride [19,20,21,22,23,24], partial transesterification reactions were achieved through the kinetic control of the chemical reaction. In this respect, supported KF catalysts were evaluated in this study as an inexpensive selective heterogeneous catalyst in the partial methanolysis of sunflower oil to produce an optimal mix with two FAME molecules and one MG molecule for every TG molecule. This biofuel, named Ecodiesel, is applicable to diesel engines because it exhibits similar properties to conventional biodiesel and does not produce glycerol as a by-product. Thus, according to the results the fact that in no case the slightest amount of glycerol was obtained according the GC analysis of the reaction products highlights the undoubted selective character of the consecutive methanolysis process.

    We have therefore shown that with any of the three supported KF catalysts studied, the selected experimental conditions represent a significant optimization of the process to obtain in one step a biofuel with kinematic viscosity values around 4.5–8.5 cSt, very similar to conventional biodiesel, without generation of any type of residue, since only one phase is obtained, containing FAME, MG, and some little amount of diacylglycerol (DG) as well as the non-reacted methanol, unlike what happens when a larger amount of methanol is used, where two phases are produced. In such case, a conventional transesterification process is developed [38] and variable amounts of glycerol are collected in the lower methanolic phase when a 121 molar methanol to oil ratio is used.

    On the other hand, some studies [39,40,41,42] have proven that blends of diesel fuel and some short chain alcohols, like methanol, with biodiesel produced some less maximum power output than regular diesel. Besides, no significant difference in the emissions of CO2, CO, and NOx between regular diesel and biodiesel, methanol and diesel blends was observed. However, the use of these blends resulted in some reduction of particulate matter. Consequently, such blends can be used in a diesel engine without any modification, taking into account the limited changes obtained respect to the use of pure diesel.

    On the other hand, the use of conventional biodiesel as a diesel fuel extender and lubricity improver is rapidly increasing. While most of the properties of biodiesel are comparable to those of petroleum-based diesel fuel, improvement of its low temperature flow characteristic still remains one of the major challenges when using biodiesel as an alternative fuel for diesel engines. However, a considerable reduction in pour point has been noticed by using some alcohol as cold flow improver [41]. In this respect, Ecodiesel will display some higher cloud points and pour points than conventional biodiesel; however the presence of methanol as a surplus of the methanolysis reaction will compensate the low temperature flow characteristics. Besides, several additives may be used to maintain the basic chemical functions to improve ignition and combustion efficiency and to stabilize such fuel mixtures [42]. Thus, it can be used directly after its production because it is obtained in only one phase and no purification step of residual glycerol or methanol is necessary.

    Furthermore, to obtain this biofuel it is not necessary operate at high pressures and temperatures. On the contrary, this new biodiesel is obtained under mild reaction conditions, at atmospheric pressure, 61 methanol to oil molar ratio, 7 wt% catalyst respect to oil, 65 °C reaction temperature and 60 min reaction time. Besides, a comparatively higher yield is obtained respect to the conventional biodiesel reaction, because no glycerol is generated as byproduct.

    Finally, although it was seen that after the second reuse a decrease in the catalytic activity occurs, this low cost heterogeneous process may be comparatively more profitable than the enzymatic process, due to the higher cost of commercial lipases.

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